Low-lying spin states of iron(II) porphine

被引：118

作者：

Kozlowski, PM

Spiro, TG ^{[1
]}

Bérces, A

Zgierski, MZ

机构：

[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

[2] Natl Res Council Canada, Steacie Inst Mol Sci, Ottawa, ON K1A 0R6, Canada

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 1998年 / 102卷 / 14期

关键词：

D O I：

10.1021/jp973346d

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：

Geometries and force-fields of the low-lying spin states of iron(II) porphine are calculated with nonlocal density functional methods. The ground state is identified as the (3)A(2g), state. It is shown that the Fe atom is in the porphine plane for all spin states, but that the high-spin state potential surface intersects the triplet-state potential surfaces along the doming-mode coordinate when the iron atom is displaced about 0.4 Angstrom from the NNNN plane. This intersection is the result of an electron occupying the antibonding d(x2-y2) orbital in the quintet states. The doming mode of the porphine is predicted to be at 71 cm(-1), close to the 75 cm(-1) frequency determined from coherent reaction dynamics in myoglobin.

引用

页码：2603 / 2608

页数：6

共 71 条

[1] ELECTRON CORRELATION IN TETRAPYRROLES - AB-INITIO CALCULATIONS ON PORPHYRIN AND THE TAUTOMERS OF CHLORIN [J].