THEORETICAL DETERMINATION OF THE ELECTRONIC-SPECTRUM OF FREE-BASE PORPHIN

被引：94

作者：

MERCHAN, M ^{[1
]}

ORTI, E ^{[1
]}

ROOS, BO ^{[1
]}

机构：

[1] CHEM CTR LUND,DEPT THEORET CHEM,S-22100 LUND,SWEDEN

来源：

CHEMICAL PHYSICS LETTERS | 1994年 / 226卷 / 1-2期

关键词：

D O I：

10.1016/0009-2614(94)00681-4

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：

The main features of the electronic spectrum of free base porphin are determined by means of multiconfigurational second-order perturbation (CASPT2) theory. The calculations comprise the optically allowed singlet states associated to the Q and B bands and the corresponding triplet states. The computed excitation energies deviate from the available experimental data by less than 0.3 eV in all the cases where a comparison is possible. It is found that both sigma- and pi-electron correlation contributions have to be taken into account in order to give a balanced description of the ''cited states. A limited theoretical treatment, based on only pi-electron correlation or only partially including the correlation of the sigma electrons, is not sufficient.

引用

页码：27 / 36

页数：10

共 43 条

[1] GENERAL CONTRACTION OF GAUSSIAN-BASIS SETS .1. ATOMIC NATURAL ORBITALS FOR 1ST-ROW AND 2ND-ROW ATOMS [J].