Abstract
We report calculations of the reaction rates of O(3P) + CH4 → OH + CH3 and O(3P) + CD4 → OD + CD3 over the temperature range 300-2500 K. The calculations are based on variational transition state theory in curvilinear coordinates with transmission coefficients calculated by the microcanonical optimized multi-dimensional tunneling approximation. A dual-level algorithm is used for the dynamical calculations. The higher level is UMP2/cc-pVTZ, and two lower levels are employed: PM3-SRP and an analytical potential energy surface. Using the canonical unified statistical model with microcanonical optimized multidimensional tunneling contributions, we obtain good agreement with experimental rate constants.
Original language | English (US) |
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Pages (from-to) | 4899-4910 |
Number of pages | 12 |
Journal | Journal of Physical Chemistry A |
Volume | 102 |
Issue number | 25 |
DOIs | |
State | Published - Jun 18 1998 |