A new (multi-reference configuration interaction) potential energy surface for H 2 CO and preliminary studies of roaming

We report a new global potential energy surface (PES) for H2 CO, based on precise fitting of roughly 67 000 MRCI/cc-pVTZ energies. This PES describes the global minimum, thecis - andtrans -HCOH isomers, and barriers relevant to isomerization, formation of the molecular (H2 +CO) and radical (H+HCO) products, and the loose so-called roaming transition-state saddle point. The key features of the PES are reviewed and compared with a previous PES, denoted by PES04, based on five local fits that are ‘stitched’ together by switching functions (Zhanget al. 2004J. Phys. Chem. A 108 , 8980–8986 (doi:10.1021/jp048339l )). Preliminary quasi-classical trajectory calculations are performed at the total energy of 36 233 cm−1 (103 kcal mol−1 ), relative to the H2 CO global minimum, using the new PES, with a particular focus on roaming dynamics. When compared with the results from PES04, the new PES findings show similar rotational distributions, somewhat more roaming and substantially higher H2 vibrational excitation.This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’.