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Report No.

Direct ab initio molecular dynamics study of the two photodissociation channels of formic acid

Kurosaki, Yuzuru; Yokoyama, Keiichi; Teranishi, Yoshiaki

A total of $$sim$$ 1200 trajectories have been integrated for the two dissociation channels of formic acid, HCOOH $$rightarrow$$ H$$_{2}$$O + CO (1) and HCOOH $$rightarrow$$ CO$$_{2}$$ + H$$_{2}$$ (2), which occur with 248 and 193 nm photons, using the direct ab initio molecular dynamics method at the RMP2(full)/cc-pVDZ level of theory. It was found that the percentage of the energy distributed to a relative translational mode in reaction 2 is much larger than that in reaction 1. This is mainly due to the difference in the geometry of transition state (TS); the H$$_{2}$$O geometry in the TS of reaction 1 was predicted to significantly deviate from the equilibrium one, whereas the CO$$_{2}$$ and H$$_{2}$$ geometries in the TS of reaction 2 were found to be more similar to their equilibrium ones. It was also found that the product diatomic molecules, CO and H$$_{2}$$, are both vibrationally and rotationally excited. The calculated relative population of the vibrationally excited CO for the 248 nm photodissociation was consistent with experiment.



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Category:Chemistry, Physical



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