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First hyperpolarizabilities of triazine derivatives. Ab initio studies and Hammett correlation
Author(s) -
Park Gyoosoon,
Cho Bong Rae
Publication year - 2004
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.709
Subject(s) - chemistry , substituent , delocalized electron , ab initio , computational chemistry , chromophore , molecule , triazine , ab initio quantum chemistry methods , stereochemistry , photochemistry , organic chemistry
First hyperpolarizabilities (β) of triazine derivatives were studied by the ab initio method (HF/6–31G). The β values of these molecules increase with a stronger donor and as the conjugation length increases, probably because the electronic charge becomes more delocalized and the HOMO–LUMO energy gap (Δ E ) and the bond length alternation (BLA) decrease with variation of the chromophore structure. Also, the susceptibility of β to the donor strength is found to be larger for a more elongated substrate. Noteworthy is the excellent linear relationship between β and BLA and also the gas‐phase substituent constants (σ + gas ). This result may serve as a useful guideline for the design of two‐dimensional octupoles with large first hyperpolarizabilities. Copyright © 2004 John Wiley & Sons, Ltd.