Rotational excitations in para-H2+para-H2 collisions: full- and reduced-dimensional quantum wave packet studies comparing different potential energy surfaces.
We study the process of rotational excitation in the collisions of para-H(2) with para-H(2) by propagating wave packets with the multiconfiguration time-dependent Hartree (MCTDH) algorithm. Transition probabilities are then calculated by the method of Tannor and Weeks based on time-correlation functions. Calculations were carried out up to a total angular momentum of J=70 to compute integral cross sections up to 1.2 eV in collision energy and thermal rate coefficients from 100 to 3000 K. The process is studied on the full-dimensional potential energy surface of Boothroyd-Martin-Keogh-Peterson (BMKP) as well as on the rigid rotor surface of Diep and Johnson. We test the validity of the rigid rotor approximation by also considering two rigid rotor restrictions of the BMKP potential energy surface (PES). Additionally, we investigate a variant of the BMKP PES suggested by Pogrebnya and Clary [Chem. Phys. Lett. 363, 523 (2002)] with reduced anisotropy. We compare our results with previous theoretical data for the cross sections and with experimental data for the rate coefficients at low temperatures.
Otto
Frank
F
Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany. frank.otto@pci.uni-heidelberg.de
Gatti
Fabien
F
Meyer
Hans-Dieter
HD