Summary of current and recent research at the
Research Group of Theoretical Molecular Electronics and Spintronics
of Institute of Theoretical Physics and Astronomy of Vilnius University

Research during 2013, 2012, 2011, 2010 and 2009 years

senior researcher Arvydas Tamulis¹, PhD student Sarunas Krisciukaitis⁵

Alumni students: Magister student Vidmantas Feiza⁴, postgraduated Bachelor students Lukas Berteska², Vaidas Maciulis², and Martynas Misevicius³, Magister of sciences Mantas Grigalavicius presently is PhD student at Institute for Cancer Research, The Norwegian Radium Hospital, Norway

¹Independent expert of European Commission; Home address: Vilnius, Didlaukio street 27-40;

Mobile: +370-69919397; e-mail: tamulis9@gmail.com

²Vilnius University, Faculty of Physics, Sauletekio avenue 9, Vilnius

³Vilnius University, Faculty of Chemistry, Naugarduko street 24, Vilnius

⁴Vilnius University, Faculty of Natural Sciences, M. K. Ciurlionio street 21/27, Vilnius

⁵Barclays bank established IT centre in Lithuania, Vilnius

^{List of scientific publications}

Quantum Mechanical Origin of Simplest Forms of Life, Design of Artificial Living Systems and NanoBioRobots

1. Quantum Mechanical Self-Assembly of Artificial Minimal Living Cells [1-19, 22, 26-30]

2. Quantum Mechanical Origin of Emergence of Genetic Material in Minimal Cells [1-19, 22]

3. Influence of Water Molecules on Quantum Self-Assembly Energy of Guanine and Cytosine Molecules [2, 6, 7, 9, 11-14, 17-18, 20]

4. Quantum modeling of photo-induced electron transfer in minimal cell photosynthetic centers containing a Ru(bipyridine)₃²⁺ sensitizer molecule [2, 6, 7, 9-11, 16, 17, 19, 22]
5. Quantum Mechanical Design of Molecular Electronics OR, NotAND Gates for the Regulation of Artificial Minimal Living Cell Functions [2, 6, 7, 9-11, 15, 17, 20. 26-28, 30]

6. Hardware of Molecular Electronics Digital and NMR Quantum Computing Living Systems Designed Quantum Mechanically [2, 6, 7. 9-11, 15, 27, 30]

Abstract of 2013-2009 years research: Quantum mechanical density functional theory nonlocal gradient electron correlation interactions methods are used for investigations of various self-assembled photoactive fatty acid micelles. The micelle systems studied are based on a photoactive squarine sensitizer, an 8-oxo-guanine electron donor, cytosine, a fatty acid and its precursor (pFA) molecules [12]. The systems include a water environment and consist of some 400 atoms and are up to about 4.5 nm in diameter. The quantum mechanical based electron correlation interactions are the source of the weak hydrogen and Van der Waals chemical bonds that are critical to the behavior of these systems. Polar solvent molecules such as water increase the strength of these bonds and thus play a central role in the self assembly and functioning of the systems studied. The distances between the separated sensitizer, precursor of fatty acid, and water molecules are comparable to Van der Waals and hydrogen bonding radii. As a result, these nonlinear quantum interactions compress the overall molecular system resulting in a smaller gap between the HOMO and LUMO electron energy levels allowing enhanced tunneling of photoexcited electrons from the sensitizer to pFA. The most intense excited states of the photoactive fatty acid micelles are partially composed of LUMO+n states located on the fatty acid precursors when the bis(4-diphenylamine-2-phenyl)-squarine molecule is covalently attached to the 8-oxo-guanine. This coupling also promotes electron hopping (tunneling) to the pFA molecules during the most intense absorption excited state. The photoexcited electron tunnels to the waste end of the pFA molecules where it causes these molecules to split due to intense rotation and vibration of the weak chemical bond that joins the waste piece to the fatty acid section of the pFA molecule. The most intense absorption lines of the squarine-8-oxo-guanine supermolecule were found to be shifted to the red when these molecules were associated with fatty acid micelles. In addition, the 8-oxoguanine:: cytosine-squarine supramolecule was observed to have an absorption region that covered more of the visible spectrum than a squarine-8-oxo-guanine supermolecule. The redward shift of the intense absorption lines would allow a self reproducing micelle to absorb the light in the longer wavelength region, which may have been important in the environment that life might have developed, in addition to extending the photoactive period into the earlier morning and later evening hours. That allowed better compete for such a kind of evolved photoactive micelles of Fatty Acids World life in getting the food molecules. Furthermore, one notes that the nucleotide caused wavelength shift and broadening of the absorption pattern potentially gives the nucleotides an additional valuable role, other than just a purely genetic one in the early stages of the development of life. The main quantum mechanical research result of our research group is that life in the Earth or elsewhere in the Space could have emerged in the form of self-reproducing photoactive fatty acid micelles, which step by step evolved to nucleotide containing micelles due to an enhanced ability to absorb visible light. The nucleotide molecules and their sequences, which in the first period of evolution of fatty acid molecules were useful just for better absorbency of the light in the longer wavelength region, later in the peptide nucleic acid (PNA) or RNA World living organisms took on the role of genetic information storage. From the information theory point of view, the nucleotide molecules sequences in the Fatty Acids World micelles carry positional information how to directly provide better relaxation electron transport along the nucleotide-sensitizer chain and in addition providing complimentary copies of that information to the next generation. The result of self-assembly of molecules in minimal cells depends on the electromagnetic forces between electrons and in general is predicted by existence of the universal physical constants. Molecules are built from atoms therefore for the thermonuclear reactions and atom synthesis in the stars are important also the rest three fundamental forces: strong and weak nuclear interactions and gravitation (for the self-formation of stars). Universal constants of physical interactions did not changed in the Universe during last 13.73 billion years therefore the emergence of life was predicted before the time of expansion of the Universe [19, 29].

The new alternative forms of life based on molecular quantum information processing and logically controlling are proposed in our research in early 1998 year (see, for example http://www.fondazione-delbianco.org/accademici/tamulis.htm) which we are still developing [16].

^{A. Tamulis research group dissemination knowledge during 2013, 2012, 2011, 2010 and 2009 years}

[31] Arvydas Tamulis, Mantas Grigalavicius, “Quantum Entanglement in Photoactive Prebiotic Systems. journal Systems and Synthetic Biology”, vol. 8, p.p. 117-140., 2014.

[30] Arvydas Tamulis, Mantas Grigalavicius, Sarunas Krisciukaitis, „Quantum Entanglement in a System Composed of Two Prebiotic Kernels with Molecular Spintronics Logic Devices for Control of Photosynthesis“ Journal of Computational and Theoretical Nanoscience, vol. 11, p.p. 1597-1608, 2014.

[29] Arvydas Tamulis and Mantas Grigalavicius, “Quantum Mechanical Origin of Fatty Acid Life and Correlations with Anthropic Principle and Old Testament”, journal Quantum Matter of the American Scientific Publishers, vol. 3, p.p.460-468, 2014.

[28] Arvydas Tamulis, Mantas Grigalavicius and Jonas Baltrusaitis, (2013) „Phenomenon of Quantum Entanglement in a System Composed of Two Minimal Protocells“, Origins of Life and Evolution of Biospheres, 43:49–66, DOI 10.1007/s11084-012-9323-0, available in electronic version at http://link.springer.com/article/10.1007%2Fs11084%C2%AD012%C2%AD9323%C2%AD0,

[27] Arvydas Tamulis and Mantas Grigalavicius, “Molecular Spintronics Control of Photosynthesis in Artificial Cell”, “Journal of Computational and Theoretical Nanoscience”, vol. 10, No 4, p.p. 989-995, 2013.

[26] Arvydas Tamulis, Mantas Grigalavicius, Giedrius Medzevicius, Sarunas Krisciukaitis, „Quantum Entangled Photosynthesis and OR Logic Gates Controlling Minimal Artificial Cell“ Journal of Computational and Theoretical Nanoscience, vol. 9, No 3, p.p. 351-359, 2012.

[25] Arvydas Tamulis, Mantas Grigalavicius, Jonas Baltrusaitis, „Quantum Evolution of Fatty Acid World Life and Applications for Magnetically Controlled Artificial Minimal Cells“, book of abstracts of Chembiogenesis, p.p. 26-27, 2011, 27-30 October, Heraclion-Crete, Greece.

[24] Arvydas Tamulis, Mantas Grigalavicius, Jonas Baltrusaitis, „Quantum Evolution of Fatty Acid World Life and Applications for Magnetically Controlled Artificial Minimal Cells“, book of abstracts of 39^th Lithuanian National Physics conference, p. 150, 2011, October 06-08, Vilnius University, Lithuania.

[23] Arvydas Tamulis, „Quantum Evolution of Fatty Acid World Life and Applications for Magnetically Controlled Artificial Minimal Cells“, Fift International NanoSchool, 2011, November 15 – 17, Faculty of Chemistry, Vilnius University, Naugarduko st. 24, Vilnius, Lithuania.

[22] Arvydas Tamulis, „Quantum Mechanical Investigations of Photosynthetic Systems of Artificial Minimal Cells Based on 8-Oxo-Guanine-Ru(bipyridine)₃²⁺", Journal of Computational and Theoretical Nanoscience, Volume 8, Number 4, April 2011, pp. 624-636.

[21] Arvydas Tamulis appointed as one of the Editorial Board members of Open Journal of Inorganic Chemistry (OJIC, website: http://www.scirp.org/journal/ojic ).

