Theoretical investigation on the second hyperpolarizabilities of open-shell singlet systems by spin-unrestricted density functional theory with long-range correction

Range separating parameter dependence

Sean Bonness, Hitoshi Fukui, Kyohei Yoneda, Ryohei Kishi, Benoît Champagne, Edith Botek, Masayoshi Nakano

Research output: Contribution to journalArticle

Abstract

The long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method has been used to determine the second hyperpolarizabilities (γ) of open-shell singlet π-conjugated diradical compounds, i.e., p-quinodimethane, 1,4-bis-(imidazole-2-ylidene)-cyclohexa-2,5-diene, pentalene and s-indacene. Analysis of the dependence of γ on the range separating parameter (μ) was carried out along with comparison to spin-unrestricted coupled cluster singles, doubles and perturbative triples [UCCSD(T)] calculations. Our investigation shows that the LC-UBLYP method with μ = 0.3-0.5 is adequate for calculating γ values for conjugated diradical systems and does not suffer from the catastrophic behavior found in conventional exchange-correlation functionals.

Original languageEnglish
Pages (from-to)195-199
Number of pages5
JournalChemical Physics Letters
Volume493
Issue number1-3
DOIs
Publication statusPublished - 17 Jun 2010

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Density functional theory
density functional theory
dienes
imidazoles
functionals
imidazole

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title = "Theoretical investigation on the second hyperpolarizabilities of open-shell singlet systems by spin-unrestricted density functional theory with long-range correction: Range separating parameter dependence",
abstract = "The long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method has been used to determine the second hyperpolarizabilities (γ) of open-shell singlet π-conjugated diradical compounds, i.e., p-quinodimethane, 1,4-bis-(imidazole-2-ylidene)-cyclohexa-2,5-diene, pentalene and s-indacene. Analysis of the dependence of γ on the range separating parameter (μ) was carried out along with comparison to spin-unrestricted coupled cluster singles, doubles and perturbative triples [UCCSD(T)] calculations. Our investigation shows that the LC-UBLYP method with μ = 0.3-0.5 is adequate for calculating γ values for conjugated diradical systems and does not suffer from the catastrophic behavior found in conventional exchange-correlation functionals.",
author = "Sean Bonness and Hitoshi Fukui and Kyohei Yoneda and Ryohei Kishi and Beno{\^i}t Champagne and Edith Botek and Masayoshi Nakano",
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TY - JOUR

T1 - Theoretical investigation on the second hyperpolarizabilities of open-shell singlet systems by spin-unrestricted density functional theory with long-range correction

T2 - Range separating parameter dependence

AU - Bonness, Sean

AU - Fukui, Hitoshi

AU - Yoneda, Kyohei

AU - Kishi, Ryohei

AU - Champagne, Benoît

AU - Botek, Edith

AU - Nakano, Masayoshi

PY - 2010/6/17

Y1 - 2010/6/17

N2 - The long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method has been used to determine the second hyperpolarizabilities (γ) of open-shell singlet π-conjugated diradical compounds, i.e., p-quinodimethane, 1,4-bis-(imidazole-2-ylidene)-cyclohexa-2,5-diene, pentalene and s-indacene. Analysis of the dependence of γ on the range separating parameter (μ) was carried out along with comparison to spin-unrestricted coupled cluster singles, doubles and perturbative triples [UCCSD(T)] calculations. Our investigation shows that the LC-UBLYP method with μ = 0.3-0.5 is adequate for calculating γ values for conjugated diradical systems and does not suffer from the catastrophic behavior found in conventional exchange-correlation functionals.

AB - The long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method has been used to determine the second hyperpolarizabilities (γ) of open-shell singlet π-conjugated diradical compounds, i.e., p-quinodimethane, 1,4-bis-(imidazole-2-ylidene)-cyclohexa-2,5-diene, pentalene and s-indacene. Analysis of the dependence of γ on the range separating parameter (μ) was carried out along with comparison to spin-unrestricted coupled cluster singles, doubles and perturbative triples [UCCSD(T)] calculations. Our investigation shows that the LC-UBLYP method with μ = 0.3-0.5 is adequate for calculating γ values for conjugated diradical systems and does not suffer from the catastrophic behavior found in conventional exchange-correlation functionals.

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JF - Chemical Physics Letters

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