Strong geometric-phase effects in the hydrogen-exchange reaction at high collision energies.
We report quantum wave packet calculations of state-to-state reaction probabilities and cross sections for the reaction H+H(2)(v(0)=0,j(0)=0)-->H(2)(v,j)+H, at total energies up to 4.5 eV above the ground state potential minimum. The calculations are repeated using (i) the ground electronic state only, (ii) the ground state plus the diagonal non-Born-Oppenheimer correction, (iii) the ground state, diagonal non-Born-Oppenheimer correction and geometric phase (GP), and (iv) both electronic states including all nonadiabatic couplings, using the diabatic potential approach of Mahapatra et al. [J. Phys. Chem. A 105, 2321 (2001)]. The results for calculations (iii) and (iv) are in very close agreement, showing that the upper electronic state makes only a very small contribution to the state-to-state dynamics, even at energies much higher than the conical intersection minimum (at 2.74 eV). At total energies above 3.5 eV, many of the state-to-state reaction probabilities show strong GP effects, indicating that they are dominated by interference between one- and two-transition-state (1-TS and 2-TS) reaction paths. These effects survive the coherent sum over partial waves to produce features in the state-to-state differential cross sections which could be detected in an experiment with an angular resolution of approximately 20 degrees . Efficient dephasing of the interference between the 1-TS and 2-TS contributions causes almost complete cancellation of the GP in the integral cross sections, thus continuing a trend observed at lower energies in earlier work.
Bouakline
Foudhil
F
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Althorpe
Stuart C
SC
Peláez Ruiz
Daniel
D