[20] A. Tamulis science presentaiton „Quantum Entangled OR Logic Gates Controlling Photosynthesis and Melodies in Minimal Artificial Cells“, on 2011 January 27, 11 hours, at Vilnius University Institute of Theoretical Physics and Astronomy, Library hall, A Goštauto str. 12

[19] Arvydas Tamulis and Mantas Grigalavicius, "Quantum Mechanical Evolution of Fatty Acids World Life", Viva Origino, Vol. 38 (No. 2), pages 4-17, 2010, Available at: http://www.origin-life.gr.jp/3802/3802004/3802004.html

[18] A. Tamulis was accepted for research in COST Action CM0805 “The Chemical Cosmos: Understanding Chemistry in Astronomical Environments”, in working group WG3: Chemistry of planetary atmospheres (Models and observations). Participated with science presentation in WG3 workshop on “Carbon in the Solar system”, Brussels December 6 to 8 2010. Abstract of our presentation available at: http://ulisse.busoc.be/cost/abstracts_uploads/AbstractEmergenceLife.txt

       Title

of our presentation: “The
Emergence of Life was Predicted”,

authors:
Arvydas Tamulis and Mantas Grigalavicius

[17] A. Tamulis presented thee invited lectures in the Fourth International NanoSchool, Faculty of Chemistry, Vilnius University, November 30 – December 3, 2010, Vilnius.

[16] A. Tamulis, M. Grigalavicius, S. Krisciukaitis, G. Medzevicius, “Quantum Processes in 8-Oxo-Guanine-Ru(bipyridine)₃²⁺ Photosynthetic Systems of Artificial Minimal Cells”, Central European Journal of Physics, vol. 9(3), ( 2011), p.p. 775-791. DOI: 10.2478/s11534-010-0092-y, electronic version since June 24, 2010, available at: http://www.springerlink.com/content/dn06077114p41327/.

[15] Arvydas Tamulis, Mantas Grigalavičius, „Magnetically controlled artificial minimal living cells“, book of abstracts of conference ICAMDATA 7, 21–24 September 2010, Vilnius, p. 69.

[14] Arvydas Tamulis and Mantas Grigalavicius, “Quantum Mechanical Origin of Genetic Material in Minimal Cells”, J. Comput. Theor. Nanosci. 7, 1831-1841 (2010)

[13] Arvydas Tamulis, “The Emergence of Life was Predicted”, The scientific seminar in headquarter of Lithuanian Scout Organization on May 31, 19-22 hours, Vilnius, Pylimo street 11-1.

[12] Arvydas Tamulis, Mantas Grigalavicius, „The Emergence and Evolution of Life in a “Fatty Acid World” Based on Quantum Mechanics”, Origins of Life and Evolution of Biospheres, 2011) vol. 41, pages 51-71. Electronical version of this article available since May 05, 2010 at http://www.springerlink.com/content/7122n16869843314/fulltext.html

[11] The reportage about our current research is placed in the website where you can see moving self-assembled micelles due to quantum mechanical interactions and some pictures from Los Alamos "Protocell Assembly" project: http://tv.delfi.lt/video/gkUbPraW/

[10] Article in Lithuanian language Arvydas Tamulis “Kvantinės mechaninės sąveikos tarp molekulių sąlygojo pirminės gyvybės ir genetinės medžiagos atsiradimą”, see more in website:
http://mokslofestivalis.eu/lt/news/337/40/Kvantines-mechanines-saveikos-tarp-molekuliu-salygojo-pirmines-gyvybes-ir-genetines-medziagos-atsiradima

[9] Arvydas Tamulis, “Quantum Mechanical Interactions Between Molecules are the Origin of Emergence of Protolife and Genetic Material”, lecture in the Seminar of Intracellular Signalization at the Institute of Cardiology, Kaunas University of Medicine, Sukileliu Ave.17, Kaunas, Lithuania, February 05, 2010, 11 hours. See http://www.kmu.lt/cellculture/rengin_1.htm [www.kmu.lt]

[8] Prof. Arunas Ramanavicius and Dr. Arvydas Tamulis, Joint experimental and theoretical meeting “Synthesis and Quantum Level ]Investigations of Elements of Nanobiorobots and Molecular Quantum Computers”, Vilnius University, Faculty of Chemistry, at centre NANOTECHNAS, Naugarduko str. 24, February 02, 2010, 12 hours.

[7] Arvydas Tamulis, “Quantum Mechanical Interactions Between Molecules are the Origin of Emergence of Protolife and Genetic Material”, lecture in Vilnius University Institute of Theoretical Physics and Astronomy, at library hall, January 14, 2010, 11 hours.

[6] Arvydas Tamulis, “Quantum Mechanical Design of Molecular Computing Devices Controlling Photosynthesis in NanoMedicine BioRobots”, Multiscale Modeling and Simulation in Science, AlbaNova University Campus, Stockholm, November 23 - 27, 2009, see: http://agenda.albanova.se/internalPage.py?pageId=257&confId=1122

[5] A. Tamulis, M. Grigalavicius, “The origin of genetic material in minimal cells is based on quantum mechanics”, Multiscale Modeling and Simulation in Science, AlbaNova University Campus, Stockholm, November 2 - 13, 2009, see http://agenda.albanova.se/conferenceDisplay.py?confId=1122

[4] A. Tamulis, M. Grigalavicius, “Quantum mechanical origin of genetic material in minimal cells”, book of abstracts of conference Chemistry 2009 , October 16, Institute of Chemistry, A, Gostauto str. 9, Vilnius, page 115.

[3] Mantas Grigalavicius, “Quantum Mechanical Investigations of Photosynthetic Centers of Artificial Cells”, Workshop on NanoBioTechnolgies at Molecular and Quantum Level, Vilnius University, Faculty of Chemistry, Naugarduko str. 24, October 01, 2009.

[2] Arvydas Tamulis, “Artificial Cells – New Trend in Quantum Molecular Nano BioTechnologies” , Workshop on NanoBioTechnolgies at Molecular and Quantum Level , Vilnius University, Faculty of Chemistry, Naugarduko str. 24, October 01, 2009.

[1] Arvydas Tamulis, Mantas Grigalavicius, “Quantum mechanical origin of genetic material in minimal cells”, book of abstracts of 38th Lithuanian national physics conference, Vilnius, June 8-10, 2009, page 218.

^{A. Tamulis worked as European Commission expert of FP7 projects in Brussels 2008 July - 2011 July.}

^{Mantas Grigalavicius completed his Magister thesis, June 2011.}

^{We have organized Joint COST actions Workshop on NanoBioTechnolgies at Molecular and Quantum Level, Vilnius University, Faculty of Chemistry, Naugarduko str. 24, October 01, 2009.}

^{Agency for International Science and Technology Development Programmes (Lithuania) on June 04, 2009 approved A. Tamulis project for the participation in the COST CM0703 action „Systems Chemistry“, see: http://w3.cost.esf.org/index.php?id=188&action_number=CM0703}

Vidmantas Feiza compleated his Bachelor thesis “Quantum mechanical design of artificial cells controled by molecular electronic's logical devices“, supervisor Arvydas Tamulis. Faculty of Natural Sciences commission evaluated these thesis by mark: ten (10), June 2009.

Mantas Grigalavicius compleated his Bachelor thesis “QUANTUM MECHANICAL ARTIFICIAL CELLS FOTOSYNTHETIC CENTRES RESEARCH“, supervisor A. Tamulis. Faculty of Physics commission evaluated these thesis by mark: nine (9), June 2009.

Martynas Misevicius compleated his Bachelor thesis “QUANTUM MECHANICAL INVESTIGATION OF GUANINE-CYTOSINE INTERACTIONS IN WATER ENVIROMENT“, supervisor A. Tamulis. Faculty of Natural Sciences commission evaluated these thesis by mark: eight (8), June 2009.

Arvydas Tamulis is member of Managament Committee of COST D35 action “From Molecules to Molecular Devices: Control of Electronic, Photonic, Magnetic and Spintronic Behaviour”, see: http://www.cost.esf.org/domains_actions/cmst/Actions/From_Molecules_to_Molecular_Devices

Our institution and Arvydas Tamulis are among the founding members of European Centre for Living Technology, see: http://www.ecltech.org/ecltech_j/index.php/about-eclt/organization.html

^{List of scientific publications}

Our research group this year continuing science works on EU COST D35 action ”From Molecules to Molecular Devices: Control of Electronic, Photonic, Magnetic and Spintronic Behaviour”^$

^$This research is partially financed by the Agency for International Science and Technology Development Programmes (Lithuania) during 2009 year.

Research during 2008 year

Our research group this year continuing science works on EU COST D35 action ”From Molecules to Molecular Devices: Control of Electronic, Photonic, Magnetic and Spintronic Behaviour”^$ and
during first half of this year performed research on FP6 project “Programmable Artificial Cell Evolution (PACE)”^$$

senior researcher Arvydas Tamulis, Sarunas Krisciukaitis, Martynas Misevicius*, Mantas Grigalavicius**,

Vidmantas Feiza***, Giedrius Medzevicius****

Vilnius University Institute of Theoretical Physics and Astronomy, A. Gostauto street 12, Vilnius, Lithuania, e-mail:

*Vilnius University, Faculty of Chemistry, Naugarduko street 24, Vilnius

**Vilnius University, Faculty of Physics, Sauletekio avenue 9, Vilnius

*** Vilnius University, Faculty of Natural Sciences, M. K. Ciurlionio street 21/27, Vilnius

****Vilnius “Minties” gymnasium, Erfurto street 23, Vilnius

We used quantum mechanical (QM) nonlocal gradient electron correlation interactions density functional theory (DFT) methods to investigate various self-assembled photoactive bioorganic systems of artificial minimal living cells (see movie below) . The cell systems studied are based on peptide nucleic acid (PNA) and consisted of up to 360 atoms (not including the associated water or methanol solvent shells) and are up to 3.0-4.2 nm in diameter. The electron correlations interactions originating the hydrogen bonds and Van der Waals weak chemical bonds that increase due to the addition of a polar solvent (water or methanol) molecules, and fatty acid (FA) and precursor fatty acid (pFA) molecules play a critical role in the QM interaction based self-assembly of the photosynthetic center and functioning of the photosynthetic processes of the artificial minimal living cells. The distances between the separated sensitizer, precursor fatty acid, and water or methanol molecules are comparable to Van der Waals and hydrogen bonding radii. As a result these nonlinear quantum interactions compress the overall system resulting in a smaller gap between the HOMO and LUMO electron energy levels and photoexcited electron tunneling occurs from the sensitizer (either a 1,4-bis(N,N-dimethylamino) naphthalene or a squarine molecule, or a [Ru(bpy)2(4,4'-Me-2-2'-bpy)]²⁺) to pFA molecules (notation used: Me = methyl; bpy = bipyridine).

