Collision dynamics of symmetric top molecules: A comparison of the rotationally inelastic scattering of CD3 and ND3 with He

Ondrej Tkac*, Andrew J. Orr-Ewing, Paul J. Dagdigian, Millard H. Alexander, Jolijn Onvlee, Ad van der Avoird

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

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Abstract

We compare rotationally inelastic scattering of deuterated methyl radicals (CD3) and ammonia (ND3) in collisions with helium using close-coupling quantum-mechanical scattering calculations performed with ab initio potential energy surfaces (PESs). The theoretical methods have been rigorously tested against angle-resolved experimental measurements obtained using crossed molecular beam apparatuses in combination with velocity map imaging [O. Tkac, A. G. Sage, S. J. Greaves, A. J. Orr-Ewing, P. J. Dagdigian, Q. Ma, and M. H. Alexander, Chem. Sci. 4, 4199 (2013); O. Tkac, A. K. Saha, J. Onvlee, C.-H. Yang, G. Sarma, C. K. Bishwakarma, S. Y. T. van de Meerakker, A. van der Avoird, D. H. Parker, and A. J. Orr-Ewing, Phys. Chem. Chem. Phys. 16, 477 (2014)]. Common features of the scattering dynamics of these two symmetric top molecules, one closed-shell and the other an open-shell radical, are identified and discussed. Two types of anisotropies in the PES influence the interaction of an atom with a nonlinear polyatomic molecule. The effects of these anisotropies can be clearly seen in the state-to-state integral cross sections out of the lowest CD3 rotational levels of each nuclear spin symmetry at a collision energy of 440 cm(-1). Similarities and differences in the differential cross sections for the ND3-He and CD3-He systems can be linked to the coupling terms derived from the PESs which govern particular initial to final rotational level transitions. (C) 2014 AIP Publishing LLC.

Original languageEnglish
Article number134308
Number of pages10
JournalJournal of Chemical Physics
Volume140
Issue number13
DOIs
Publication statusPublished - 7 Apr 2014

Bibliographical note

Accepted 13/03/2014

Keywords

  • DIFFERENTIAL CROSS-SECTIONS
  • NH3-HE COLLISIONS
  • ENERGY-TRANSFER
  • AR
  • EXCITATION
  • AMMONIA
  • ORTHO-NH3
  • INVERSION
  • PARA-NH3
  • RADICALS

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