FORMYL FLUORIDE PHOTODISSOCIATION - POTENTIAL-ENERGY SURFACE-FEATURES OF SINGLET HFCO

被引:50
作者
GODDARD, JD [1 ]
SCHAEFER, HF [1 ]
机构
[1] UNIV GEORGIA,CTR COMPUTAT QUANTUM CHEM,ATHENS,GA 30602
基金
美国国家卫生研究院; 美国国家科学基金会;
关键词
D O I
10.1063/1.458679
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 unimolecular dissociation of formyl fluoride to hydrogen fluoride and carbon monoxide and its unimolecular rearrangement to fluorohydroxymethylene have been examined theoretically. Methods ranged from double zeta plus polarization self-consistent-field to triple zeta plus double polarization coupled cluster singles and doubles. The coupled cluster method including single, double, and linearized triple excitations (CCSDT-1 ) was applied as well with the double zeta plus polarization basis. The present studies predict a barrier height of ∼47 kcal mol-1 to the molecular dissociation which is ∼11 kcal mol-1 lower than previous theoretical work and in reasonable agreement with experiments that indicate this barrier lies in the range 40 to 43 kcal mol-1. The existence of singlet trans- and cis-fluorohydroxymethylenes at ∼43 kcal mol-1. above formyl fluoride is further confirmed theoretically. The 1,2-hydrogen shift transition state connecting formyl fluoride to the trans-fluorohydroxymethylene lies at ∼77 kcal mol-1. The trans- and cis-fluorohydroxymethylenes are separated by an internal rotation barrier of ∼17 kcal mol-1. © 1990 American Institute of Physics.
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页码:4907 / 4915
页数:9
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