ABINITIO STUDY OF STRUCTURE, STABILITY AND IONIZATION-POTENTIALS OF THE ANIONS PF6- AND P2F11-

被引：35

作者：

KOLMEL, C ^{[1
]}

PALM, G ^{[1
]}

AHLRICHS, R ^{[1
]}

BAR, M ^{[1
]}

BOLDYREV, AI ^{[1
]}

机构：

[1] ACAD SCI USSR, INST CHEM PHYS, MOSCOW 117334, USSR

来源：

CHEMICAL PHYSICS LETTERS | 1990年 / 173卷 / 2-3期

关键词：

D O I：

10.1016/0009-2614(90)80069-P

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：

Equilibrium geometries of PF5 (D3h), PF-6 (Oh) and P2F-11 (D4d and D4h) were determined on the SCF level employing extended basis sets. Total energies of anions and the corresponding neutral systems were calculated. The anions PF-6 and P2F-11 are stable with respect to dissociation into PF5+F- (92.6 kcal/mol) and PF-6+PF5 (4.0 kcal/mol), respectively, but the neutral systems PF6 and P2F11 are unstable towards loss of an F atom. The open-shell radicals PF6 and P2F11 exhibit a strong tendency for symmetry breaking, i.e. a localization of the "hole" on an F atom, which leads to computed vertical ionization potentials of 8.7 and 10.3 eV for PF-6 and P2F-11 on the ΔSCF level. CPF calculations for PF6 and PF-6 confirm the reliability of the ΔSCF description based on localized holes. © 1990.

引用

页码：151 / 156

页数：6

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