Theoretical study of the electronic ground state of iron(II) porphine. II

被引:73
作者
Choe, YK
Nakajima, T
Hirao, K
Lindh, R
机构
[1] Univ Tokyo, Grad Sch Engn, Dept Appl Chem, Bunkyo Ku, Tokyo 1138656, Japan
[2] Univ Lund, Ctr Chem, Dept Theoret Chem, S-22100 Lund, Sweden
关键词
D O I
10.1063/1.479687
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
Ten low-lying electronic states of Fe(II) porphine, (5)A(1g), E-5(g), B-5(2g), (3)A(2g), B-3(2g), E-3(g)(A), E-3(g)(B), (1)A(1g), B-1(2g), and E-1(g) states, are studied with multiconfigurational second-order perturbation (CASPT2) calculations with complete active space self-consistent field (CASSCF) reference functions with larger active space and basis sets. The enlargement of active space and basis sets has no influence on the conclusion of a previous multireference Moller-Plesset perturbation (MRMP) study. The present CASPT2 calculation concludes that the (5)A(1g) state is the ground state. A relativistic correction has been performed by the relativistic scheme of eliminating small components (RESC). For energetics, no significant contribution from the relativistic correction was found. The relative energies and orbital energies are not changed appreciably by the introduction of a relativistic correction. The present result does not agree with all the spectroscopic observations, but is consistent with a magnetic moment study. (C) 1999 American Institute of Physics. [S0021-9606(99)30233-6].
引用
收藏
页码:3837 / 3845
页数:9
相关论文
共 50 条
[1]   2ND-ORDER PERTURBATION-THEORY WITH A COMPLETE ACTIVE SPACE SELF-CONSISTENT FIELD REFERENCE FUNCTION [J].
ANDERSSON, K ;
MALMQVIST, PA ;
ROOS, BO .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (02) :1218-1226
[2]   2ND-ORDER PERTURBATION-THEORY WITH A CASSCF REFERENCE FUNCTION [J].
ANDERSSON, K ;
MALMQVIST, PA ;
ROOS, BO ;
SADLEJ, AJ ;
WOLINSKI, K .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (14) :5483-5488
[3]  
ANDERSSON K, 1997, MOLCAS VERSION 4 1
[4]  
BAUSCHLICHER CW, 1989, J CHEM PHYS, V91, P399
[5]   PARAMAGNETIC ANISOTROPY, AVERAGE MAGNETIC-SUSCEPTIBILITY, AND ELECTRONIC-STRUCTURE OF INTERMEDIATE-SPIN S = 1 (5,10,15,20-TETRAPHENYLPORPHYRIN)IRON(II) [J].
BOYD, PDW ;
BUCKINGHAM, DA ;
MCMEEKING, RF ;
MITRA, S .
INORGANIC CHEMISTRY, 1979, 18 (12) :3585-3591
[6]  
Choe Y.-K., UNPUB
[7]   Theoretical study of the electronic ground state of iron(II) porphine [J].
Choe, YK ;
Hashimoto, T ;
Nakano, H ;
Hirao, K .
CHEMICAL PHYSICS LETTERS, 1998, 295 (04) :380-388
[8]   SYNTHESIS, STEREOCHEMISTRY, AND STRUCTURE-RELATED PROPERTIES OF ALPHA, BETA, GAMMA, "DELTA-TETRAPHENYLPORPHINATOIRON(II) [J].
COLLMAN, JP ;
HOARD, JL ;
KIM, N ;
LANG, G ;
REED, CA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (10) :2676-2681
[9]   ABINITIO CALCULATIONS OF METALLOPORPHYRINS [J].
DEDIEU, A ;
ROHMER, MM ;
VEILLARD, A .
ADVANCES IN QUANTUM CHEMISTRY, 1982, 16 :43-95
[10]   DENSITY FUNCTIONAL-STUDY OF IRON(II)-PORPHINE [J].
DELLEY, B .
PHYSICA B-CONDENSED MATTER, 1991, 172 (1-2) :185-193