### Résumé

We have developed a method for analyzing the (hyper)polarizabilities of open-shell molecular systems. This method employs the (hyper)polarizability densities based on the natural orbitals and occupation numbers, which enables us to analyze the contributions of odd electrons having various open-shell (diradical) characters. Within broken-symmetry, i. e., spin-unrestricted, single-determinant molecular orbital and density functional theory approaches, we can also remove the spin contamination effects on these quantities through spin projection. To do that, an approximate spin projected method has been elaborated and applied to the analysis of the (hyper)polarizability of multi-radical systems. As examples, typical open-shell singlet systems, 1,3-dipoles and rectangular graphene nanoflakes, are examined.

langue | Anglais |
---|---|

Pages | 711-724 |

Nombre de pages | 14 |

journal | Theoretical Chemistry Accounts |

Volume | 130 |

Numéro | 4-6 |

Les DOIs | |

état | Publié - 1 déc. 2011 |

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*Theoretical Chemistry Accounts*,

*130*(4-6), 711-724. DOI: 10.1007/s00214-010-0871-y

}

*Theoretical Chemistry Accounts*, VOL 130, Numéro 4-6, p. 711-724. DOI: 10.1007/s00214-010-0871-y

**(Hyper)polarizability density analysis for open-shell molecular systems based on natural orbitals and occupation numbers.** / Nakano, Masayoshi; Fukui, Hitoshi; Minami, Takuya; Yoneda, Kyohei; Shigeta, Yasuteru; Kishi, Ryohei; Champagne, Benoît; Botek, Edith; Kubo, Takashi; Ohta, Koji; Kamada, Kenji.

Résultats de recherche: Recherche - Revue par des pairs › Article

TY - JOUR

T1 - (Hyper)polarizability density analysis for open-shell molecular systems based on natural orbitals and occupation numbers

AU - Nakano,Masayoshi

AU - Fukui,Hitoshi

AU - Minami,Takuya

AU - Yoneda,Kyohei

AU - Shigeta,Yasuteru

AU - Kishi,Ryohei

AU - Champagne,Benoît

AU - Botek,Edith

AU - Kubo,Takashi

AU - Ohta,Koji

AU - Kamada,Kenji

PY - 2011/12/1

Y1 - 2011/12/1

N2 - We have developed a method for analyzing the (hyper)polarizabilities of open-shell molecular systems. This method employs the (hyper)polarizability densities based on the natural orbitals and occupation numbers, which enables us to analyze the contributions of odd electrons having various open-shell (diradical) characters. Within broken-symmetry, i. e., spin-unrestricted, single-determinant molecular orbital and density functional theory approaches, we can also remove the spin contamination effects on these quantities through spin projection. To do that, an approximate spin projected method has been elaborated and applied to the analysis of the (hyper)polarizability of multi-radical systems. As examples, typical open-shell singlet systems, 1,3-dipoles and rectangular graphene nanoflakes, are examined.

AB - We have developed a method for analyzing the (hyper)polarizabilities of open-shell molecular systems. This method employs the (hyper)polarizability densities based on the natural orbitals and occupation numbers, which enables us to analyze the contributions of odd electrons having various open-shell (diradical) characters. Within broken-symmetry, i. e., spin-unrestricted, single-determinant molecular orbital and density functional theory approaches, we can also remove the spin contamination effects on these quantities through spin projection. To do that, an approximate spin projected method has been elaborated and applied to the analysis of the (hyper)polarizability of multi-radical systems. As examples, typical open-shell singlet systems, 1,3-dipoles and rectangular graphene nanoflakes, are examined.

KW - Broken-symmetry method

KW - Diradical

KW - Hyperpolarizability

KW - Natural orbital

KW - Open-shell molecule

KW - Spin projection

UR - http://www.scopus.com/inward/record.url?scp=81855163388&partnerID=8YFLogxK

U2 - 10.1007/s00214-010-0871-y

DO - 10.1007/s00214-010-0871-y

M3 - Article

VL - 130

SP - 711

EP - 724

JO - Theoretical Chemistry Accounts: Theory, Computation, and Modeling

T2 - Theoretical Chemistry Accounts: Theory, Computation, and Modeling

JF - Theoretical Chemistry Accounts: Theory, Computation, and Modeling

SN - 1432-881X

IS - 4-6

ER -