Lithuanian Journal of Physics article / Lietuvos fizikos žurnalo straipsnis

NONLINEAR CORRELATIONS BETWEEN ν₁ RAMAN BAND AND GLOBAL SCALAR PROPERTIES FOR DIFFERENT LENGTH CAROTENOIDS
Mindaugas Mačernis
Institute of Chemical Physics, Faculty of Physics, Vilnius University, Saulėtekio 3, 10257 Vilnius, Lithuania
E-mail: mindaugas.macernis@ff.vu.lt
Received 22 March 2018; revised 15 May 2018; accepted 21 June 2018

The Raman ν₁ band corresponding to the polarization of various length carotenoid (Car) and polyene molecules was theoretically analysed using the density functional theory (DFT) approach. The polarization and other properties of Car and polyene monomers were estimated by using global scalar properties. The results demonstrate a linear dependence between the frequency of the so-called ν₁ Raman band corresponding to the C=C stretching modes, and the global hardness (and global softness) for all molecules of different conjugation lengths. Linear correlations between all global scalar properties and the conjugation length were for polyene structures only. From these calculations an additional relationship was also identified: upon s-cis-isomerisation the effective conjugation length and global softness increased for polyenes, while the effective conjugation length and global softness decreased for carotenoids containing β-rings at their ends. According to the electrophilicity index study, charge transfer processes (CT) should be favourable in longer carotenoid and polyene structures. A linear dependence of electronegativity was found for polyene and particular Cars subgroups. The electrophilicity index was very sensitive to special groups bonded to the polyene chain of Cars. Finally, the conjugation length of the Cars did not have a linear dependence on the electronegativity, chemical potential and electrophilicity index, but almost a linear dependence was seen on the global hardness while the polyene models had a linear dependence in all cases.

Keywords: carotenoid, polyene, resonance Raman, quantum chemistry, polarizability
PACS: 31.15.E-, 31.15.ee, 31.15.eg, 31.15.V-, 31.15.vj

RAMANO ν₁ JUOSTOS IR GLOBALIŲ SKALIARINIŲ SAVYBIŲ NETIESINĖS KORELIACIJOS ĮVAIRAUS ILGIO KAROTINOIDUOSE
Mindaugas Mačernis

Vilniaus universiteto Cheminės fizikos institutas, Vilnius, Lietuva

Skirtingo ilgio karotinoidų ir polienų molekulių poliarizacinės savybės, kurios sietinos su Ramano ν₁ juosta, buvo teoriškai analizuotos naudojant tankio funkcionalų metodiką. Karotinoidų ir polienų monomerų poliarizacija ir kitos savybės buvo skaičiuojamos naudojant globalias skaliarines savybes. Rezultatai rodo tiesinę priklausomybę tarp Ramano ν₁ juostos atitinkamo virpesinio dažnio, kuris atitinka C=C jungties pailgėjimo modą, ir globalaus kietumo (ir globalaus minkštumo) visoms skirtingo ilgio molekulėms. Visos tiesinės priklausomybės tarp jungties ilgio ir visų globalių skaliarinių savybių buvo tik polieninėms struktūroms. Remiantis skaičiavimų rezultatais buvo nustatytas papildomas sąryšis: dėl s-cis-izomerizacijos padidėjo polienų efektyvusis jungties ilgis ir globalus minkštumas, o karotinoidų, kurie turi galuose β-žiedus, efektyvus jungties ilgis ir globalus minkštumas sumažėjo. Pagal elektrofiliškumo indeksų analizę krūvio pernašos (CT) vyksmai turėtų lengviau vykti ilgesniuose karotinoidų ir polienų dariniuose. Elektroneigiamumo tiesinės priklausomybės buvo tarp polienų ir tarp atskirų karotinoidų pogrupių molekulių. Prie karotinoidų polieninės grandinėlės prijungtos įvairios grupės ypač turėjo reikšmės elektrofiliškumo indeksui. Karotinoidų efektyvus jungties ilgis nėra tiesiškai susijęs su elektroneigiamumu, cheminiu potencialu ir elektrofiliškumo indeksu, tačiau beveik tiesinė priklausomybė matoma su globaliu kietumu, tuo tarpu polieninių darinių modeliai tiesines priklausomybes turėjo visada.

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