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Title: Collision dynamics of symmetric top molecules: A comparison of the rotationally inelastic scattering of CD{sub 3} and ND{sub 3} with He

Abstract

We compare rotationally inelastic scattering of deuterated methyl radicals (CD{sub 3}) and ammonia (ND{sub 3}) 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. Tkáč, 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. Tkáč, 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 CD{sub 3} rotational levels of each nuclear spin symmetry at a collision energy of 440 cm{sup −1}. Similarities and differences inmore » the differential cross sections for the ND{sub 3}–He and CD{sub 3}–He systems can be linked to the coupling terms derived from the PESs which govern particular initial to final rotational level transitions.« less

Authors:
;  [1];  [2];
  1. School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (United Kingdom)
  2. Department of Chemistry and Biochemistry and Institute for Physical Science and Technology, University of Maryland, College Park, Maryland 20742-2021 (United States)
Publication Date:
OSTI Identifier:
22253305
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 140; Journal Issue: 13; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; AMMONIA; ANISOTROPY; COLLISIONS; COUPLING; DEUTERIDES; DIFFERENTIAL CROSS SECTIONS; INELASTIC SCATTERING; INTEGRAL CROSS SECTIONS; INTERACTIONS; METHYL RADICALS; MOLECULAR BEAMS; POTENTIAL ENERGY; QUANTUM MECHANICS

Citation Formats

Tkáč, Ondřej, Orr-Ewing, Andrew J., Dagdigian, Paul J., E-mail: pjdagdigian@jhu.edu, Alexander, Millard H., Onvlee, Jolijn, and Avoird, Ad van der, E-mail: avda@theochem.ru.nl. Collision dynamics of symmetric top molecules: A comparison of the rotationally inelastic scattering of CD{sub 3} and ND{sub 3} with He. United States: N. p., 2014. Web. doi:10.1063/1.4869596.
Tkáč, Ondřej, Orr-Ewing, Andrew J., Dagdigian, Paul J., E-mail: pjdagdigian@jhu.edu, Alexander, Millard H., Onvlee, Jolijn, & Avoird, Ad van der, E-mail: avda@theochem.ru.nl. Collision dynamics of symmetric top molecules: A comparison of the rotationally inelastic scattering of CD{sub 3} and ND{sub 3} with He. United States. https://doi.org/10.1063/1.4869596
Tkáč, Ondřej, Orr-Ewing, Andrew J., Dagdigian, Paul J., E-mail: pjdagdigian@jhu.edu, Alexander, Millard H., Onvlee, Jolijn, and Avoird, Ad van der, E-mail: avda@theochem.ru.nl. 2014. "Collision dynamics of symmetric top molecules: A comparison of the rotationally inelastic scattering of CD{sub 3} and ND{sub 3} with He". United States. https://doi.org/10.1063/1.4869596.
@article{osti_22253305,
title = {Collision dynamics of symmetric top molecules: A comparison of the rotationally inelastic scattering of CD{sub 3} and ND{sub 3} with He},
author = {Tkáč, Ondřej and Orr-Ewing, Andrew J. and Dagdigian, Paul J., E-mail: pjdagdigian@jhu.edu and Alexander, Millard H. and Onvlee, Jolijn and Avoird, Ad van der, E-mail: avda@theochem.ru.nl},
abstractNote = {We compare rotationally inelastic scattering of deuterated methyl radicals (CD{sub 3}) and ammonia (ND{sub 3}) 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. Tkáč, 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. Tkáč, 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 CD{sub 3} rotational levels of each nuclear spin symmetry at a collision energy of 440 cm{sup −1}. Similarities and differences in the differential cross sections for the ND{sub 3}–He and CD{sub 3}–He systems can be linked to the coupling terms derived from the PESs which govern particular initial to final rotational level transitions.},
doi = {10.1063/1.4869596},
url = {https://www.osti.gov/biblio/22253305}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 13,
volume = 140,
place = {United States},
year = {Mon Apr 07 00:00:00 EDT 2014},
month = {Mon Apr 07 00:00:00 EDT 2014}
}