Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems

Ryohei Kishi, Sean Bonness, Kyohei Yoneda, Hideaki Takahashi, Masayoshi Nakano, Edith Botek, Benoit Champagne, Takashi Kubo, Kenji Kamada, Koji Ohta, Takao Tsuneda

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Within the spin-unrestricted density functional theory (DFT) the long-range correction (LC) scheme combined with the Becke-Lee-Yang-Parr exchange-correlation functional, referred to as LC-UBLYP method, has been applied to the calculation of the second hyperpolarizability (γ) of open-shell singlet diradical systems of increasing complexity and has demonstrated good performance: (i) for the simplest H2 dissociation model, the γ values calculated by the LC-UBLYP method significantly overshoot the full configuration interaction result but reproduce qualitatively the evolution of γ as a function of the diradical character, (ii) for small singlet diradical 1,3-dipole systems, the diradical character dependence of γ determined by the UCCSD and UCCSD(T) reference methods is reproduced semiquantitatively by the LC-UBLYP method except in the small diradical character region, where the spin-unrestricted solutions coincide with spin-restricted solutions, (iii) the LC-UBLYP method also closely reproduces the UCCSD(T) results on the diradical character dependence of γ of the p -quinodimethane model system, particularly in the intermediate and large diradical character regions, whereas it shows an abrupt change for a diradical character (y) close to 0.2 originating from the triplet instability, (iv) the reliability of LC-UBLYP to reproduce reference coupled cluster results on open-shell singlet systems with intermediate and large diradical characters has also been substantiated in the case of γ of 1,4-bis-(imidazol-2-ylidene)- cyclohexa-2,5-diene (BI2Y), then (v), for real systems built from a pair of phenalenyl radicals separated by a conjugated linker, the LC-UBLYP results have been found to closely match the UBHandHLYP values-which, for small systems are in good agreement with those obtained using correlated molecular orbital methods-whereas the UB3LYP results can be much different. These results are not only important from the viewpoint of an efficient determination of the nonlinear optical properties of open-shell singlet systems, but also from the viewpoint of defining new challenges for elaborating improved exchange-correlation functionals.

langue originaleAnglais
Numéro d'article094107
journalThe journal of chemical physics
Volume132
Numéro de publication9
Les DOIs
étatPublié - 19 mars 2010

Empreinte digitale

Density functional theory
density functional theory
Molecular orbitals
Optical properties
dienes
imidazoles
functionals
configuration interaction
molecular orbitals
dissociation
dipoles
optical properties

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Kishi, Ryohei ; Bonness, Sean ; Yoneda, Kyohei ; Takahashi, Hideaki ; Nakano, Masayoshi ; Botek, Edith ; Champagne, Benoit ; Kubo, Takashi ; Kamada, Kenji ; Ohta, Koji ; Tsuneda, Takao. / Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems. Dans: The journal of chemical physics. 2010 ; Vol 132, Numéro 9.
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title = "Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems",
abstract = "Within the spin-unrestricted density functional theory (DFT) the long-range correction (LC) scheme combined with the Becke-Lee-Yang-Parr exchange-correlation functional, referred to as LC-UBLYP method, has been applied to the calculation of the second hyperpolarizability (γ) of open-shell singlet diradical systems of increasing complexity and has demonstrated good performance: (i) for the simplest H2 dissociation model, the γ values calculated by the LC-UBLYP method significantly overshoot the full configuration interaction result but reproduce qualitatively the evolution of γ as a function of the diradical character, (ii) for small singlet diradical 1,3-dipole systems, the diradical character dependence of γ determined by the UCCSD and UCCSD(T) reference methods is reproduced semiquantitatively by the LC-UBLYP method except in the small diradical character region, where the spin-unrestricted solutions coincide with spin-restricted solutions, (iii) the LC-UBLYP method also closely reproduces the UCCSD(T) results on the diradical character dependence of γ of the p -quinodimethane model system, particularly in the intermediate and large diradical character regions, whereas it shows an abrupt change for a diradical character (y) close to 0.2 originating from the triplet instability, (iv) the reliability of LC-UBLYP to reproduce reference coupled cluster results on open-shell singlet systems with intermediate and large diradical characters has also been substantiated in the case of γ of 1,4-bis-(imidazol-2-ylidene)- cyclohexa-2,5-diene (BI2Y), then (v), for real systems built from a pair of phenalenyl radicals separated by a conjugated linker, the LC-UBLYP results have been found to closely match the UBHandHLYP values-which, for small systems are in good agreement with those obtained using correlated molecular orbital methods-whereas the UB3LYP results can be much different. These results are not only important from the viewpoint of an efficient determination of the nonlinear optical properties of open-shell singlet systems, but also from the viewpoint of defining new challenges for elaborating improved exchange-correlation functionals.",
author = "Ryohei Kishi and Sean Bonness and Kyohei Yoneda and Hideaki Takahashi and Masayoshi Nakano and Edith Botek and Benoit Champagne and Takashi Kubo and Kenji Kamada and Koji Ohta and Takao Tsuneda",
year = "2010",
month = "3",
day = "19",
doi = "10.1063/1.3332707",
language = "English",
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journal = "The journal of chemical physics",
issn = "0021-9606",
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Kishi, R, Bonness, S, Yoneda, K, Takahashi, H, Nakano, M, Botek, E, Champagne, B, Kubo, T, Kamada, K, Ohta, K & Tsuneda, T 2010, 'Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems', The journal of chemical physics, VOL. 132, Numéro 9, 094107. https://doi.org/10.1063/1.3332707

Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems. / Kishi, Ryohei; Bonness, Sean; Yoneda, Kyohei; Takahashi, Hideaki; Nakano, Masayoshi; Botek, Edith; Champagne, Benoit; Kubo, Takashi; Kamada, Kenji; Ohta, Koji; Tsuneda, Takao.