The electron tunneling and associated light absorption of most intense transitions as calculated by the time dependent density functional theory (TD DFT) method differs from spectroscopic experiments by only 0.3 or 0.2 nm, which is within the value of experiment errors. This agreement implies that the quantum mechanically self-assembled structures of minimal living cells very closely approximate the realistic ones.

Quantum mechanical electron correlation experiments of self-assembly of above described artificial minimal living cells show that these cells are complex systems because only entire ensemble of PNA, and sensitizer, and pFA, and FA and water molecules is stable and perform quantum photosynthetic processes. Removing the small part of nucleobase, FA and water molecules leads to the structural changes in comparison with realistic structures and difference in comparison with the spectroscopic values of photoexcited electron tunneling from sensitizer (1,4-bis(N,N-dimethylamino)naphthalene to pFA molecules. QM electron correlation experiments of self-assembly of artificial minimal living cells removing the main part of nucleobase, and FA and water molecules leads to the degradation of these cells. We can state what the inclusion of ever more water, and fatty acid, and pFA molecules, and waste pieces of the pFA molecules and nucleobase molecules in the different artificial minimal living cells results in a shift of the absorption spectrum to the red for the artificial protocell photosynthetic centre, leading to an ever closer approach to the real experimental value and indicates the measure of the complexity of this quantum complex system, i.e. a minimal protocell. It is important to say that only QM electron correlation TD-DFT experiments with minimal living cells gives results exactly comparable with spectroscopic results and all other more simplified QM methods such as local gradient DFT or ab initio Hartree-Fock gives structures and spectra far from the experimentally measured.

The corresponding of experimental absorption spectra peaks and our QM calculated confirm that our chosen method of designing single electron nano photocells might be useful not only for artificial living organisms but also for wide implementation in the nano photodevices, and molecular computers.

Our goals are by using quantum mechanical experiments to predict the possibility of biochemical experimental synthesis of molecular electronics and spintronics logical elements information based artificial living organisms or nanobiorobots for nanomedicine and cleaning of nuclear, chemical and microbial pollutions.

We are creating molecular electronics logic gates regulating the photosynthesis, growing and dividing of artificial living cells and nanobiorobots. It was performed the study of G-C self-assembling energies in various H₂O molecules clusters correlating these energies with the G-C dehybridization energies due to charge transfer in the H₂O molecules clusters surrounded the photosynthetic center of artificial minimal living cell controlled by the last chain of genome, i.e. hydrogen bonded G-C supramolecule.

Implementation of quantum information bits based on spatially localized electron spins in stable molecular radicals was investigated by unrestricted time dependent functional theory methods. The g-tensor shift calculations of neutral radical molecules was performed for beta-diketone and syringate. beta-diketone neutral radical moiety with an attached hydrocarbon chain. Beta-diketone is suitable for construction of quantum computing processing devices because the qubit is relatively stable due to the small magnitude of g-tensor shift component that is aligned with the external magnetic field, i.e. the direction of hydrocarbon chain which provide the self-assembled monolayer an attachment of the molecule to a substrate.

TD DFT simulations of the artificial minimal living cells with implemented molecular electronics and spintronics gates done using self-assembled neutral radical molecules beta-diketone and syringate show that it is possible to construct more general ContrlNOT and NAND logic functions suitable for the production of the nanobiorobots. Analysis of time dependent density functional theory method calculated absorption spectrum and images of electron transfer trajectories in the different excited states allow to separate two different logically controlled functions of molecular device consisting of guanine-c-PNA-1,4-dihydroquinoxaline-1,4-bis(N,N-dimethylamino)naphthalene supermolecule and Van der Waals bonded precursor of fatty acid molecule. These two different logically controlled functions of artificial minimal living cells 1) initiation of metabolic fatty acid production in five excited states or 2) initiation of gene dehybridization in one excited state. This designed supermolecule works in the artificial minimal cell as molecular electronics classic OR logic function (Boolean logics OR gate). Designed of variety of the molecular spintronics devices will regulate photosynthesis and growth of artificial minimal living cells in the conditions of external magnetic fields, while also providing a perspective of the requirements for success in the synthesis of new forms of artificial living organisms.

A. Tamulis research group dissemination knowledge during 2008 year

1. Publications in International journals, published, in press or accepted for publication

1) Arvydas Tamulis and Vykintas Tamulis, “Quantum Mechanical Design of Molecular Electronics OR Gate for Regulation of Minimal Cell Functions”, Journal of Computational and Theoretical Nanoscience, vol. 5 No 4, p.p. 545-553, 2008.

2) Arvydas Tamulis, “Quantum Self-assembly of Artificial Minimal Living Cells and Molecular Electronics Control”, Viva Origino, vol 36, No 2, p.p. 10-19, 2008.
http://www.origin-life.gr.jp/3602/3602J.html

3) A. Tamulis, “Quantum Mechanical Control of Artificial Minimal Living Cells”, NeuroQuantology, vol. 6, p.p. 311-322, 2008.
http://www.neuroquantology.com/journal/index.php/nq/issue/current/showToc

2. Publications: Books & Conference Proceedings, Published or In Press

1) A. Tamulis, V. Tamulis, H. Ziock, S. Rasmussen, “Influence of Water and Fatty Acid Molecules on Quantum Photoinduced Electron Tunnelling in Photosynthetic Systems of PNA Based Self-Assembled Protocells”, Chapter #2 in book “Multi-scale Simulation Methods for Nanomaterials”, eds. R. Ross and S. Mohanty, John Wiley & Sons, Inc., New Jersey, pages 9-28, January 2008.

2) S. Rasmussen, J. Bailey, J. Boncella, L. Chen, G. Collis, S. Colgate, M. DeClue, H. Fellermann, G. Goranovic, Y. Jiang, C. Knutson, P.-A. Monnard, F. Moufouk, P. E. Nielsen, A. Sen, A. Shreve, A. Tamulis, B. Travis, P. Weronski, W. H. Woodruff, J. Zhang, X. Zhou, and H. Ziock, “Assembly of a minimal protocell”, in MIT Press book, “Protocells: Bridging nonliving and living matter”, Editors: S. Rasmussen, M. A. Bedau, L. Chen, D. C. Krakauer, D. Deamer, N. H. Packard, and P. F. Stadler, pages 125-156, 2008 .

3) Arvydas Tamulis, “Quantum Mechanical Interpretation of the Origin of Life”, in “Science in the Faculty of Natural Sciences of Vilnius University”, Proceedings of 5^th science conference, Vilnius, October 03, 2008, Publishing house of Vilnius University, pages 7-11.

4) PACE Project Final Report Website http://www.istpace.org//index.html It was made contribution from our research group.

5) A. Tamulis, “Self-Assembly of Complex Systems: Artificial Living Cells?”, in book of abstracts of First International Academy of Astronautics
Symposium on “Search for Life Signatures” page 21, UNESCO, Paris, France, September 22-26, 2008.

3. Talks, lectures and conference presentations

1) Arvydas Tamulis, invited lecture "Quantum Mechanical Self-assembling of Artificial Minimal Cells and Control by Molecular Electronics and Spintronics Logical Devices" in international Nanotechnology School on "Nanostructured materials for biosensors and medicine", 2008, February 18-22, School place: “Klaipeda hotel“, L. Stuokos–Guceviciaus street 3, Vilnius.

2) Arvydas Tamulis, “Quantum Self-Assembly of Artificial Living Cell and Molecular Electronics Control of Photosynthesis and Gene Dehybridization”, presentation in European Center For Living Technology Workshop on Protocell Modelling, March, 10-12, 2008, Venice.

3) Arvydas Tamulis, invited lecture “Quantum mechanical processes of self-assembly, photosynthesis and control of artificial living cells”, Workshop of „Biomedicine Physics and Nanophotonics Studies Center“, 2008-04-29, Hotel Best Western „Naujasis Vilnius“, Konstitucijos ave. No 14, Vilnius, Lithuania.

4) Arvydas Tamulis, invited lecture “Quantum mechanical self-assembly of artificial living cells, photosynthesis and control”, International conference on „Innovative Medicine“, May 22-24, 2008, Hotel „ARTIS“, Liejyklos str. No 11/25, Vilnius, Lithuania.

5) Arvydas Tamulis, lecture “Quantum Mechanical Modeling of Artificial Minimal Living Cells”, in “Cell Model Systems Summer School” CNR, Rome, 8-13 June, 2008.

6) A. Tamulis, invited lecture “Programmable Artificial Living Cells – New Kind of Information Technologies”, Seminar on “NanoBio Technologies and Genomics”, September 16, 2008, Vilnius University Faculty of Chemistry, Naugarduko street 24, Vilnius.

7) A. Tamulis, lecture “Self-Assembly of Complex Systems: Artificial Living Cells?”, in First International Academy of Astronautics
Symposium on “Search for Life Signatures” , UNESCO, Paris, France, September 22-26, 2008.

8) Arvydas Tamulis, invited lecture “Quantum Mechanical Control of Artificial Living Cells Using Molecular Electronics and Spintronics Devices”,
in 5^th conference “Science in the Faculty of Natural Sciences”, Vilnius University, Vilnius, October 03, 2008.

