An ab initio based global potential energy surface describing CH5+ --> CH3+ + H2.
A full-dimensional, ab initio based potential energy surface (PES) for CH(5)(+), which can describe dissociation is reported. The PES is a precise fit to 36173 coupled-cluster [CCSD(T)] calculations of electronic energies done using an aug-cc-pVTZ basis. The fit uses a polynomial basis that is invariant with respect to permutation of the five H atoms, and thus describes all 120 equivalent minima. The rms fitting error is 78.1 cm(-1) for the entire data set of energies up to 30,000 cm(-1) and a normal-mode analysis of CH(5)(+) also verifies the accuracy of the fit. Two saddle points have been located on the surface as well and compared with previous theoretical work. The PES dissociates correctly to the fragments CH(3)(+) + H(2) and the equilibrium geometry and normal-mode analyses of these fragments are also presented. Diffusion Monte Carlo calculations are done for the zero-point energies of CH(5)(+) (and some isotopologs) as well as for the separated fragments of CH(5)(+), CH(3)(+) + H(2) and those of CH(4)D(+), CH(3)(+) + HD and CH(2)D(+) + H(2). Values of D(0) are reported for these dissociations. A molecular dynamics calculation of CH(4)D(+) dissociation at one total energy is also performed to both validate the applicability of the PES for dynamics studies as well as to test a simple classical statistical prediction of the branching ratio of the dissociation products.
Jin
Zhong
Z
Cherry L. Emerson Center of Scientific Computation, Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
Braams
Bastiaan J
BJ
Bowman
Joel M
JM