Inelastic scattering matrix elements for the nonadiabatic collision B(P1∕22)+H2(Σg+1,j)↔B(P3∕22)+H2(Σg+1,j′)

Abstract

Inelastic scattering matrix elements for the nonadiabatic collision B(P1∕22)+H2(Σg+1,j)↔B(P3∕22)+H2(Σg+1,j′) are calculated using the time dependent channel packet method (CPM). The calculation employs 1A′2, 2A′2, and 1A″2 adiabatic electronic potential energy surfaces determined by numerical computation at the multireference configuration-interaction level [M. H. Alexander, J. Chem. Phys. 99, 6041 (1993)]. The 1A′2 and 2A′2, adiabatic electronic potential energy surfaces are transformed to yield diabatic electronic potential energy surfaces that, when combined with the total B+H2 rotational kinetic energy, yield a set of effective potential energy surfaces [M. H. Alexander et al., J. Chem. Phys. 103, 7956 (1995)]. Within the framework of the CPM, the number of effective potential energy surfaces used for the scattering matrix calculation is then determined by the size of the angular momentum basis used as a representation. Twenty basis vectors are employed for these calculations, and the corresponding effective potential energy surfaces are identified in the asymptotic limit by the H2 rotor quantum numbers j=0, 2, 4, 6 and B electronic states Pja2, ja=1∕2, 3∕2. Scattering matrix elements are obtained from the Fourier transform of the correlation function between channel packets evolving in time on these effective potential energy surfaces. For these calculations the H2 bond length is constrained to a constant value of req=1.402a.u. and state to state scattering matrix elements corresponding to a total angular momentum of J=1∕2 are discussed for j=0↔j′=0,2,4 and P1∕22↔P1∕22, P3∕22 over a range of total energy between 0.0 and 0.01a.u.