4. Press releases (press/radio/TV)

1) Arvydas Tamulis proposed idea of Molecular Quantum Computing Life is publishing in The Encyclopedia of Science http://www.daviddarling.info/encyclopedia/M/molecular_quantum_computing_cloud.html

2) Arvydas Tamulis, A talk about quantum mechanical control of artificial living cells in Lithuanian TV movie on March 29 (see Negali Buti LRT 2008-03-29), and in the Lithuanian webserver SciencePlus http://mokslasplius.lt/mokslo-naujienos/2008/04/24/nano-bio-robotai . Download MOV file

3) Description and movie about the Venice nano biotechnology 2008 spring conferences in Lithuanian webserver SciencePlus http://mokslasplius.lt/mokslo-naujienos/2008/04/24/dirbtine-gyvybe-moksline- konferencija-venecijoje

4) Description and movie about A. Tamulis lecture in the Council of Vilnius University Institute of Theoretical Physics and Astronomy on March 20, 2008 entitled “Self-Assembly of Artificial Cells and Quantum Mechanical Control” in Lithuanian webserver SciencePlus http://mokslasplius.lt/mokslo-naujienos/2008/04/28/kvantinis-mechaninis-dirbtiniu-minimaliu-gyvu-lasteliu-kontroliavimas

5) Arvydas Tamulis, talk “Programmable Artificial Living Cells – New Generation Tools Against the Cancer and Environmental Pollutions” (in Lithuanian language: „Programuojamos dirbtinės gyvos ląstelės – naujos kartos ginklai prieš vėžį ir aplinkos taršą”), Lithuanian Science Festival, in Vilnius University Central Palace, Theater hall, September 16, 2008. Review of
A. Tamulis lecture was written by Dr. R. Maskoliunas, editor in chief of Lithuanian journal Science and Technologies and placed at address http://mokslofestivalis.eu/lt/news/191/17.

^$This research is partially financed by the Agency for International Science and Technology Development Programmes (Lithuania).

^$$This work was funded via the PACE (Programmable Artificial Cell Evolution), the European Integrated Project in the EU FP6-IST-FET Complex Systems Initiative.

Quantum mechanically modeled processes of the last 1762 steps of self-assembly of micelle. Photoinduced electron is hoping from squarine molecule (in the center) to the precursor of fatty acid molecule and split it. The new fatty acid join to the entire micelle which is growing and after reaching some critical size spontaneusly dividing in to two separate small self-reproduced micelles.

Our newest public article in Lithuanian journal “Science and Technology” ("Mokslas ir Technika") No 12, p.p. 26-28, 2007

Research during 2007 year

Quantum Processes of Self-Assembly, Photosynthesis and Molecular Computing in Artificial Minimal Living Cells

senior researcher Arvydas Tamulis

Vilnius University Institute of Theoretical Physics and Astronomy, A. Gostauto 12, Vilnius, Lithuania

We used quantum mechanical (QM) electron correlation interactions density functional theory (DFT) methods (i.e. high precision quantum mechanical simulations) to investigate various self-assembled photoactive bioorganic systems of artificial minimal living cells [1-6]. The cell systems studied are based on peptide nucleic acid (PNA) and consisted of up to 360 atoms (not including the associated water or methanol solvent shells) and are up to 3.0-4.2 nm in diameter. The electron correlations interactions originating the hydrogen bonds and Van der Waals weak chemical bonds that increase due to the addition of a polar solvent (water or methanol) molecules, and fatty acid (FA) and precursor fatty acid (pFA) molecules play a critical role in the QM interaction based self-assembly of the photosynthetic center and functioning of the photosynthetic processes of the artificial minimal living cells. The distances between the separated sensitizer, precursor fatty acid, and water or methanol molecules are comparable to Van der Waals and hydrogen bonding radii. As a result these nonlinear quantum interactions compress the overall system resulting in a smaller gap between the HOMO and LUMO electron energy levels and photoexcited electron tunneling occurs from the sensitizer (either a 1,4-bis(N,N-dimethylamino) naphthalene or a [Ru(bpy)2(4,4'-Me-2-2'-bpy)]²⁺) to pFA molecules (notation used: Me = methyl; bpy = bipyridine).
The electron tunneling and associated light absorption of most intense transitions as calculated by the time dependent density functional theory (TD DFT) method differs from spectroscopic experiments by only 0.3 or 0.2 nm, which is within the value of experiment errors [6]. This agreement implies that the quantum mechanically self-assembled structures of minimal living cells very closely approximate the realistic ones.
Quantum mechanical electron correlation experiments of self-assembly of above described artificial minimal living cells show that these cells are complex systems because only entire ensemble of PNA, and sensitizer, and pFA, and FA and water molecules is stable and perform quantum photosynthetic processes. Removing the small part of nucleobase, FA and water molecules leads to the structural changes in comparison with realistic structures and difference in comparison with the spectroscopic values of photoexcited electron tunneling from sensitizer (1,4-bis(N,N-dimethylamino)naphthalene to pFA molecules. QM electron correlation experiments of self-assembly of artificial minimal living cells removing the main part of nucleobase, and FA and water molecules leads to the degradation of these cells [3-5]. We can state what the inclusion of ever more water, and fatty acid, and pFA molecules, and waste pieces of the pFA molecules and nucleobase molecules in the different artificial minimal living cells results in a shift of the absorption spectrum to the red for the artificial protocell photosynthetic centre, leading to an ever closer approach to the real experimental value and indicates the measure of the complexity of this quantum complex system, i.e. a minimal protocell. It is important to say that only QM electron correlation TD-DFT experiments with minimal living cells gives results exactly comparable with spectroscopic results and all other more simplified QM methods such as local gradient DFT or ab initio Hartree-Fock gives structures and spectra far from the experimentally measured.
The corresponding of experimental absorption spectra peaks and our QM calculated confirm that our chosen method of designing single electron nano photocells might be useful not only for artificial living organisms but also for wide implementation in the nano photodevices, and molecular computers.
Our goals are by using quantum mechanical experiments to predict the possibility of biochemical experimental synthesis of molecular electronics and spintronics logical elements information based artificial living organisms or nanobiorobots for nanomedicine and cleaning of nuclear, chemical and microbial pollutions.
We are creating molecular electronics logic gates regulating the photosynthesis, growing and dividing of artificial living cells and nanobiorobots [7-13]. It was performed the study of G-C self-assembling energies in various H₂O molecules clusters correlating these energies with the G-C dehybridization energies due to charge transfer in the H₂O molecules clusters surrounded the photosynthetic center of artificial minimal living cell controlled by the last chain of genome, i.e. hydrogen bonded G-C supramolecule.
Implementation of quantum information bits based on spatially localized electron spins in stable molecular radicals was investigated by unrestricted time dependent functional theory methods [8-10]. The g-tensor shift calculations of neutral radical molecules was performed for beta-diketone and syringate. beta-diketone neutral radical moiety with an attached hydrocarbon chain. Beta-diketone is suitable for construction of quantum computing processing devices because the qubit is relatively stable due to the small magnitude of g-tensor shift component that is aligned with the external magnetic field, i.e. the direction of hydrocarbon chain which provide the self-assembled monolayer an attachment of the molecule to a substrate [12].
TD DFT simulations of the artificial minimal living cells with implemented molecular electronics and spintronics gates done using self-assembled neutral radical molecules beta-diketone and syringate show that it is possible to construct more general ContrlNOT and NAND logic functions suitable for the production of the nanobiorobots. Designed of variety of the molecular spintronics devices will regulate photosynthesis and growth of artificial minimal living cells in the conditions of external magnetic fields, while also providing a perspective of the requirements for success in the synthesis of new forms of artificial living organisms.
[1] Jelena Tamuliene, Arvydas Tamulis, “Quantum Mechanical Investigations of Self-Assembled System Consisting of Peptide Nucleic Acid, Sensitizer, and Lipid Precursor Molecules”, Lithuanian Journal of Physics, vol 45, No 3, p.p. 167-174, 2005.
[2] A. Tamulis, V. Tamulis A. Graja, “Quantum mechanical modeling of self-assembly and photoinduced electron transfer in PNA based artificial living organism”, Journal of Nanoscience and Nanotechnology, 6, 965-973 (2006).
[3] Arvydas Tamulis and Vykintas Tamulis, "Quantum Self-Assembly and Photoinduced Electron Tunneling in Photosynthetic System of Minimal Living Cell", Viva Origino, vol. 35, p.p. 66-72, 2007.
[4] Arvydas Tamulis and Vykintas Tamulis, "Quantum Self-Assembly and Photoinduced Electron Tunneling in Photosynthetic Systems of Artificial Minimal Living Cells", Origins of Life and Evolution of Biospheres, vol. 37, 473-476, 2007.
[5] A. Tamulis, V. Tamulis, H. Ziock, S. Rasmussen, "Influence of Water and Fatty Acid Molecules on Quantum Photoinduced Electron Tunnelling in Photosynthetic Systems of PNA Based Self-Assembled Protocells, chapter #2 in book "Multiscale Simulation Methods for Nanomaterials", Edited by Richard B. Ross and Sanat Mohanty, John Wiley & Sons, Inc., New Jersey, ISBN: 978-0-470-10528-3, pages 9-28, January 2008.
[6] S. Rasmussen, J. Bailey, J. Boncella, L. Chen, G. Collins, S. Colgate, M. DeClue, H. Fellermann, G. Goranovic, Y. Jiang, C. Knutson, P.-A. Monnard, F. Moufouk, P. Nielsen, A. Sen, A. Shreve, A. Tamulis, B. Travis, P. Weronski, W. Woodruff, J. Zhang, X. Zhou, and H. Ziock, “Assembly of a minimal protocell”, in MIT Press book, “Protocells: Bridging nonliving and living matter”, eds S. Rasmussen, M. Bedau, L. Chen, D. Krakauer, D. Deamer, N. Packard, and P. Stadler, 2007, in press.
[7] Arvydas Tamulis, Jelena Tamuliene, Vykintas Tamulis, Aiste Ziriakoviene, “Quantum Mechanical Design of Molecular Computers Elements Suitable for Self-Assembling to Quantum Computing Living Systems”, Solid State Phenomena, Scitec Publications, Switzerland, Vols. 97-98, p.p. 175-180, 2004.
[8] A. Tamulis, V. I. Tsifrinovich, S. Tretiak, G. P. Berman, D. L. Allara, ”Neutral Radical Molecules Ordered in Self-Assembled Monolayer Systems for Quantum Information Processing”, Chem. Phys. Lett., 436, p.p. 144 - 149 (2007).
[9] J. Tamuliene, A. Tamulis, J. Kulys, “Electronic Structure of Dodecyl Syringate Radical Suitable for ESR Molecular Quantum Computers”, Nonlinear Analysis: Modeling and Control, Vol. 9, No 2, p.p. 185-196 (2004).
[10] A. Tamulis, V. Tamulis, “Variety of Self-Replicating Complex Living System Based on Quantum Information”, book of abstracts of conference “Chembiogenesis 2005”, Venice, Italy, Sept. 28 – Oct. 01, 2005, page 18.
[11] Jelena Tamuliene, Arvydas Tamulis, Aiste Ziriakoviene, Andrzej Graja, „Quantum Chemical Design of Two Logical Functions Molecular Device“, Lithuanian Journal of Physics, vol. 46, p.p. 163-167 (2006).
[12] Z. Rinkevicius, Arvydas Tamulis, Jelena Tamuliene. “Beta-Diketo Structure for Quantum Information Processing”, Lithuanian Journal of Physics, vol. 46, p.p. 413-416 (2006).
[13] Arvydas Tamulis and Vykintas Tamulis, “Quantum Mechanical Design of Molecular Electronics OR Gate for Regulation of Minimal Cell Functions”, Journal of Computational and Theoretical Nanoscience, vol. 5, 2007, in press.

