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Role of isomerization channel in unimolecular dissociation reaction H2CO→H2+CO: Ab initio global potential energy surface and classical trajectory analysis

2002; American Institute of Physics; Volume: 117; Issue: 24 Linguagem: Inglês

10.1063/1.1523058

1520-9032

Takehiro Yonehara, Shigekí Kato,

Quantum, superfluid, helium dynamics

We constructed a full dimensional potential energy function of H2CO that can describe both the dissociation and isomerization channels by the modified Shepard interpolation method. Ab initio calculations at the MP2/cc-pVTZ level were carried out to obtain the local potential functions at about 4700 points. The interpolant points were sampled by classical trajectory calculations and by the grid searches in the internal coordinate space. Classical trajectory calculations were performed to examine the intramolecular dynamics associated with the dissociation as well as the product state distributions. The time scale of intramolecular vibrational energy randomization was much faster than that of the dissociation reaction. The dissociation rate was obtained from the classical trajectory results and the effect of the isomerization channel on the dissociation was estimated. The calculated rate constants were compared with those by Rice–Ramsperger–Kassel–Marcus theory.