Dans: The journal of chemical physics, Vol 132, Numéro 9, 094107, 19.03.2010.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems

AU - Kishi, Ryohei

AU - Bonness, Sean

AU - Yoneda, Kyohei

AU - Takahashi, Hideaki

AU - Nakano, Masayoshi

AU - Botek, Edith

AU - Champagne, Benoit

AU - Kubo, Takashi

AU - Kamada, Kenji

AU - Ohta, Koji

AU - Tsuneda, Takao

PY - 2010/3/19

Y1 - 2010/3/19

N2 - Within the spin-unrestricted density functional theory (DFT) the long-range correction (LC) scheme combined with the Becke-Lee-Yang-Parr exchange-correlation functional, referred to as LC-UBLYP method, has been applied to the calculation of the second hyperpolarizability (γ) of open-shell singlet diradical systems of increasing complexity and has demonstrated good performance: (i) for the simplest H2 dissociation model, the γ values calculated by the LC-UBLYP method significantly overshoot the full configuration interaction result but reproduce qualitatively the evolution of γ as a function of the diradical character, (ii) for small singlet diradical 1,3-dipole systems, the diradical character dependence of γ determined by the UCCSD and UCCSD(T) reference methods is reproduced semiquantitatively by the LC-UBLYP method except in the small diradical character region, where the spin-unrestricted solutions coincide with spin-restricted solutions, (iii) the LC-UBLYP method also closely reproduces the UCCSD(T) results on the diradical character dependence of γ of the p -quinodimethane model system, particularly in the intermediate and large diradical character regions, whereas it shows an abrupt change for a diradical character (y) close to 0.2 originating from the triplet instability, (iv) the reliability of LC-UBLYP to reproduce reference coupled cluster results on open-shell singlet systems with intermediate and large diradical characters has also been substantiated in the case of γ of 1,4-bis-(imidazol-2-ylidene)- cyclohexa-2,5-diene (BI2Y), then (v), for real systems built from a pair of phenalenyl radicals separated by a conjugated linker, the LC-UBLYP results have been found to closely match the UBHandHLYP values-which, for small systems are in good agreement with those obtained using correlated molecular orbital methods-whereas the UB3LYP results can be much different. These results are not only important from the viewpoint of an efficient determination of the nonlinear optical properties of open-shell singlet systems, but also from the viewpoint of defining new challenges for elaborating improved exchange-correlation functionals.

AB - Within the spin-unrestricted density functional theory (DFT) the long-range correction (LC) scheme combined with the Becke-Lee-Yang-Parr exchange-correlation functional, referred to as LC-UBLYP method, has been applied to the calculation of the second hyperpolarizability (γ) of open-shell singlet diradical systems of increasing complexity and has demonstrated good performance: (i) for the simplest H2 dissociation model, the γ values calculated by the LC-UBLYP method significantly overshoot the full configuration interaction result but reproduce qualitatively the evolution of γ as a function of the diradical character, (ii) for small singlet diradical 1,3-dipole systems, the diradical character dependence of γ determined by the UCCSD and UCCSD(T) reference methods is reproduced semiquantitatively by the LC-UBLYP method except in the small diradical character region, where the spin-unrestricted solutions coincide with spin-restricted solutions, (iii) the LC-UBLYP method also closely reproduces the UCCSD(T) results on the diradical character dependence of γ of the p -quinodimethane model system, particularly in the intermediate and large diradical character regions, whereas it shows an abrupt change for a diradical character (y) close to 0.2 originating from the triplet instability, (iv) the reliability of LC-UBLYP to reproduce reference coupled cluster results on open-shell singlet systems with intermediate and large diradical characters has also been substantiated in the case of γ of 1,4-bis-(imidazol-2-ylidene)- cyclohexa-2,5-diene (BI2Y), then (v), for real systems built from a pair of phenalenyl radicals separated by a conjugated linker, the LC-UBLYP results have been found to closely match the UBHandHLYP values-which, for small systems are in good agreement with those obtained using correlated molecular orbital methods-whereas the UB3LYP results can be much different. These results are not only important from the viewpoint of an efficient determination of the nonlinear optical properties of open-shell singlet systems, but also from the viewpoint of defining new challenges for elaborating improved exchange-correlation functionals.

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U2 - 10.1063/1.3332707

DO - 10.1063/1.3332707

M3 - Article

VL - 132

JO - The journal of chemical physics

JF - The journal of chemical physics

SN - 0021-9606

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M1 - 094107

ER -