Strong electron correlation effects on first- And second-order hyperpolarizabilities in zwitterionic σ-conjugated systems: Its dependence on substituents, conformations, spacer size, and basis sets

Yuuichi Orimoto, Yuriko Aoki

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13 Citations (Scopus)

Abstract

Nonlinear optical properties of zwitterionic σ-conjugated systems were theoretically investigated with relation to the electron correlation effects at the ab initio molecular orbital level. We examined the strong electron correlation effects on the first- and second-order hyperpolarizabilities in the specific systems with effective "π-σ-π" and (or) "π-σ-n" interactions. The electron correlation effects on the hyperpolarizabilities strongly depend on the type of substituents, conformations, spacer size, and basis sets. It was found that the Hartree-Fock level calculations qualitatively predict the behavior of the hyperpolarizabilities after considering the correlation effects. Through-space/-bond interaction analysis quantitatively revealed that the electron correlation effects on the hyperpolarizabilities were induced mainly by the σ-conjugations on the spacer unit in the zwitterionic σ-systems.

Original languageEnglish
Pages (from-to)8241-8249
Number of pages9
JournalJournal of Physical Chemistry A
Volume111
Issue number33
DOIs
Publication statusPublished - Aug 23 2007

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Electron correlations
spacers
Conformations
electrons
Molecular orbitals
conjugation
Optical properties
molecular orbitals
interactions
optical properties

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Nonlinear optical properties of zwitterionic σ-conjugated systems were theoretically investigated with relation to the electron correlation effects at the ab initio molecular orbital level. We examined the strong electron correlation effects on the first- and second-order hyperpolarizabilities in the specific systems with effective {"}π-σ-π{"} and (or) {"}π-σ-n{"} interactions. The electron correlation effects on the hyperpolarizabilities strongly depend on the type of substituents, conformations, spacer size, and basis sets. It was found that the Hartree-Fock level calculations qualitatively predict the behavior of the hyperpolarizabilities after considering the correlation effects. Through-space/-bond interaction analysis quantitatively revealed that the electron correlation effects on the hyperpolarizabilities were induced mainly by the σ-conjugations on the spacer unit in the zwitterionic σ-systems.",
author = "Yuuichi Orimoto and Yuriko Aoki",
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TY - JOUR

T1 - Strong electron correlation effects on first- And second-order hyperpolarizabilities in zwitterionic σ-conjugated systems

T2 - Its dependence on substituents, conformations, spacer size, and basis sets

AU - Orimoto, Yuuichi

AU - Aoki, Yuriko

PY - 2007/8/23

Y1 - 2007/8/23

N2 - Nonlinear optical properties of zwitterionic σ-conjugated systems were theoretically investigated with relation to the electron correlation effects at the ab initio molecular orbital level. We examined the strong electron correlation effects on the first- and second-order hyperpolarizabilities in the specific systems with effective "π-σ-π" and (or) "π-σ-n" interactions. The electron correlation effects on the hyperpolarizabilities strongly depend on the type of substituents, conformations, spacer size, and basis sets. It was found that the Hartree-Fock level calculations qualitatively predict the behavior of the hyperpolarizabilities after considering the correlation effects. Through-space/-bond interaction analysis quantitatively revealed that the electron correlation effects on the hyperpolarizabilities were induced mainly by the σ-conjugations on the spacer unit in the zwitterionic σ-systems.

AB - Nonlinear optical properties of zwitterionic σ-conjugated systems were theoretically investigated with relation to the electron correlation effects at the ab initio molecular orbital level. We examined the strong electron correlation effects on the first- and second-order hyperpolarizabilities in the specific systems with effective "π-σ-π" and (or) "π-σ-n" interactions. The electron correlation effects on the hyperpolarizabilities strongly depend on the type of substituents, conformations, spacer size, and basis sets. It was found that the Hartree-Fock level calculations qualitatively predict the behavior of the hyperpolarizabilities after considering the correlation effects. Through-space/-bond interaction analysis quantitatively revealed that the electron correlation effects on the hyperpolarizabilities were induced mainly by the σ-conjugations on the spacer unit in the zwitterionic σ-systems.

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