Direct Dynamics Studies on the Isomerization Reaction H3PO→H2POH

Abstract

Abstract: The isomerization reaction of H₃PO(1)H₂POH(trans)(2)H₂POH(cis) was studied by using the direct ab initio dynamic method. The optimized geometries and frequencies were calculated at the QCISD/6-311C⁺⁺G(d,p) level of theory for the reactant, products, and transition states as well as 18 selected points along the minimum energy pathway. In order to obtain more reliable energies, the single-point calculations were carried out at the QCISD(T)/6-311C⁺⁺G(2df,2pd) level of theory. The barrier of reaction(1), in which the hydrogen atom transfers from phosphor atom to oxygen atom, is more higher than that of reaction(2), the former is 250.0 kJ/mol and the latter is 12.3 kJ/mol. Therefore, reaction(1) is the rate controlling step of the isomerization reaction. The rate constants of reaction(1) were evaluated in the temperature range of 200-2000 K by the classical transition state theory, the classical transition state theory with Eckart tunneling model, the canonical variational transition state theory, and canonical variational transition state theory incorporating small-curvature tunneling correction, respectively. The fitted three-parameter expression from the CVT/SCT and TST/Eckart in the temperature range of 200-2000 K is k_CVT/SCT=2.747×10^-68 T^24.01exp(-1.0094×10⁴/T)s^-1 and k_TST/Eckart=1.423×10^-69 T^24.46exp(-1.0182×10⁴/T)s^-1, respectively. The results show that the tunneling effect is significant and the variational effect is small for the calculation of the rate constant.

Key words: H₃PO, Isomerizazion reaction, QCISD, Reaction pathway, Rate constant

CLC Number:

O641

TrendMD:

WANG Wen-Liang, WANG Wei-Na, LUO Qiong, FANG Yu, LI Qian-Shu. Direct Dynamics Studies on the Isomerization Reaction H₃PO→H₂POH[J]. Chem. J. Chinese Universities, 2005, 26(2): 299.

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Direct Dynamics Studies on the Isomerization Reaction H₃PO→H₂POH

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