SCF PERTURBATION-THEORY FOR UNIMOLECULAR REACTIONS

被引：3

作者：

BACHLER, V ^{[1
]}

OLBRICH, G ^{[1
]}

POLANSKY, OE ^{[1
]}

PAN, YK ^{[1
]}

机构：

[1] BOSTON COLL,DEPT CHEM,CHESTNUT HILL,MA 02167

来源：

THEORETICA CHIMICA ACTA | 1979年 / 50卷 / 04期

关键词：

potential energy surfaces of ∼; SCF perturbation theory; Unimolecular reactions;

D O I：

10.1007/BF00551340

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 CNDO/2 SCF perturbation theory is presented for interpreting the form of CNDO/2 potential energy surfaces of unimolecular reactions. The analysis is performed by calculating the energy change Δ E arising from a distortion of the molecular geometry along the reaction coordinate. Δ E is decomposed into different perturbational contributions which are appropriate for an interpretation of the perturbation energy Δ E. Moreover, Δ E is resolved into energy parts arising from a single occupied orbital and contributions due to pairwise orbital interactions. In this way one evaluates numerically how the form of the occupied and unoccupied orbitals determines the magnitude of Δ E. If the distortion occurs along a definite symmetry coordinate, group-theoretical arguments can be applied to discuss the magnitude of characteristic components of the perturbation energy. The SCF perturbation theory is used to analyze the isomerization of ethylene, cis-2-butene and cis-2-butenenitrile. © 1979 Springer-Verlag.

引用

页码：327 / 342

页数：16

共 27 条

[11]

Hirschfelder J.O., 1964, ADV QUANTUM CHEM, V1, P255, DOI [10.1016/s0065-3276(08)60381-0, DOI 10.1016/S0065-3276(08)60381-0]

[12] ORBITAL CORRESPONDENCE ANALYSIS IN MAXIMUM SYMMETRY - FORMULATION AND CONCEPTUAL FRAMEWORK [J].

KATRIEL, J ;

HALEVI, EA .

THEORETICA CHIMICA ACTA, 1975, 40 (01) :1-15

[13] INTEGRAL HELLMANN-FEYNMAN THEOREM [J].

KIM, HJ ;

PARR, RG .

JOURNAL OF CHEMICAL PHYSICS, 1964, 41 (09) :2892-+

[14]

KLOPMAN G, 1974, CHEM REACTIVITY REAC, P54

[15]

KLOPMAN G, 1974, CHEM REACTIVITY REAC, P10

[16]

OSHEA SF, 1973, CHEM PHYS LETT, V22, P447, DOI 10.1016/0009-2614(73)87004-6

[17] THEOREM GOVERNING CHANGES IN MOLECULAR CONFORMATION [J].

PARR, RG .

JOURNAL OF CHEMICAL PHYSICS, 1964, 40 (12) :3726-&

[18] SYMMETRY RULES FOR CHEMICAL REACTIONS [J].

PEARSON, RG .

ACCOUNTS OF CHEMICAL RESEARCH, 1971, 4 (04) :152-&

[19]

PEARSON RG, 1976, SYMMETRY RULES CHEM, P13

[20]

POPLE JA, 1970, APPROXIMATE MOLECULA, P77

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