A PERTURBATIVE CORRECTION TO RESTRICTED OPEN-SHELL CONFIGURATION-INTERACTION WITH SINGLE SUBSTITUTIONS FOR EXCITED-STATES OF RADICALS

被引:160
作者
HEADGORDON, M [1 ]
MAURICE, D [1 ]
OUMI, M [1 ]
机构
[1] UNIV CALIF BERKELEY,LAWRENCE BERKELEY LAB,DIV CHEM SCI,BERKELEY,CA 94720
关键词
D O I
10.1016/0009-2614(95)01111-L
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
A perturbative correction, termed RCIS(D), to restricted open shell single excitation configuration interaction (ROCIS) is formulated and implemented for excited states of radicals. RCIS(D) gives spin-pure energies (but not wavefunctions), is size-consistent, and has computational complexity scaling with the fifth power of molecular size. All these properties are analogous to second order restricted Moller-Plesset theory for the ground state. Comparison of calculated vertical excitation energies against experiment for a diverse series of small radicals, BeH, BeF, CH, CH3, CN, CO+, NO and OH, suggests that RCIS(D) constitutes a useful improvement over ROCIS.
引用
收藏
页码:114 / 121
页数:8
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