Dependence of the rate constants on the treatment of internal rotation modes: the reaction OH + CH3SH --> CH3S + H2O as an example.
The title reaction has been used as an example to test the importance of using a hindered rotor treatment instead of a harmonic oscillator model for calculating vibrational partition functions corresponding to low-frequency internal rotation modes. First, a normal-mode analysis according to the Ayala and Schlegel's algorithm has been used to identify the internal rotation modes of methanethiol and the transition state structure. Then, after calculation of the energy barrier for each internal rotation, the corresponding hindered rotor partition functions have been calculated following the CW scheme of Chuang and Truhlar. The results show that the anharmonic treatment produces a rather modest improvement of the rate constants at room temperature or below.
Masgrau
Laura
L
Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra (Barcelona), Spain.
González-Lafont
Angels
A
Lluch
José M
JM