Quantum Mechanical Modeling of Minimal Living Organisms and Programmable Nano Biorobots during 2006 year

senior researcher Arvydas Tamulis and student Vykintas Tamulis

Institute of Theoretical Physics and Astronomy of Vilnius University, A. Goštauto 12, Vilnius, Lithuania

We used quantum mechanical (QM) electron correlation time dependent density functional theory (TD DFT) method in both the Gaussian 03 and GAMESS-US packages to investigate various self-assembled photoactive bioorganic systems of artificial minimal cells based on peptide nucleic acid (PNA) [1].
The electron correlation hydrogen bonds and Van der Waals interactions that result from the addition of water and fatty acid molecules play the critical role in quantum self-assembly of photosynthetic center and functioning of the photosynthetic processes in artificial minimal cells. The distances between the separated sensitizer, fatty acid precursor (pFA) and water molecules are comparable to Van der Waals and hydrogen bonding radii and therefore we may regard these minimal cells as single electron conjugated supramolecules that we can deal with using an electron correlated TD DFT models. These nonlinear quantum interactions compress the overall system resulting in a smaller gap between the HOMO - LUMO and photoexcited electron tunneling from sensitizer to pFA molecules [2].
Our presenting quantum self-assembled model of the photosynthetic systems includes a PNA fragment which is covalently bonded to a 1,4-bis(N,N-dimethylamino) naphthalene or Ru(bipyridine)₃²⁺ sensitizer molecules, pFA, fatty acid (FA) molecules constituting the 4 nm size micellar container’s inner monolayer with water. The small 10 nm difference of the experimental absorption spectra peaks in comparison with our QM calculated it is possible to understand because of more water and fatty acid molecules exist in the real photosynthetic center of minimal protocells and makes possible to search for new sensitizers. The slightly shorter wavelength given by the model is also consistent with our finding that the inclusion of more water and fatty acid molecules in the models resulted in longer wavelengths for the absorption spectrum. The shift of the absorption spectrum to the red for the artificial minimal cell photosynthetic center might be considered as the measure of the complexity of this system [2].
The small 10 nm difference of the experimental absorption spectra peaks in comparison with our QM calculated confirm that our chosen method of designing single electron transfer minimal cells might be useful also for wide implementation in the nano photodevices and molecular computers.
We have performed quantum mechanical investigations of effective photosynthetic system consisting of good sensitizer Ru(bipyridine)₃²⁺ working under the exciting of visible light in the region from 455.18 nm to 402.85 nm and relaxing due to passing electron from good electron donor 8-oxo-guanine-PNA molecule [3].
Influence of hydrogen bonded cytosine molecule result the shift of the lowest intense excited state wavelength from 455.18 nm to 456.99 nm, i.e. 1.81 nm to red region. The highest intense excited state shifted from 402.85 nm to 401.49 nm, i.e. 1.36 nm to blue region. This is usual process of splitting of spectrum of complex quantum system due to hydrogen bonding interaction with additional molecule.
TD-DFT simulations of the bioorganic complex with implemented neutral radical molecules show that it is ossible to construct ContrlNOT and AND logic functions in the nanobiorobots. Quantum logic functions should control metabolic photodissociation of lipid precursor molecule.
Our quantum simulations show on the possibility of experimental synthesis of quantum logically controlled artificial organisms. The experimentally made artificial molecular quantum computing organisms might be already were in the first stages of life emergency in the Earth or still exist somewhere in the Space.

[1] A. Tamulis, V. Tamulis A. Graja. “Quantum mechanical modeling of self-assembly and photoinduced electron transfer in PNA based artificial living organism”, Journal of Nanoscience and Nanotechnology, 6, 965-973 (2006).
[2] A. Tamulis, V. Tamulis, H. Ziock, S. Rasmussen, “Influence of Water and Fatty Acid Molecules on Quantum Photoinduced Electron Tunneling in Photosynthetic Systems of PNA Based Self-Assembled Protocells”, printing process in “Multi-scale Simulation Methods for Materials”, eds. R. Ross and S. Mohanty, John Wiley & Sons, Inc., New Jersey, 2006.
[3] S. Rasmussen, J. Bailey, J. Boncella, L. Chen, G. Collins, S. Colgate, M. DeClue, H. Fellermann, G. Goranovic, Y. Jiang, C. Knutson, P.-A. Monnard, F. Moufouk, P. Nielsen, A. Sen, A. Shreve, A. Tamulis, B. Travis, P. Weronski, W. Woodruff, J. Zhang, X. Zhou, and H. Ziock, “Assembly of a minimal protocell”, to be published in MIT Press book, “Protocells: Bridging nonliving and living matter”, eds S. Rasmussen, M. Bedau, L. Chen, D. Krakauer, D. Deamer, N. Packard, and P. Stadler, 2007.

Quantum Mechanical Design of Artificial Living Organisms During 2005 year

senior researcher Arvydas Tamulis and student Vykintas Tamulis
Vilnius University Institute of Theoretical Physics and Astronomy, A. Gostauto 12, Vilnius 01108, Lithuania

In order to better understand the origin of life and support the production of artificial living organisms in Los Alamos National Laboratory and programmable nano-biorobots, we have modeled the self-assembly of artificial organisms composed of hundreds of thousands of atoms. For the self-assembly of nucleobases and light harvesting systems in water solution, we used quantum mechanical (QM) density functional theory (DFT) and the semiempirical PM3 method in the Gaussian 03 and GAMESS-US packages. For the self-assembly of double-layers of lipid molecules in water solution and the formation of the overall artificial protocell we used molecular mechanics (MM) in GROMACS software. Self-assembly modeling of peptide nucleic acid (PNA) based minimal living organisms was performed using software we developed for building PNA double helices. QM DFT simulations, which include electron correlations confirm that the water molecules which surround the entire bioorganic complex stabilize it. The complex modeled consists of a 1,4-bis(N,N-dimethylamino) naphthalene sensitizer molecule which is covalently bonded to a PNA fragment, a lipid precursor molecule, and a fragment of the lipid molecule monolayer which bounds the complex.
The usage of exact QM DFT and MM GROMACS modeling indicates the possibility of the emergence of PNA based minimal life some 3.8 – 3.5 billion years ago in the hot, harsh conditions of the early Earth.
In order to make lipid molecules, time dependent (TD-DFT) simulations show that the energy of excitation and charge transfer trajectories depend on the distance and orientation between sensitizer and lipid precursor molecules.
TD-DFT simulations of artificial living systems predict that from the first OR the fifth excited electronic states of a bioorganic complex implemented with either 1,4-dihydroquinoxaline or 1,4-bis(N,Ndimethylamino) naphthalene sensitizer molecules, electron charge transfer can occur from the sensitizer molecules to the lipid precursor molecule. This is the OR function in classic Boolean logic, but there exists a small possibility of reversible electron tunneling back to the sensitizer molecule, it is actually a quantum logic OR function. This reversible OR logic function controls the metabolic photodissociation of the lipid precursor molecule that will obviously show localization of the lowest unoccupied molecular orbital (LUMO) in the first and fifth excited states of the waste end of the lipid precursor molecule. Analysis of the highest occupied molecular orbital (HOMO) and LUMO in the third excited state shows the trajectory of the electron tunneling being from the sensitizer to the cytosine-PNA where it should induce photodissociation of complementary C-G hydrogen bonds or other processes related to PNA replication.
TD-DFT simulations of the bioorganic complex implemented with a syringate molecule show that in the first excited electronic state electron charge and spin density transfer will occur from this neutral radical to the lipid precursor molecule when the electron spin is up in the second electronic excited state while there is no electron and spin density transfer when the electron spin is down in the first electronic excited state. This is a NOT logic function in quantum logic. This NOT quantum logic function should be able to control metabolic photodissociation of lipid precursor molecule that will obviously show localization in the LUMO of the first excited state of the waste end of the lipid precursor molecule.
Our quantum simulations show the possibility of experimental synthesis of quantum logic controlled artificial organisms. Creation of molecular quantum computing organisms may have already occurred in the first stages of life’s emergence on Earth or may exist elsewhere on the hot planets near the stars possessing strong magnetic fields.

