Direct ab initio dynamics study of the reaction of the hydrogen atom with formyl chloride

作者：Li QS^*; Luo QN

来源：Journal of Physical Chemistry A, 2003, 107(48): 10435-10440.

DOI：10.1021/jp0360568

A direct A initio dynamics study is presented on two channels of the gas-phase reaction of the hydrogen atom with formyl chloride, HCOCl. The geometries, harmonic vibrational frequencies, energies, and enthalpies of all of the stationary points are calculated at the BHandHLYP, MP2, and QCISD levels of theory with the cc-pVDZ basis set. The minimum energy paths (MEPs) of both channels of the title reaction are also computed with the same methods and basis set. The energies of stationary points and the points along the MEP for each channel are refined by means of some single-point multilevel energy calculations (HL). The rate constants are evaluated with the conventional transition state theory (TST), the improved canonical varitional transition state theory (ICVT), and the improved canonical varitional transition state theory with small-curvature tunneling correction (ICVT/SCT) in the temperature range of 300-2500 K. The fitted Arrhenius expressions of the calculated ICVT/SCT rate constants at the HL//BHandHLYP/cc-pVDZ and HL//QCISD/cc-pVDZ levels of theory are k(1)(ICVT/SCT)(T) = 1.16 x 10(-19) T-2.61 e((-1018.4/T)) and k(1)(ICVT/SCT)(T) = 1.64 x 10(-18) T(2.25)e((-1943.1/T)) for the H abstraction channel, and k(2)(ICVT/SCT)(T) = 1.16 x 10(-19)T(2.61) e((-1018.4/T)) and k(2)(ICVT/SCT)(T) = 1.85 x 10(-18)T(2.12)e((-3473.4/T)) for the Cl abstraction channel, respectively.

• 出版日期2003-12-4
• 单位北京理工大学