Publications of Scott M. Auerbach: Paper 5 Abstract

Scott M. Auerbach and William H. Miller, ``Efficient polynomial expansion of the scattering Green's function: Application to the D+H₂ (n=1) rate constant,'' J. Chem. Phys. 100, 1103-1112 (1994).

Abstract

We apply the absorbing boundary condition (ABC) discrete variable representation (DVR) theory of quantum reactive scattering to the initial state selected D+H₂ (n=1) -> DH+H reaction. The ABC-DVR Green's function is efficiently computed by a Newton polynomial expansion. We compute accurate reaction probabilities for the total energies and angular momenta required to obtain the thermal rate constants k(n=1,j)(T)$. At T = 310 K, a thermal average over j=(0,1,2,3) is performed to yield the final result k(n=1)(310 K) = 1.87x10^-13 cm³ molecule^-1 sec^-1, in quantitative agreement with the most recent experimental value (1.9 +/- 0.2)x10^-13 cm³ molecule^-1 sec^-1. The J-shifting approximation using accurate J=0 reaction probabilities is tested against the exact results. It reliably predicts k(n=1)(T) for temperatures up to 700 K, but individual (n=1,j)-selected rate constants are in error by as much as 41%.

Prof SM Auerbach
18 June 2004

Scott M. Auerbach and William H. Miller, ``Efficient polynomial expansion of the scattering Green's function: Application to the D+H2 (n=1) rate constant,'' J. Chem. Phys. 100, 1103-1112 (1994).

Abstract

Scott M. Auerbach and William H. Miller, ``Efficient polynomial expansion of the scattering Green's function: Application to the D+H₂ (n=1) rate constant,'' J. Chem. Phys. 100, 1103-1112 (1994).