Quantum dynamics of rovibrational transitions in H2-H 2 collisions: Internal energy and rotational angular momentum conservation effects

S. Fonseca Dos Santos, N. Balakrishnan, S. Lepp, G. Quéméner, R. C. Forrey, R. J. Hinde, P. C. Stancil

Research output: Contribution to journalArticle

36 Scopus citations

Abstract

We present a full dimensional quantum mechanical treatment of collisions between two H2 molecules over a wide range of energies. Elastic and state-to-state inelastic cross sections for ortho-H2 para-H 2 and ortho-H2 ortho-H2 collisions have been computed for different initial rovibrational levels of the molecules. For rovibrationally excited molecules, it has been found that state-to-state transitions are highly specific. Inelastic collisions that conserve the total rotational angular momentum of the diatoms and that involve small changes in the internal energy are found to be highly efficient. The effectiveness of these quasiresonant processes increases with decreasing collision energy and they become highly state-selective at ultracold temperatures. They are found to be more dominant for rotational energy exchange than for vibrational transitions. For non-reactive collisions between ortho- and para-H2 molecules for which rotational energy exchange is forbidden, the quasiresonant mechanism involves a purely vibrational energy transfer albeit with less efficiency. When inelastic collisions are dominated by a quasiresonant transition calculations using a reduced basis set involving only the quasiresonant channels yield nearly identical results as the full basis set calculation leading to dramatic savings in computational cost.

Original languageEnglish (US)
Article number214303
JournalJournal of Chemical Physics
Volume134
Issue number21
DOIs
StatePublished - Jun 7 2011

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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