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B3LYP study of the dipole moment and the static dipole (hyper)polarizabilities of para ‐nitroaniline in gas phase
Author(s) -
Soscún Humberto,
Castellano Olga,
Bermúdez Yaneth,
Toro Carlos,
Cubillán Nestor,
Hinchliffe Alan,
Phu Xuan Nguyen
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20821
Subject(s) - hyperpolarizability , dipole , moment (physics) , basis set , chemistry , polarizability , atomic physics , density functional theory , molecular physics , molecule , physics , computational chemistry , quantum mechanics
The dipole moment μ and the electronic (hyper)polarizabilities α, β, and γ tensors of paranitroaniline (PNA) has been calculated in the static regime with the B3LYP hybrid approach of the density functional theory (DFT) formalism and by using the numerical triple finite field method of Kamada et al. The calculations were performed with planar C 2 v optimized geometry and the standard 6‐31+G( d,p ), d optimized 6‐31+G( d *, p ) and the specialized Sadlej basis sets. The B3LYP/6‐31+G( d *, p ) results of μ, α, β, and γ are comparable to those of the literature. In particular, the static average γ of PNA is comparable to MP2 calculations and is able to reproduce 54% of the experimental static value from Z‐scan experiments recently reported. The origin of the differences between the experimental and theoretical values is discussed. The findings emphasize the use of the DFT methodology in conjunction with optimized basis sets for a reasonable estimated of the electron correlation in static second hyperpolarizability calculations of push–pull conjugated molecules. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006