Rotationally inelastic collisions of the CH(2) molecule in its ã(1)A(1) electronic state have been investigated. We have determined a potential energy surface (PES) for the interaction of rigid CH(2)(ã), frozen at its equilibrium geometry, with a helium atom, using a coupled-cluster method that includes all single and double excitations, as well as perturbative contributions of connected triple excitations [RSSCD(T)]. The PES is quite anisotropic, due to lack of electron density in the unoccupied CH(2) non-bonding orbital perpendicular to the molecular plane. Quantum scattering calculations have been carried out to compute state-to-state rotational energy transfer and elastic depolarization cross sections at collision energies up to 2400 cm(-1). These cross sections were thermally averaged to derive room-temperature rate constants. The total removal and elastic depolarization rate constants for the ortho k(a) = 1 levels agree well with recent experimental measurements by Hall, Sears, and their co-workers. We observe a strong even-odd alternation in the magnitude of the total rate constants which we attribute to the asymmetry splitting of the k(a) = 1 levels.
Following our earlier work on collisions of He with the methylene radical in its excited ã(1)A(1) state [L. Ma, M. H. Alexander, and P. J. Dagdigian, J. Chem. Phys. 134, 154307 (2011)], we investigate here the analogous relaxation of CH(2) in its ground X(3)B(1) electronic state. The molecule is treated as semi-rigid, with fixed bond lengths but a varying bond angle. We use an ab initio potential energy surface (PES) which is averaged over the CH(2) bending angle weighted by the square of the bending wave function. The PES for the interaction of He with CH(2) in the X state is considerably less anisotropic than for interaction with the ã state since the two 2p electrons on the C atom are evenly distributed among the bonding and non-bonding molecular orbitals. We report quantum scattering calculations of state-to-state and total removal cross sections as well as total removal rate constants at room temperature. Because of the less pronounced anisotropy, these cross sections and rate constants are considerably smaller than for collisions of CH(2)(ã) with He. Finally, we investigate the dependence of rotational inelasticity on the bending vibrational quantum number.
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