[PDF]    http://dx.doi.org/10.3952/lithjphys.46219

Open access article / Atviros prieigos straipsnis

Lith. J. Phys. 46, 169–175 (2006)


MAGNETIC SHIELDING PROPERTIES OF WATER IN VARIOUS MOLECULAR AND MOLECULAR-IONIC STRUCTURES
K. Aidas, A. Maršalka, L. Kimtys, V. Urba, and V. Balevičius
Faculty of Physics, Vilnius University, Saulėtekio 9, LT-10222 Vilnius, Lithuania
E-mail: kestutis.aidas@ff.vu.lt, arunas.marsalka@ff.vu.lt, liudvikas.kimtys@ff.vu.lt, vilhelmas.urba@ff.vu.lt, vytautas.balevicius@ff.vu.lt

Received 28 April 2006

Dedicated to Prof. Dr. Dr. h. c. Hartmut Fuess (Darmstadt Technical University, Germany) on the occasion of his 65th birthday

1H and 17O magnetic shielding tensors of water molecules in various water clusters, as well as in water–pyridine H-bond complexes and in molecular-ionic structure of Br−(H2O)6 have been calculated using density functional theory. The full geometry optimization was performed in the framework of Becke’s three parameter hybrid method and the Lee–Yang–Parr correlation functional (B3LYP) combined with 6-311++G** basis set. Magnetic shielding tensors have been calculated using the hybrid functional of Perdew, Burke, and Ernzerhof (PBE1PBE) and the gauge-including atomic orbital (GIAO) approach was applied to ensure gauge invariance of the results. Solvent effects were taken into account by polarizable continuum model (PCM). The calculated NMR parameters are compared with the corresponding experimental data for aqueous system, which exhibit an unusual critical behaviour and phase transitions.
Keywords: density functional theory, properties of molecules and molecular ions, line and band widths, shapes and shifts, NMR and relaxation
PACS: 33.15.Fm, 33.70Jg, 76.60-k


MOLEKULINIŲ VANDENS BEI VANDENS IR JONŲ DARINIŲ MAGNETINIO EKRANAVIMO SAVYBĖS
. K. Aidas, A. Maršalka, L. Kimtys, V. Urba, V. Balevičius
Vilniaus universitetas, Vilnius, Lietuva

Pastarųjų metų tyrimai kelia vis didėjantį susidomėjimą įvairių vandens darinių (tirpalų, elektrolitinių sistemų) savybėmis ir parametrais. Vanduo yra svarbiausia medžiaga gyvojoje gamtoje, todėl sparčiai auga skaičius darbų, kuriuose taikomi šiuolaikiniai branduolinio magnetinio rezonanso (BMR) tomografijos metodai. Be to, dariniuose vanduo / organinis sandas / joninė posistemė dažnai aptinkami struktūriniai bei faziniai virsmai, kurie labai skatina statistikinės kondensuotųjų terpių fizikos pažangą. Šiame darbe pateikiami įvairių vandens molekulinių ((H2O)n spiečiai (n = 1 . . . 5), H2O vandenilinio ryšio kompleksai su piridinu) bei vandens ir jonų (Br−(H2O)6) darinių 1H ir 17O branduolių magnetinio ekranavimo tenzorių skaičiavimo rezultatai kvantinės chemijos ab initio tankio matricos metodu 6-311G** bazėje visiškai optimizuojant tiriamųjų molekulių geometriją. Optimizavimui buvo panaudotas Becke hibridinis trijų parametrų metodas kartu su Lee, Yang ir Parr’o funkcionalu (B3LYP). Skaičiuota 6-311++G** funkcijų bazėje. Magnetinio ekranavimo tenzoriams skaičiuoti buvo pritaikytas hibridinis Perdew, Burke ir Ernzerhof’o funkcionalas (PBE1PBE) ir GIAO atominės orbitalės. Į tirpiklio reakcijos lauką buvo atsižvelgta, pritaikius poliarizuotojo kontinuumo modelį (PCM-IEF). Taip apskaičiuoti vandens 1H ir 17O branduolių ekranavimo parametrai gerai dera su atitinkamais eksperimentiniais BMR spektrometrijos duomenimis. Rezultatai bus pritaikyti tolesniuose tyrimuose, aiškinant vandens BMR signalų temperatūrines priklausomybes bei restruktūrizavimosi reiškinius kriziniuose vandens tirpaluose.


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