Geometric phase effects in the H+H2 reaction: quantum wave-packet calculations of integral and differential cross sections.
We report quantum wave-packet calculations on the H+H(2) reaction, aimed at resolving the controversy over whether geometric phase (GP) effects can be observed in this reaction. Two sets of calculations are reported of the state-to-state reaction probabilities, and integral and differential cross sections (ICSs and DCSs). One set includes the GP using the vector potential approach of Mead and Truhlar; the other set neglects the phase. We obtain unequivocal agreement with recent results of Kendrick [J. Phys. Chem. A 107, 6739 (2003)], predicting GP effects in the state-to-state reaction probabilities, which cancel exactly on summing the partial waves to yield the ICS. Our results therefore contradict those of Kuppermann and Wu [Chem. Phys. Lett. 349 537 (2001)], which predicted pronounced GP effects in the cross sections. We also agree with Kendrick in predicting that there are no significant GP effects in the full DCS at energies below 1.8 eV, and in the partial (0<or=J<or=10) DCS at energies above this. However, we find that in the full DCS above 1.8 eV (which was not reported by Kendrick), there are GP effects, which may be experimentally measurable.
Juanes-Marcos
Juan Carlos
JC
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Althorpe
Stuart C
SC