Research in beginning of 2004 year

Quantum Mechanical Search for Basic Elements of Molecular NMR and ESR Quantum Computers and Investigations of Programmable Artificial Photosynthetic Systems Based on Assemblies of Modified Peptide Nucleic Acids and Lipid Molecules

senior researcher Arvydas Tamulis, Jelena Tamuliene, Vykintas Tamulis, Aiste Ziriakoviene
Vilnius University Institute of Theoretical Physics and Astronomy, A. Gostauto 12, Vilnius 2600, Lithuania

Currently our group performing research in several themes related with our institution project "Quantum Mechanical Modeling of Molecular Quantum Computers” and EC FP6 project "Programmable Artificial Cell Evolution (PACE)":
1) Quantum mechanical search of molecular systems (biverdins, porphyrins, etc.) which possess the scalable set of many QuBits in NMR quantum nano-computers and design of quantum logic gates.
2) Quantum mechanical time dependent investigations of spin density transfer in neutral radical molecules (syringates) for the design of quantum logic gates of ESR quantum nano-computers.
3) For the reasons to control peptide nucleic acid (PNA) biocomputers and make them programmable it was implemented set of molecular electronics logically controlled gates. Geometry of these supermolecules are optimized by quantum mechanical methods and now we are applying time dependent method in density functional theory for the electron charge transfer investigations.
4) In order to investigate the electron charge transfer in the artificial photosynthetic system it was performed quantum mechanical optimization of the geometry of supramolecular system composed from modified PNA with implemented light harvesting sensibilizator N,N,N',N'-tetramethyl-naphthalene-1,4-diamine (photo-electron donor), phenancyl ester lipid and sulfite (electron donor) molecules. We are using time dependent method in density functional theory for the investigations of all electron relay chains starting from the excited states of sensibilizator N,N,N',N'-tetramethyl-naphthalene-1,4-diamine and electron hopping to lipid molecule, and then electron relaxation and migration from sulfite to guanine, adenine and back to sensibilizator.

Research during 2003 year

Quantum Mechanical Investigations of Electronic Structure, Spectra, Electron Charge and Spin Density Transfer and Magnetically Features of Organic Molecules Suitable for Digital, Quantum and Biological Information Processing

senior researcher Arvydas Tamulis, Jelena Tamuliene, Vykintas Tamulis, Aiste Ziriakoviene
Vilnius University Institute of Theoretical Physics and Astronomy, A. Gostauto 12, Vilnius 2600, Lithuania

Quantum mechanically designed hardware of molecular electronics digital computers and molecular NMR and ESR quantum computers are presented. Maximal lengths of these molecular electronics digital and quantum information processing logic gates are no more than four nanometres and maximal width 2.5 nm.
There are presented several two and three variable gates of molecular electronics digital computers. The results of light induced internal molecular motions in azo-dyes molecules [1-3] have been used for the design of light driven logically controlled (OR, AND, NOR, NAND) molecular machines composed from organic photoactive electron donor dithieno[3,2-b: 2',3'-d]thiophene, tetrathiofulvalene (TTF) or ferrocene molecules and electron accepting 4,5-dinitro-9-(dicyanomethylidene)-fluorene (DN9(CN)₂F), tetracyano-indane, and moving azo-benzene fragment. After detail investigations of various electron insulator bridges between electrondonor and electronacceptor parts occurs that non-conjugated bridge -CH₂-CH₂- should be applied to join thiophene and DO3 molecules in order to design OR logical function that significantly improved quality in comparison with our previous designed devices [1-3]. Density functional theory (DFT) B3PW91/6-311G model calculations were performed for the geometry optimization of these molecular electronics logical gates. Applied DFT time dependent (DFT-TD/B3PW91) method and our visualization program give absorption spectra of designed molecular gates and show from which fragments electrons are hopping in various excited states. There are designed set of single supermolecule fluorescencing devices containing OR and AND logic functions.
There are presented quantum mechanical investigations of hydrogen and nitrogen atom Nuclear Magnetic Resonance (NMR) values of Cu, Co, Zn, Mn and Fe biliverdin derivatives and their dimers and aza-fullerene C₄₈N₁₂ adducts using Hartree-Fock (HF) and DFT methods indicate that these modified derivatives should generate from one to seven and eleven, twelve, eighteen, nineteen Quantum Bits (QuBits). The chemical shifts are obtained as the difference of the values of the tetramethylsilane (Si(CH₃)₄) and ammonia (NH₃) molecules Gauge-Independent Atomic Orbital (GIAO) nuclear magnetic shielding tensor on the hydrogen and nitrogen atoms and that of the magnetically active molecules. There are designed several single supermolecule and supramolecular devices containing molecular electronics digital logic gates, photoactive molecular machines and elements of molecular NMR quantum computers that allowed to design several supramolecular ControlNOT NMR quantum computing gates and induced idea of molecular quantum computing life.
Implementation of the quantum information processing based on spatially localised electronic spins in stable molecular radicals are discussed. The necessary operating conditions for such molecules are formulated in self-assembled monolayer (SAM) systems: 1) a tailoring group, to be attached to a substrate; 2) a localised unpaired electron spin; 3) a noncompensated chemical bond, responsible for an unpaired spin must be strong enough. We suggest to use the neutral radical molecules with Shiff base which satisfy these conditions. Using first principles quantum chemical calculations we prove that these molecules have the stable localised electron spin, which may represent a qubit in quantum information processing. Geometry of neutral radical molecules were optimized by using DFT Unrestricted B3LYP (Becke exchange and Lee-Yang-Parr correlation functionals) model with polarization 6-311G** basis functions. The spin density analysis shown that unpaired spin of radical molecules is located in the region of not-compensated valence bond. There were performed analysis of overlap population of chemical bonds in the region of unpaired spin density that gives evaluation and comparison of stability of various neutral radical molecules. Using optimized geometry it were calculated isotropic Fermi contact couplings constants and anisotropic spin dipole couplings using special EPR-II basis set in the method of UB3LYP that shown that the largest hyperfine splittings (HFS) of Electron Spin Resonance (ESR) spectra are on atoms of above mentioned region of not-compensated valence bond. For the reasons of construction of logic gates of ESR molecular quantum computers were calculated electronic spectrum and electron charge and spin density transfer in various excited states of neutral radical molecules. Analysis of electron charge and spin density transfer in different excited states show that this phenomenon might be used for the construction of ControlNOT logical gate for the QuBit associated with unpaired spin in the stable neutral radical molecules.
There are developing molecular electronics devices for natural and artificial living systems using exact quantum chemical ab initio and DFT methods [4,5]. Self-assembly of various VS/UV sensitive peptide nucleic acid fragments are investigating by DFT-TD B3LYP 6-311G** method in order to design molecular information system for programmable artificial living cell.

[1] A. Tamulis, J. Tamuliene, V. Tamulis, Quantum Mechanical Design of Light Driven Molecular Logical Machines and Elements of Molecular Quantum Computers, in NATO Science Series, II. Mathematics, Physics and Chemistry, vol. 96, Molecular Electronics: Bio-sensors and Bio-computers, L. Barsanti, et al. (eds.), Kluwer Academic Publishers, 2003, p.p. 1-27.

[2] A. Tamulis, J. Tamuliene, V. Tamulis, "Quantum Mechanical Design of Photoactive Molecular Machines and Logical Devices", 11th chapter in "Handbook of Photochemistry and Photobiology", Vol. 3 "Supramolecular Photochemistry", Ed. H.S. Nalwa, American Scientific Publishers, p.p. 495-553, 2003.

[4] A. Tamulis, Z. Rinkevicius, J. Tamuliene, V. Tamulis, A. Graja, A. K. Gaigalas, Quantum Chemical Design of Light Driven Molecular Logical Machines, in A. Graja, B. R. Bulka, F. Kajzar (eds.) NATO Science Series II., vol. 59, Mathematics, Physics and Chemistry, Molecular Low Dimensional and Nanostructured Materials for Advanced Applications, Kluwer Academic Publishers, Dordrecht, 2002, p.p. 209-219.

[4] A. Tamulis, Z. Rinkevicius, J. Tamuliene, "Quantum chemical ab initio design of molecular electronics devices for natural and artificial living systems", Proceedings of the XIIth Rencontres de Blois "Frontiers of Life", June 25 - July 1, 2000, Blois, France, Printed in Vietnam The Gioi Publishers, 2003, p.p. 305-317.

[5] A. Tamulis, J. Tamuliene, V. Tamulis, "Quantum Mechanical Search for Molecular Quantum Computing Living Systems", book of abstracts of 1^st Workshop of the COST Chemistry Action D27 on "Origin of Life and Early Evolution", Ravello, Italy, October 17-20, 2002, p. 65.

Research during 2001 and 2002 years

Quantum Mechanical Design of Single Supermolecule Photoactive Machines and Molecular Classical and Quantum Logic Devices

senior researcher Arvydas Tamulis ^a, Zilvinas Rinkevicius ^b, Jelena Tamuliene ^a,
Vykintas Tamulis ^a,c, Mindaugas L. Balevicius ^d

^aVilnius University Institute of Theoretical Physics and Astronomy, A. Gostauto 12, 2600 Vilnius, Lithuania
^bKaunas Technology Univ., Faculty of Fundamental Sciences, Studentu st. 50, Kaunas 3000, Lithuania
^cVilnius Gediminas Technical Univ., Faculty of Fundamental Sciences, Sauletekio al. 11, Vilnius, Lithuania
^d Faculty of Physics, Vilnius University, Sauletekio al. 9, III rumai, 2054 Vilnius, Lithuania

Quantum mechanically ab initio and DFT-Time Dependent designed light-driven, single supermolecular devices based on fullerene, biliverdin and photoactive molecules and supermolecules could form the basis for logically-controlled organic molecular machines and molecular classical and quantum computers [1-12]. Organic and organo-metallic molecular computers have advances in nano-size and pico- or even femto-second speed as well as of in principle new quantum computation compared with conventional silicon-based chips. Theoretical molecular physics can provide the basic understanding needed to design such a single supermolecule devices by calculating the optimized geometries, quantum state energies, electron and proton charge transfer, NMR, EPR, etc. of candidate molecules and suggesting new supermolecules molecules with the desired quantum properties. Using advanced computational chemistry tools we, for instance, elucidated the energies and pathways of optically-induced charge transfer and the trans-cis isomerization of azo-dyes based supermolecules, and the electrical and magnetic properties of fullerene (ErSc₂N@[CCl₂CCl₂NCl]C₈₀, figure on left) and a biliverdin (figure on right) derivatives.

