The parabolic barrier semiclassical transition state theory (SCTST), truncated parabolic barrier SCTST and fully anharmonic SCTST were studied to motivate reaction path Hamiltonian (RPH)-SCTST. It was found that the SCTST is qualitatively correct in the low and high temperature limits. The new correction captures the effects of curvature and barrier anharmonicity with just three frequency calculations. The results show that the effect of barrier anharmonicity can result in calculated rates that are much smaller than rates predicted by truncated harmonic SCTST.
|Original language||English (US)|
|Number of pages||6|
|Journal||Journal of Chemical Physics|
|State||Published - Sep 8 2004|
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry