Elastic depolarization and polarization transfer in CN(A2Π, v = 4)+Ar collisions

Iain Ballingall, Michael F. Rutherford, Kenneth G. McKendrick, Matthew L. Costen

Research output: Contribution to journalArticle

Abstract

Rate constants for collisional loss and transfer of population and rotational angular momentum alignment have been determined for the CN(A 2?, v = 4)+Ar system. Aligned samples of CN(A2?, v = 4, F1, j = 1.5-23.5e) were prepared by optical pumping on the A-X(4,0) band. Their evolution was observed using Doppler-resolved frequency-modulated spectroscopy in stimulated emission on the A-X(4,2) band. State-resolved total population removal rate constants, and state-to-state rotational energy transfer (RET) rate constants, are found to be in excellent agreement with previous experimental measurements and theoretical predictions for the v = 3 level. Rapid elastic depolarization of rotational alignment was observed for j = 1.5-6.5, with an average rate constant of 1.1 × 10 -10 cm3 s-1. This declines with increasing j, reaching zero within experimental error for j = 23.5. The polarization transfer efficiency of the initially created alignment in state-to-state RET was also determined for the selected initial state j = 6.5, F1, e. Substantial depolarization of the alignment was observed for small ?j transitions. Alignment transfer efficiencies ranged from 0.55 ± 0.06 for ?j = -1, to 0.32 ± 0.08 for ?j = +3. These measurements are discussed with reference to recent experimental and theoretical advances on collisional depolarization of related open-shell species. We suggest that the surprisingly efficient collisional depolarization observed may be the result of the multiple potential energy surfaces involved in this system. © 2010 Taylor & Francis.

Original languageEnglish
Pages (from-to)847-863
Number of pages17
JournalMolecular Physics
Volume108
Issue number7-9
DOIs
Publication statusPublished - Oct 2010

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depolarization
alignment
collisions
polarization
rotational states
energy transfer
optical pumping
stimulated emission
angular momentum
potential energy
predictions
spectroscopy

Keywords

  • Alignment
  • Inelastic collisions
  • Polarization
  • Rate constant
  • Rotational energy transfer

Cite this

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title = "Elastic depolarization and polarization transfer in CN(A2Π, v = 4)+Ar collisions",
abstract = "Rate constants for collisional loss and transfer of population and rotational angular momentum alignment have been determined for the CN(A 2?, v = 4)+Ar system. Aligned samples of CN(A2?, v = 4, F1, j = 1.5-23.5e) were prepared by optical pumping on the A-X(4,0) band. Their evolution was observed using Doppler-resolved frequency-modulated spectroscopy in stimulated emission on the A-X(4,2) band. State-resolved total population removal rate constants, and state-to-state rotational energy transfer (RET) rate constants, are found to be in excellent agreement with previous experimental measurements and theoretical predictions for the v = 3 level. Rapid elastic depolarization of rotational alignment was observed for j = 1.5-6.5, with an average rate constant of 1.1 × 10 -10 cm3 s-1. This declines with increasing j, reaching zero within experimental error for j = 23.5. The polarization transfer efficiency of the initially created alignment in state-to-state RET was also determined for the selected initial state j = 6.5, F1, e. Substantial depolarization of the alignment was observed for small ?j transitions. Alignment transfer efficiencies ranged from 0.55 ± 0.06 for ?j = -1, to 0.32 ± 0.08 for ?j = +3. These measurements are discussed with reference to recent experimental and theoretical advances on collisional depolarization of related open-shell species. We suggest that the surprisingly efficient collisional depolarization observed may be the result of the multiple potential energy surfaces involved in this system. {\circledC} 2010 Taylor & Francis.",
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author = "Iain Ballingall and Rutherford, {Michael F.} and McKendrick, {Kenneth G.} and Costen, {Matthew L.}",
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Elastic depolarization and polarization transfer in CN(A2Π, v = 4)+Ar collisions. / Ballingall, Iain; Rutherford, Michael F.; McKendrick, Kenneth G.; Costen, Matthew L.

In: Molecular Physics, Vol. 108, No. 7-9, 10.2010, p. 847-863.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Elastic depolarization and polarization transfer in CN(A2Π, v = 4)+Ar collisions

AU - Ballingall, Iain

AU - Rutherford, Michael F.

AU - McKendrick, Kenneth G.

AU - Costen, Matthew L.

PY - 2010/10

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AB - Rate constants for collisional loss and transfer of population and rotational angular momentum alignment have been determined for the CN(A 2?, v = 4)+Ar system. Aligned samples of CN(A2?, v = 4, F1, j = 1.5-23.5e) were prepared by optical pumping on the A-X(4,0) band. Their evolution was observed using Doppler-resolved frequency-modulated spectroscopy in stimulated emission on the A-X(4,2) band. State-resolved total population removal rate constants, and state-to-state rotational energy transfer (RET) rate constants, are found to be in excellent agreement with previous experimental measurements and theoretical predictions for the v = 3 level. Rapid elastic depolarization of rotational alignment was observed for j = 1.5-6.5, with an average rate constant of 1.1 × 10 -10 cm3 s-1. This declines with increasing j, reaching zero within experimental error for j = 23.5. The polarization transfer efficiency of the initially created alignment in state-to-state RET was also determined for the selected initial state j = 6.5, F1, e. Substantial depolarization of the alignment was observed for small ?j transitions. Alignment transfer efficiencies ranged from 0.55 ± 0.06 for ?j = -1, to 0.32 ± 0.08 for ?j = +3. These measurements are discussed with reference to recent experimental and theoretical advances on collisional depolarization of related open-shell species. We suggest that the surprisingly efficient collisional depolarization observed may be the result of the multiple potential energy surfaces involved in this system. © 2010 Taylor & Francis.

KW - Alignment

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KW - Polarization

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KW - Rotational energy transfer

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