Set of gates of classical digital molecular computers are designed based on light driven charge transfer in fullerene-containing supermolecules.
Designed basic elements of quantum computers are based on EPR estimations in endohedral fullerenes (figure on left) that possess up to six quantum bits (QuBits) and proton NMR estimations in biliverdin derivatives (figure on right) that generate up to eleven QuBits for quantum computation. It were designed various biologically active, fluorescencing, small-gap semiconductor and proton-transfer switching single supermolecular devices based on biliverdin, fluorescein, CdS organic and white phosphorus organo-metallic complexes.

[1] A. Tamulis, E. Stumbrys, V. Tamulis and J. Tamuliene, "Quantum Mechanical Investigations of Photoactive Molecules, Supermolecules, Supramolecules and Design of Basic Elements Molecular Computers", in NATO ASI series, High Technology; Vol. 9, Ed. by F. Kajzar, V. M. Agranovich and C. Y.-C. Lee, Photoactive Organic Materials: Science and Applications, June 25-30, 1995, Avignon, France, Kluwer Academic Publishers, Doderecht/Boston/London, p.p. 53-66 1996.

[2] A. Tamulis, V. Tamulis, "Design of Basic Elements of Molecular Computers Based on Quantum Chemical Investigations of Photoactive Organic Molecules", Proceedings of the SPIE Photonics WEST® Conference on Optoelectronics Integrated Circuits II, held in 24-30 January, 1998, San Jose Convention Center, San Jose, California, U.S.A., Volume 3290, p.p. 315-324.

[3] A. Tamulis, V. Tamulis and J. Tamuliene, Quantum Mechanical Design of Molecular Implementation of Two, Three and Four Variable Logic Functions for Electronically Genome Regulation, Viva Origino, 26, p.p. 127-146, 1998.

[4] A. Tamulis, J. Tamuliene, M.L. Balevicius, J.M. Nunzi, "Quantum Chemical Design of Multivariable Anisotropic Random-Walk Molecular Devices Based on Stilbene and Azo-Dyes", Proceedings of the 5th International Conference on Frontiers of Polymers and Advanced Materials, 21-25 June 1999, Poznan, Poland, published in the journal Mol. Cryst. Liq. Cryst., 2000, Vol. 354, p.p. 475-484.

[5] A. Tamulis, J. Tamuliene, M.L. Balevicius, J.-M. Nunzi, "Quantum Mechanical Investigations of Photoactive Molecules and Design of Molecular Machine and Logical Devices", published in the Proceedings of Photonics West 2000 conference, SPIE Conference Organic Photonics Materials and Devices II (OE04), held in San Jose, California, USA, January 22-28, 2000. Editors: Donald D. C. Bradley, Bernard Kippelen, Vol. 3939, p.p. 61-68.

[6] A. Tamulis, J. Tamuliene, M.L. Balevicius, J.-M. Nunzi, "Quantum Chemical Investigations of Disperse Orange 3 Molecule Cis-Trans Isomerization Through Linear Transition State and Design of Molecular Machines", in Applications of Photonic Technology 4, Roger A. Lessard, George A. Lamppropoulos, Editors, Proceedings of SPIE, vol. 4087, p.p. 662-670, 2000.

[7] A. Tamulis, Z. Rinkevicius, J. Tamuliene, V. Tamulis, M.L. Balevicius, A. Graja, "Ab initio quantum chemical design of supermolecule logical devices", in Optoelectronic Integrated Circuits and Packaging V, James G. Grote, Randy A. Heyler, Editors, Proceedings of SPIE Vol. 4290, p.p. 82-93, 2001.

[8] A. Tamulis, Z. Rinkevicius, V. Tamulis, J. Tamuliene, S.P. Karna, C.M. Stickley, "Ab Initio Quantum Chemical Design of Photoactive Molecular Logical Devices", Nonlinear Optics, vol. 27, p.p. 385-393, 2001.

[9] A. Tamulis, J. Tamuliene, M.L. Balevicius, Z. Rinkevicius, "Ab Initio Quantum Chemical Search of Per Linear Transition State of Azo-Dye Molecules and Design of Molecular Logical Machines", Nonlinear Optics, vol. 27, p.p. 481-488, 2001.

[10] J. Tamuliene, A. Tamulis, "Quantum Chemical ab initio Design of Molecular Electronics Tools for Biotechnologies", Biotech News International, vol. 6, No. 5, p.p. 12-14, 2001.

[11] A. Tamulis, Z. Rinkevicius, J. Tamuliene, "Molecular Classical Computer Basic Elements", in "Decoherence and Implication in Quantum Computation and Information Transfer" edited by T. Gonis and P.E.A. Turchi, NATO Science Series III Computer and Systems Sciences, vol. 182, p.p. 358-365, 2001.

[12] A. Tamulis, Z. Rinkevicius, J. Tamuliene, V. Tamulis, A. Graja, A.K. Gaigalas, "Quantum Chemical Design of Light Driven Molecular Logical Machines", in Eds. A. Graja, B.R. Bulka, F. Kajzar, "Molecular Low Dimensional and Nanostructured Materials for Advanced Applications", KLUWER Academic Publishers in NATO ASI Series: Mathematics, Physics and Chemistry, 2002, p.p. 209-219.

Research during 1999-2000 years

Quantum Chemical ab initio Search for Novel Molecular Technologies

senior researcher Arvydas Tamulis ^a , J. Tamuliene^a, M.L. Balevicius ^b, Z. Rinkevicius^c, M.M. Olmstead^d,
A. L. Balch^d, A.K. Gaigalas^e, J.-M. Nunzi ^f, A. Graja^g, V. Tamulis^a,
R.R. Abdreimova ^h, M. Peruzziniⁱ

^aInstitute of Theoretical Physics and Astronomy, A. Gostauto 12, 2600 Vilnius, Lithuania;
^bFaculty of Physics, Vilnius University, Lithuania; ^cKaunas Technology University, Faculty of Fundamental Sciences, Studentu st. 50, Kaunas 3000, Lithuania; ^dDepartment of Chemistry, University of California, Davis, California 95616, USA; ^eNational Institute of Standards and Technology, Gaithersburg, MD 20899-8312, USA; ^fGCO-LETI-CEA, Saclay; France; ^gIFMPAN, Poznan, Poland; ^hIOCE, Almaty, Kazakhstan; ⁱISSECC, Florence, Italy

1. Quantum Chemical Design of Molecular Logically Controlled Multivariable Anisotropic Random-Walkers ^a,b,c,f

Density Functional Theory (DFT) and CIS-Hartree-Fock (HF) methods are used for the geometry optimization in ground and first excited states of both stilbene and Disperse Orange 3 (DO3) azo-dye molecules.
The geometrical structure of the both ground and excited state of the DO3 molecule have been investigated DFT and HF method with Berny geometry optimization. The investigations proved that the above-mentioned molecule can not rotate around the -N=N- bond. Thus, the alternative mechanism of the isomerization of the DO3 molecule per linear transition state is suggested and investigated (see Figure).

The obtained one- and many- electron energy diagrams are drowning. According to these diagrams the above- mentioned isomerization way might be possible.
The results of light induced internal molecular motions in stilbene and DO3 molecules have been used for the design of light driven molecular machines. Two-, three-, four- and six-variable anisotropic random-walk molecular motor devices are designed from photoactive organic molecules such as carbazole, 1,4-phenylenediamine (PhDA), TeMePhDA, stilbene, DO3 azo-dye, 4,5-dinitro-9-(dicyanomethylidene)-fluorene (DN9(CN)2F), TCNB and TCNQ molecules joined with -C₂H₂- or -N=N- bridges.
Molecular implementation of organic derivatives based two-, three-, four-variable logic functions, summators of neuromolecular networks, cells of molecular cellular automata, molecular trigger - molecular logic devices and molecular devices for electronically genome regulation were designed based on results of semiempirical and ab initio HF, DFT quantum chemical calculations of the above mentioned electron-donors, electron-insulators, electron-acceptors as well as fullerene molecules.
The molecular logical devices joined to multivariable anisotropic molecular random-walkers should be capable of moving under light exposure and therefore represent a new kind of logically controlled molecular motors. Two examples of such molecular logically controlled motors have been designed and calculated using HF\6-31G method: (1) (Cz-C₂H₂-)(NH₂-)(C₆H₃ )-C₂H₂-(DN9(CN)2F)-N=N-(C₆H₄ -NO₂) and (2) (Cz-C₂H₂-)(PhDA-C₂H ₂-)(NH₂-)(C₆H₂ )-C₂H₂-(DN9(CN)2F)-N=N-(C₆H₄ -NO₂) and analogous compounds with the more flexible bridge -N=N-. (1) random-walker is two variable AND logically controlled molecular device and (2) is three different ways two variable AND controlled molecular random-walker.

2. Quantum Chemical Investigations of Stability of Non-Covalent Fullerene C₆₀ Complexes and Dimers and Endohedral C₈₀ Derivatives. Design of Fullerene Based Molecular Devices ^a,b,c,d,g

The geometry and energy of formation of single molecules such as fullerene C₆₀, CS₂, benzene and tetrathiafulvalene (TTF) and of their complexes like C₆₀+CS₂ , C₆₀+benzene, C₆₀+TTF, C₆₀+Li were obtained using HF and DFT methods with the aim to search for new high conducting organic thin films. Weak chemical interactions were estimated satisfactorily by using HF\6-31G for a comparison of various geometrical conformations of these complexes. The energy of formation of the c charge-transfer complex C60+TTF has been performed calculating the complex with far-separated molecules.
The system consisting of two C₆₀ molecules and a single CS₂ solvent molecule was investigated by HF method using 6-31G basis in order to find the geometry with the positive energy of packing of such a clathrate. The minimal energy point of this complex was determined when the distance between the C atom of the CS₂ molecule and the symmetry center of the line connecting two C₆₀ molecules is 5.46 Å and the distance between two C₆₀ is 10.98 Å (Figure left). The positive energy of formation is equal to 0.483 kcal/mol for this complex. It implies that the presence of the CS₂ molecule stabilizes the complex consisting of two C₆₀ and CS₂ molecule in value of 0.281 kcal/mol.

