An ab Initio and Semiempirical Study of the First- and Third-Order Polarizabilities in Benzene and Thiophene Derivatives: Electron Correlation Effects

Autor:	J. L. Bredas, C. Adant, Michel Dupuis
Rok vydání:	1997
Předmět:	Electronic correlation Chemistry Ab initio Configuration interaction Molecular physics chemistry.chemical_compound Polarizability Computational chemistry Physics::Atomic and Molecular Clusters Thiophene Molecule Physical and Theoretical Chemistry Basis set Excitation
Zdroj:	The Journal of Physical Chemistry A. 101:3025-3031
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp9630129
Popis:	The static first- and third-order polarizabilities of several benzene and thiophene derivatives are evaluated at the ab initio level via an efficacious general finite field approach. The impact of electron correlation is explored by calculating the molecular polarizabilities at the Moller−Plesset second-order perturbation (MP2) theory level using an extended basis set. Further, we examine the influence of molecular architecture on the nonlinear optical response, in particular the switch from an arylethenyl type of structure to a quinoid structure. Finally, we apply the correction vector method combined with the intermediate neglect of differential overlap−single and double excitation configuration interaction (INDO-SDCI) technique to evaluate the optical nonlinearities at the semiempirical level. The reliability of this procedure is established by comparison with the corresponding high-level ab initio polarizability values. The results clearly show the sensitive dependence of the nonlinear optical propert...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::9df41785db044f4ef0ee5f4bdc3110c9 https://doi.org/10.1021/jp9630129 Zobrazit plný text záznamu