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Ab Initio Study of the ClO NH2Reaction:  Prediction of the Total Rate Constant and Product Branching Ratios.

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Title: Ab Initio Study of the ClO NH2Reaction:  Prediction of the Total Rate Constant and Product Branching Ratios.
Authors: R. S. Zhu1, M. C. Lin1
Source: Journal of Physical Chemistry A. May2007, Vol. 111 Issue 19, p3977-3983. 7p.
Subjects: Physical & theoretical chemistry, Science, Chemistry, Physical sciences
Abstract: The mechanism for ClO NH2has been investigated by ab initio molecular orbital and transition-state theory calculations. The species involved have been optimized at the B3LYP/6-311G(3df,2p) level and their energies have been refined by single-point calculations with the modified Gaussian-2 method, G2M(CC2). Ten stable isomers have been located and a detailed potential energy diagram is provided. The rate constants and branching ratios for the low-lying energy channel products including HCl HNO, Cl NH2O, and HOCl 3NH (X3-) are calculated. The result shows that formation of HCl HNO is dominant below 1000 K; over 1000 K, Cl NH2O products become dominant. However, the formation of HOCl 3NH (X3-) is unimportant below 1500 K. The pressure-independent individual and total rate constants can be expressed as k1(HCl HNO) 4.7 × 10-8(T-1.08) exp(-129/T), k2(Cl NH2O) 1.7 × 10-9(T-0.62) exp(-24/T), k3(HOCl NH) 4.8 × 10-29(T5.11) exp(-1035/T), and ktotal5.0 × 10-9(T-0.67) exp(-1.2/T), respectively, with units of cm3molecule-1s-1, in the temperature range of 200−2500 K. [ABSTRACT FROM AUTHOR]
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Abstract:The mechanism for ClO NH2has been investigated by ab initio molecular orbital and transition-state theory calculations. The species involved have been optimized at the B3LYP/6-311G(3df,2p) level and their energies have been refined by single-point calculations with the modified Gaussian-2 method, G2M(CC2). Ten stable isomers have been located and a detailed potential energy diagram is provided. The rate constants and branching ratios for the low-lying energy channel products including HCl HNO, Cl NH2O, and HOCl 3NH (X3-) are calculated. The result shows that formation of HCl HNO is dominant below 1000 K; over 1000 K, Cl NH2O products become dominant. However, the formation of HOCl 3NH (X3-) is unimportant below 1500 K. The pressure-independent individual and total rate constants can be expressed as k1(HCl HNO) 4.7 × 10-8(T-1.08) exp(-129/T), k2(Cl NH2O) 1.7 × 10-9(T-0.62) exp(-24/T), k3(HOCl NH) 4.8 × 10-29(T5.11) exp(-1035/T), and ktotal5.0 × 10-9(T-0.67) exp(-1.2/T), respectively, with units of cm3molecule-1s-1, in the temperature range of 200−2500 K. [ABSTRACT FROM AUTHOR]
ISSN:10895639
DOI:10.1021/jp067178d