Quantum chemical investigations of isolated fullerene C₆₀ and TTF molecules and stability of non-covalent bond complex C₆₀+TTF (Figure right) have been performed by ab initio HF and DFT B3PW91 model with various basis sets. The lowest energy of the isolated C₆₀ molecule has obtained by B3PW91/6-311G** model.
The isolated TTF molecule and its positive ion have been investigated by B3PW91 model in the 6-311G** basis set. After full geometry optimization mentioned above molecule and its positive ion possess the planar structure. Comparison of HOMO and LUMO shows that TTF molecule is electron donor relatively the fullerene molecule. One of the lowest total energy displacements of TTF molecule above the fullerene molecule has been obtained during partial optimization of distances and dihedral angle between center of C₆₀ and TTF molecule using HF\6-31G method. The investigation of the above complex indicates it as Van der Waals type with partial charge transfer and energy of formation of 0.30 kcal/mol. The double bond connecting two pentagonal rings of the TTF molecule was 7.97 Å above the center of the hexagonal ring of the fullerene.
The HF/6-31G calculations show the stability of dimer of C₆₀[2+2] molecule (Figure left). The influence of orto-dichloro-benzene solvent molecule in the crystal of C₁₂₀ gives up to 0.015-electron charge differences on the atoms of square bridge and nearby. Endohedral fullerene C₈₀ derivatives: Sc₃N@C₈₀ (Figure right) with Sc₃N molecule inside and ErSc₂N@C₈₀ were investigated by DFT B3PW91 model using 6-311G** and WTBS basis sets in order to find stabilization energies and geometries of above endohedral fullerenes. It was designed and calculated light controlled electric and magnetic field molecular switches based on above endohedral fullerenes properties.

Azafullerene HNC₅₉ and dimer NC₅₉-NC₅₉ was investigated by HF/6-31G that allowed designing and calculating photoactive charge transfer light driven molecular machine (see Figure bellow).

Molecular Implementation (MI) of carbon based two, three, four variable logic functions, summators of neuromolecular networks, cells of molecular cellular automata, molecular trigger - molecular logic devices and molecular devices for electronically genome regulation were designed based on results of semiempirical and ab initio HF, DFT quantum chemical calculations of the electron donors, electron insulators, electron acceptors and fullerene molecules. Complete set of sixteen MIs of two variable logic functions (for example: OR, AND, Implication, Equivalence, Difference, etc.) was designed and also proposed using MIs of two variable molecular logic function initial basic sets: {OR, AND, Negation} or {NOR} and, or {NAND}. We have described in more detail the designed MIs of: a) two variable logic functions OR, NOR, AND, NAND (from fullerene molecules), Converse Unitary Negation-1, Converse Unitary Negation-0, Unitary Negation-1, Unitary Negation-0, "0" and "1" Matrix Constants; b) three variable logic functions AND, NAND, OR, NOR analogs; c) four variable logic functions OR, NOR, AND, NAND analogs. The electron hoping via the insulator bridges in the supermolecules: electron donor-bridge-electron acceptor phenomenon was investigated by using CNDO/S-Configuration Interaction method.
We are performing design of molecular logical devices based on planar electron donor and electron acceptor molecules, series of fullerene C₆₀ substituted derivatives: C₆₀CH₂, C₆₀C₂ H₄, C₆₀C₃H₆, C₆₀ C₄H₈, electron donor-bridge-electron acceptor dyads and triads. Design of new series of more correctly organic molecules based MIs of two variable logic functions: OR, NOR, AND, NAND (two sets: one from planar molecules and another from fullerene molecules), Converse Unitary Negation-1, Converse Unitary Negation-0, Unitary Negation-1, Unitary Negation-0, "0" and "1" Matrix Constants is based on geometry optimization procedure in ground and excited states.

3. Quantum Chemical ab initio Investigations of Optimized Monoanion and Dianion Fluorescein Structures in Ground and Excited States ^a,c,e

Fluorescence has become the dominant indicator in biological assays both immunological and genetically based. For quantitative measurements, the intensity of the fluorochrome fluorescence has to be related to the number of fluorochromes. In order to enhance the quantitation of fluorescence intensity means have to be developed to decrease the sensitivity of the fluorochrome to the microenvironment. One approach has been to develop nano crystals another approach is to control the sensitivity to the microenvironment of known dyes. The later approach, which is pursued in this work, requires that we understand in detail the various mechanisms, which influence the quantum yield of the fluorescence.
Quantum chemical ab initio calculations along with full geometry optimizations of dianion and monoanion fluorescein molecules in the ground state were performed applying the DFT B3PW91/6=311G** model. The ZINDO method was applied performing the spectra calculations of the isolated photoactive molecule using optimized geometries in ground states. The comparison of geometrical, electronical and spectral features of two fluorescein forms is done:
1. The highest total energy in the regions near 90 degrees means that fluorescein dianion molecule needs to some conjugation between single-ring and triple-ring planes.
2. Important it is value of overlapping population between C-C connecting single-ring with triple-ring in fluorescein dianion molecule. This value it is relatively small but positive: 0.351 x 2 = 0.702.
3. The main transition of fluorescein monoanion calculated by ZINDO using geometry taken from Cambridge data basis (not optimized geometry) is equal to 441.79 nm f = 1.0056. The Hartree-Fock 6-311G** optimized geometry and ZINDO calculations gives the main transition equal to 445.67 nm, f = 1.1488. The better optimized method B3PW91/6-311G** shifts spectrum to the longest wavelength region 2.7567 eV or 449.75 nm, f = 1.12 that corresponds to the experiment observations.
4. The small out of plane deviations are in dianion three-ring plane: D₁ = -1.92 and D₂ = 178.06 degrees. The three-ring part of monoanion is distorted out of plane by D₃= -6.40 degrees therefore the dihedral angles D₄ = -88.82 and D₅ = 90.03 degrees differs from D₆= 71.36 and D₇= -109.80 degrees. The one-ring it is slightly out of plane distorted by D₈ = -0.21 and D₉= 0.23 degrees.
5. The gap between HOMO and LUMO in dianion is equal to 0.11046 a. u. = 3.006 eV = 69.31 kcal/mol and in monoanion it is equal to 0.1158 a. u. = 3.151 eV = 72.67 kcal/mol. That means what fluorescein monoanion kinetically is more stable in comparison with kinetic stability of dianion.
6. The -CO₂ group in dianion it should be easier to remove because the overlapping population value on C-C it is smaller (0.005) and large total negative charge (-0.592) in comparison with monoanion.
7. The main transition of calculated monoanion single molecule is in the near UV region and it is not so intensive (397.51 nm, f=0.8301) in comparison with dianion spectrum that corresponds to experiment.
8. The possibility of clathrates arrangements of monoanion molecule in polar solvents it is larger because the dianion molecule dipole moment it is smaller (8.99 Debyes) in comparison of monoanion.

4. Quantum Chemical Investigations of Tetraphosphorus Activation within Coordination Sphere of Transition Metal Complexes ^a,b,h,i

The ecologically friendly catalytic P-O coupling reaction for the synthesis of trialkyl phosphates is proposed. A slightly distorted octahedral symmetry was used for the design and optimization by B3PW91 of the initial starting geometry in different transition metal (M = Pt, Pd, Ni) complexes:
(1) [MX₃(CH₃OH)(h ²-P₄)]^-1, (2) [MX₃(CH₃OH)(h ²-P₄)]⁺¹,
(3) [MX₃(CH₃OH) (H₂O) (h¹-P₄)] ^-1, (4) [MX₃(CH₃OH)(H₂O)( h¹-P₄)] ⁺¹,
(5) [MX₃(CH₃OH)( h²-P₄)] ^-1, (6) [MX₃(CH₃OH) (h²-P₄)] ⁺¹,
(7) [MX₃(CH₃OH)(H₂O) (h¹-P₄)] ^-1, (8) [MX₃(CH₃OH)(H₂O)( h¹-P₄)]⁺¹, ( X = Cl, Br) and complexes [CuCl(CH₃OH) (H₂O)₃( h¹-P₄)]⁺¹ and [CuCl₃ (CH₃OH) (HO)(h ¹-P₄)]^-2.
Suitable conditions for the intersphere nucleophilic attack of the tetraphosphorus P₄ molecule by the alkoxide-ion RO^- are better matched with cationic complexes with highly oxidized M(IV) transition metals.

Research presented in this web page was financed by: Institute of Theoretical Physics and Astronomy of Vilnius University, Lithuanian Government; Agency for International Science and Development Programs in Lithuania; Lithuanian State Science and Studies Foundation; EU FP6 "Programmable Artificial Cell Evolution" grant, NorFA "Quantum Modeling of Molecular Materials" grant, EU COST D27 Prebiotic Chemistry and Early Evolution" sources, Center for Nonlinear Studies at USA Los Alamos National Laboratory; USA Airforce Department EOARD contract F61775-00-WE050; European Union contract ERBIC15CT960746; French CIES and CEA-Saclay; USA NRC Twinning Program with Baltic States; NATO-CNR Italy; George Soros Foundation; Swedish Institute.

Computing support: Prof. S. Rasmussen supplied Altix 3000 in Los Alamos National Laboratory with installed Gaussian03 package, Prof. A. Graja supplied CRAY and Origin 3000 in Poznan's Supercomputing and Networking Center with installed Gaussian03 and Gaussian98 packages; Dr. A.K. Gaigalas supplied accounts in United States NIST computer system with installed G98 A.7; Dr. N.A. Kotov in Oklahoma State University supplied DEC-AXP-OSF/1 computer with installed Gaussian94 and G98 packages.

GRANTS obtained by dr. Arvydas Tamulis group during last seventeen years