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

被引：132

作者：

Nakano, Masayoshi ^{[1
]}

Fukui, Hitoshi ^{[1
]}

Minami, Takuya ^{[1
]}

Yoneda, Kyohei ^{[1
]}

Shigeta, Yasuteru ^{[1
]}

Kishi, Ryohei ^{[1
]}

Champagne, Benoit ^{[2
]}

Botek, Edith ^{[2
]}

Kubo, Takashi ^{[3
]}

Ohta, Koji ^{[4
]}

Kamada, Kenji ^{[4
]}

机构：

[1] Osaka Univ, Grad Sch Engn Sci, Dept Mat Engn Sci, Toyonaka, Osaka 5608531, Japan

[2] Fac Univ Notre Dame Paix FUNDP, Lab Chim Theor, B-5000 Namur, Belgium

[3] Osaka Univ, Grad Sch Sci, Dept Chem, Toyonaka, Osaka 5600043, Japan

[4] Natl Inst Adv Ind Sci & Technol, Res Inst Ubiquitous Energy Devices, Ikeda, Osaka 5638577, Japan

来源：

THEORETICAL CHEMISTRY ACCOUNTS | 2011年 / 130卷 / 4-6期

基金：

日本学术振兴会;

关键词：

Hyperpolarizability; Open-shell molecule; Diradical; Natural orbital; Broken-symmetry method; Spin projection; 2ND HYPERPOLARIZABILITIES GAMMA; NUMERICAL LIOUVILLE APPROACH; DIRADICAL CHARACTER; FUNCTIONAL THEORY; GROUND-STATE; CONFIGURATION-INTERACTION; ELECTRONIC-STRUCTURES; GRAPHENE NANOFLAKES; AB-INITIO; SPIN;

D O I：

10.1007/s00214-010-0871-y

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：711 / 724

页数：14

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