Molecular simulation of static hyper-Rayleigh scattering: A calculation of the depolarization ratio and the local fields for liquid nitrobenzene

Janssen, RHC; Theodorou, DN; Raptis, S; Papadopoulos, MG

dc.contributor.author	Janssen, RHC	en
dc.contributor.author	Theodorou, DN	en
dc.contributor.author	Raptis, S	en
dc.contributor.author	Papadopoulos, MG	en
dc.date.accessioned	2014-03-01T01:14:50Z
dc.date.available	2014-03-01T01:14:50Z
dc.date.issued	1999	en
dc.identifier.issn	0021-9606	en
dc.identifier.uri	https://dspace.lib.ntua.gr/xmlui/handle/123456789/13243
dc.relation.uri	http://www.scopus.com/inward/record.url?eid=2-s2.0-0000838007&partnerID=40&md5=cb3b38c52c2392dc501311f27f85398a	en
dc.subject.classification	Physics, Atomic, Molecular & Chemical	en
dc.subject.other	GAUSSIAN-TYPE BASIS	en
dc.subject.other	LIGHT-SCATTERING	en
dc.subject.other	ORGANIC-MOLECULES	en
dc.subject.other	ORBITAL METHODS	en
dc.subject.other	BASIS-SETS	en
dc.subject.other	DYNAMICS	en
dc.subject.other	FLUIDS	en
dc.subject.other	2ND	en
dc.title	Molecular simulation of static hyper-Rayleigh scattering: A calculation of the depolarization ratio and the local fields for liquid nitrobenzene	en
heal.type	journalArticle	en
heal.language	English	en
heal.publicationDate	1999	en
heal.abstract	Molecular dynamics (MD) simulation is used to assess the hyper-Rayleigh scattering (HRS) depolarization ratio of liquid nitrobenzene subject to vertically polarized light. In contrast to previous theoretical work, we have quantified both incoherent and coherent scattering arising from positional and orientational inhomogeneities in the molecular distribution. Although coherent scattering is shown to be much less important than in the case of Rayleigh scattering, it can not be neglected. Therefore, our analysis supports the current practice of working with dilute solutions (for which coherent contributions to HRS are truly negligible) to extract the first molecular hyperpolarizability from HRS measurements. In cases where experiments with pure liquids can not be circumvented, our analysis may be used to separate coherent and incoherent signals. Our work, which uses as input static "gas-phase" (hyper)polarizabilities obtained from ab initio calculations, also provides information on the orientations and magnitudes of the local electric fields experienced by the individual molecules in the liquid. For nitrobenzene it is found that the local fields are largely determined by specific dipolar alignment between neighboring pairs of molecules, with consequences on the HRS signal. (C) 1999 American Institute of Physics. [S0021-9606(99)51143-4].	en
heal.publisher	AMER INST PHYSICS	en
heal.journalName	Journal of Chemical Physics	en
dc.identifier.isi	ISI:000083685400035	en
dc.identifier.volume	111	en
dc.identifier.issue	21	en
dc.identifier.spage	9711	en
dc.identifier.epage	9719	en