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First hyperpolarizabilities of 1,3,5‐tricyano‐2,4,6‐tris(styryl)benzene derivatives: ab initio studies and Hammett correlation
Author(s) -
Park Gyoosoon,
Cho Bong Rae
Publication year - 2005
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.809
Subject(s) - chemistry , ab initio , delocalized electron , computational chemistry , ab initio quantum chemistry methods , benzene , oxyanion , tris , molecule , polarizability , organic chemistry , catalysis , biochemistry
Abstract First hyperpolarizabilities (β) of the 1,3,5‐tricyano‐2,4,6‐tris(styryl)benzene derivatives were studied by an ab initio method (HF/6–31G). The β values of these molecules increase with increase in donor strength, reaching a maximum value of 262 × 10 −30 esu with an oxyanion as the donor. Also, the electronic charge is more delocalized, and the HOMO–LUMO energy gap (Δ E ) and the bond length alternation (BLA) decrease with the same variation of the donor. Noteworthy is the excellent linear relationship between β and 1/Δ E 2 and σ gas + . These results may serve as a useful guideline for the design of two‐dimensional octupoles with large first hyperpolarizabilities. Copyright © 2004 John Wiley & Sons, Ltd.