Static hyperpolarizability of the van der Waals complex CH₄N₂

Abstract

The static first hyperpolarizability of the van der Waals CH(4)-N(2) complex was calculated. The calculations were carried out in the approximation of the rigid interacting molecules for a broad range of intermolecular separations (R = 6-40 a(0)) and for six configurations at CCSD(T) level of theory using the correlation consistent aug-cc-pVTZ basis set with the basis set superposition error correction. It was shown that the long-range classical approximation, including the terms up to R(-6), is in a good agreement with ab initio calculations for R > 11 a(0). It was found out that for the family of most stable configurations of the complex, the first hyperpolarizability invariants practically do not change (the changes are less than 0.1%). Under forming the stable van der Waals CH(4)-N(2) complex, the intensity and degree of depolarization of the hyper-Rayleigh scattering are noticeable decreased (by ∼10%) to be compared with the free CH(4) and N(2) molecules.

Crystal Field Effects on Atomic and Functional-Group Distributed Polarizabilities of Molecular Materials

“…The strategies used here are useful tools for rationally design organic optical materials from a building-block (functionalgroup) reasoning, but further investigations are necessary to test their suitability for other chemical systems, such as those formed by only weaker intermolecular interactions (van der Waals aggregates) 48 or by stronger covalent bonds (organic polymers). 36 We are currently performing work in this direction.…”

A Computational Study of the Interaction and Polarization Effects of Complexes Involving Molecular Graphene and C60 or a Nucleobases

“…The supermolecular approach, used for the computation of the interaction-induced NLO properties of the present study eq , accounts directly for exchange-repulsion effects . The negative sign of the interaction induced properties may be interpreted by invoking the orbital contraction (compression) effect between the interacting centers. − …”

Multipole electric moments and higher polarizabilities of molecules: The methodology and some results of ab initio calculations

“…-ýëåê-òðè÷åñêîå ïîëå èëè åãî ãðàäèåíòû, íàâåäåííûå íà ìîëåêóëå âçàèìîäåéñòâóþùèìè ñ íåé äðóãèìè ìîëåêóëàìè. Êàê ñëåäñòâèå, ìóëüòèïîëüíûå ìîìåíòû è (âûñøèå) ïîëÿðèçóåìîñòè ñèñòåìû âçàèìîäåéñòâóþùèõ ÷àñòèö áóäóò çàâèñåòü êàê îò ðàññòîÿíèÿ ìåaeäó íèìè, òàê è îò èõ âçàèìíîé îðèåíòàöèè [16][17][18][19].…”

“…Äàëüíåéøåå âû÷èñëåíèå ìóëüòèïîëüíûõ ìîìåíòîâ è âûñøèõ ïîëÿðèçóåìîñòåé ìîaeåò áûòü ïðîâåäåíî äâóìÿ ñïîñîáàìè: ñ èñïîëüçîâàíèåì àíàëèòè÷åñêîãî âû÷èñëåíèÿ ïðîèçâîäíûõ â (3) èëè ÷èñëåííûõ ìåòîäîâ. Ïðåèìóùåñòâîì àíàëèòè÷åñêèõ ðàñ÷åòîâ, êàê óaeå îòìå÷àëîñü âûøå, ÿâëÿåòñÿ âîçìîaeíîñòü àíàëèòè÷åñêîãî îïèñàíèÿ ïîâåðõíîñòè âçàèìîäåéñòâóþùèõ ìîëåêóë (èëè ÷àñòåé ìîëåêóëû), êîãäà ïîñëåäíèå íàõîäÿòñÿ äðóã îò äðóãà íà áîëüøèõ ðàññòîÿíèÿõ, ïðåâûøàþùèõ ñóììó èõ âàí-äåð-âààëüñîâñêèõ ðàäèóñîâ, è â áîëüøîé ñòåïåíè ñîõðàíÿþò ñâîþ èíäèâèäóàëüíîñòü, ÷òî ñîáñòâåííî è îáåñïå÷èâàåò âîçìîaeíîñòü âûðàçèòü ýíåðãèþ âçàèìîäåéñòâèÿ, à ñëåäîâàòåëüíî è ìóëüòèïîëüíûå ìîìåíòû è âûñøèå ïîëÿðèçóåìîñòè ìîëåêóëÿðíûõ êîìïëåêñîâ ÷åðåç õàðàêòåðèñòèêè (ìóëüòèïîëüíûå ìîìåíòû, ïîëÿðèçóåìîñòè) âçàèìîäåéñòâóþùèõ ìîëåêóë (àòîìîâ) [9][10][11][16][17][18][19].…”