Vibration-vibration and vibration-translation energy transfer in H 2-H2 collisions: A critical test of experiment with full-dimensional quantum dynamics

S. Fonseca Dos Santos, N. Balakrishnan, R. C. Forrey, P. C. Stancil

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Quantum scattering calculations of vibration-vibration (VV) and vibration-translation (VT) energy transfer for non-reactive H2-H 2 collisions on a full-dimensional potential energy surface are reported for energies ranging from the ultracold to the thermal regime. The efficiency of VV and VT transfer is known to strongly correlate with the energy gap between the initial and final states. In H2(v=1, j=0) H 2(v=0, j=1) collisions, the inelastic cross section at low energies is dominated by a VV process leading to H2(v=0, j=0) H 2(v=1, j=1) products. At energies above the opening of the v=1, j=2 rotational channel, pure rotational excitation of the para-H2 molecule leading to the formation of H2(v=1, j=2) H2(v=0, j=1) dominates the inelastic cross section. For vibrationally excited H 2 in the v 2 vibrational level colliding with H2(v=0), the efficiency of both VV and VT process is examined. It is found that the VV process leading to the formation of 2H2(v=1) molecules dominates over the VT process leading to H2(v=1) H2(v=0) products, consistent with available experimental data, but in contrast to earlier semiclassical results. Overall, VV processes are found to be more efficient than VT processes, for both distinguishable and indistinguishable H 2-H2 collisions confirming room temperature measurements for v=1 and v 2.

Original languageEnglish (US)
Article number104302
JournalJournal of Chemical Physics
Volume138
Issue number10
DOIs
StatePublished - Mar 14 2013

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Energy transfer
energy transfer
vibration
Potential energy surfaces
Molecules
collisions
Temperature measurement
Energy gap
Experiments
Scattering
Hot Temperature
cross sections
products
temperature measurement
energy
molecules

All Science Journal Classification (ASJC) codes

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

Cite this

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title = "Vibration-vibration and vibration-translation energy transfer in H 2-H2 collisions: A critical test of experiment with full-dimensional quantum dynamics",
abstract = "Quantum scattering calculations of vibration-vibration (VV) and vibration-translation (VT) energy transfer for non-reactive H2-H 2 collisions on a full-dimensional potential energy surface are reported for energies ranging from the ultracold to the thermal regime. The efficiency of VV and VT transfer is known to strongly correlate with the energy gap between the initial and final states. In H2(v=1, j=0) H 2(v=0, j=1) collisions, the inelastic cross section at low energies is dominated by a VV process leading to H2(v=0, j=0) H 2(v=1, j=1) products. At energies above the opening of the v=1, j=2 rotational channel, pure rotational excitation of the para-H2 molecule leading to the formation of H2(v=1, j=2) H2(v=0, j=1) dominates the inelastic cross section. For vibrationally excited H 2 in the v 2 vibrational level colliding with H2(v=0), the efficiency of both VV and VT process is examined. It is found that the VV process leading to the formation of 2H2(v=1) molecules dominates over the VT process leading to H2(v=1) H2(v=0) products, consistent with available experimental data, but in contrast to earlier semiclassical results. Overall, VV processes are found to be more efficient than VT processes, for both distinguishable and indistinguishable H 2-H2 collisions confirming room temperature measurements for v=1 and v 2.",
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Vibration-vibration and vibration-translation energy transfer in H 2-H2 collisions : A critical test of experiment with full-dimensional quantum dynamics. / Dos Santos, S. Fonseca; Balakrishnan, N.; Forrey, R. C.; Stancil, P. C.

In: Journal of Chemical Physics, Vol. 138, No. 10, 104302, 14.03.2013.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Vibration-vibration and vibration-translation energy transfer in H 2-H2 collisions

T2 - A critical test of experiment with full-dimensional quantum dynamics

AU - Dos Santos, S. Fonseca

AU - Balakrishnan, N.

AU - Forrey, R. C.

AU - Stancil, P. C.

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AB - Quantum scattering calculations of vibration-vibration (VV) and vibration-translation (VT) energy transfer for non-reactive H2-H 2 collisions on a full-dimensional potential energy surface are reported for energies ranging from the ultracold to the thermal regime. The efficiency of VV and VT transfer is known to strongly correlate with the energy gap between the initial and final states. In H2(v=1, j=0) H 2(v=0, j=1) collisions, the inelastic cross section at low energies is dominated by a VV process leading to H2(v=0, j=0) H 2(v=1, j=1) products. At energies above the opening of the v=1, j=2 rotational channel, pure rotational excitation of the para-H2 molecule leading to the formation of H2(v=1, j=2) H2(v=0, j=1) dominates the inelastic cross section. For vibrationally excited H 2 in the v 2 vibrational level colliding with H2(v=0), the efficiency of both VV and VT process is examined. It is found that the VV process leading to the formation of 2H2(v=1) molecules dominates over the VT process leading to H2(v=1) H2(v=0) products, consistent with available experimental data, but in contrast to earlier semiclassical results. Overall, VV processes are found to be more efficient than VT processes, for both distinguishable and indistinguishable H 2-H2 collisions confirming room temperature measurements for v=1 and v 2.

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