Doppler-resolved kinetics of saturation recovery

Forthomme, Damien; Hause, Michael L.; Yu, Hua -Gen; Dagdigian, Paul J.; Sears, Trevor J.; Hall, Gregory E.

doi:10.1021/acs.jpca.5b00628

Title: Doppler-resolved kinetics of saturation recovery

Journal Article · Wed Apr 08 00:00:00 EDT 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.5b00628 · OSTI ID:1183291

Forthomme, Damien ^[1]; Hause, Michael L. ^[1]; Yu, Hua -Gen ^[1]; Dagdigian, Paul J. ^[2]; Sears, Trevor J. ^[3]; Hall, Gregory E. ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
John Hopkins Univ., Baltimore, MD (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)

Frequency modulated laser transient absorption has been used to monitor the ground state rotational energy transfer rates of CN radicals in a double-resonance, depletion recovery experiment. When a pulsed laser is used to burn a hole in the equilibrium ground state population of one rotational state without velocity selection, the population recovery rate is found to depend strongly on the Doppler detuning of a narrow-band probe laser. Similar effects should be apparent for any relaxation rate process that competes effectively with velocity randomization. Alternative methods of extracting thermal rate constants in the presence of these non-thermal conditions are evaluated. Total recovery rate constants, analogous to total removal rate constants in an experiment preparing a single initial rotational level, are in good agreement with quantum scattering calculations, but are slower than previously reported experiments and show qualitatively different rotational state dependence between Ar and He collision partners. As a result, quasi-classical trajectory studies confirm that the differing rotational state dependence is primarily a kinematic effect.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1183291

Report Number(s):: BNL--107780-2015-JA; KC0301020

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 28 Vol. 119; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Doppler-resolved kinetics of saturation recovery

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