Rotationally specific rates of vibration-vibration energy exchange in collisions of NO(X 2II1/2, v=3) with NO(X 2II, v=0)

Meez Islam, Ian W. M. Smith

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Abstract

Infrared ultraviolet double resonance (IRUVDR) experiments have been performed to investigate the rotational specificity of the vibrational-vibrational (V-V) exchange process, NO(X 2II1/2,ν = 3,Ji) + NO(ν = 0)→NO(X 2II1/2,ν = 2,Jf) + NO(ν=1), for which the vibrational energy discrepancy corresponds to 55.9 cm-1. Radiation from an optical parametric oscillator was used to excite NO molecules into a specific rotational level (Ji) in the X2II, Ω=1/2, ν=3 state. Laser-induced fluorescence (LIF) spectra of the (0,2) band of the A 2+ -X 2II1/2 system were then recorded at delays corresponding to a fraction of a collision. From the relative line intensities, rate coefficients were determined for transfer of the excited NO molecule from the level X 2II1/2, ν = 3, Ji to different final rotational levels (Jf) in the X 2II1/2, ν=2 state. Results are reported for Ji=3.5, 4.5, 7.5, 10.5, and 15.5. The data show a significant, though not strong, propensity for J to decrease by one; i.e., for ΔJ=Jf-Ji= -1, especially for the higher Ji levels. This result is interpreted as arising from a combination of (a) the tendency to minimize the energy that has to be accommodated in the relative translation of the collision partners, and (b) the favoring of ΔJ = ±1 changes when V- V intermolecular exchange occurs under the influence of dipole-dipole interactions.

Original languageEnglish
Pages (from-to)9296-9302
JournalJournal of Chemical Physics
Volume111
Issue number20
DOIs
Publication statusPublished - 22 Nov 1999

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energy transfer
Optical parametric oscillators
vibration
Molecules
collisions
Fluorescence
dipoles
Infrared radiation
Radiation
Lasers
parametric amplifiers
laser induced fluorescence
molecules
tendencies
Experiments
energy
radiation
coefficients
interactions

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title = "Rotationally specific rates of vibration-vibration energy exchange in collisions of NO(X 2II1/2, v=3) with NO(X 2II, v=0)",
abstract = "Infrared ultraviolet double resonance (IRUVDR) experiments have been performed to investigate the rotational specificity of the vibrational-vibrational (V-V) exchange process, NO(X 2II1/2,ν = 3,Ji) + NO(ν = 0)→NO(X 2II1/2,ν = 2,Jf) + NO(ν=1), for which the vibrational energy discrepancy corresponds to 55.9 cm-1. Radiation from an optical parametric oscillator was used to excite NO molecules into a specific rotational level (Ji) in the X2II, Ω=1/2, ν=3 state. Laser-induced fluorescence (LIF) spectra of the (0,2) band of the A 2∑+ -X 2II1/2 system were then recorded at delays corresponding to a fraction of a collision. From the relative line intensities, rate coefficients were determined for transfer of the excited NO molecule from the level X 2II1/2, ν = 3, Ji to different final rotational levels (Jf) in the X 2II1/2, ν=2 state. Results are reported for Ji=3.5, 4.5, 7.5, 10.5, and 15.5. The data show a significant, though not strong, propensity for J to decrease by one; i.e., for ΔJ=Jf-Ji= -1, especially for the higher Ji levels. This result is interpreted as arising from a combination of (a) the tendency to minimize the energy that has to be accommodated in the relative translation of the collision partners, and (b) the favoring of ΔJ = ±1 changes when V- V intermolecular exchange occurs under the influence of dipole-dipole interactions.",
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Rotationally specific rates of vibration-vibration energy exchange in collisions of NO(X 2II1/2, v=3) with NO(X 2II, v=0). / Islam, Meez; Smith, Ian W. M.

In: Journal of Chemical Physics, Vol. 111, No. 20, 22.11.1999, p. 9296-9302.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Rotationally specific rates of vibration-vibration energy exchange in collisions of NO(X 2II1/2, v=3) with NO(X 2II, v=0)

AU - Islam, Meez

AU - Smith, Ian W. M.

N1 - Author can archive publisher's version/PDF.

PY - 1999/11/22

Y1 - 1999/11/22

N2 - Infrared ultraviolet double resonance (IRUVDR) experiments have been performed to investigate the rotational specificity of the vibrational-vibrational (V-V) exchange process, NO(X 2II1/2,ν = 3,Ji) + NO(ν = 0)→NO(X 2II1/2,ν = 2,Jf) + NO(ν=1), for which the vibrational energy discrepancy corresponds to 55.9 cm-1. Radiation from an optical parametric oscillator was used to excite NO molecules into a specific rotational level (Ji) in the X2II, Ω=1/2, ν=3 state. Laser-induced fluorescence (LIF) spectra of the (0,2) band of the A 2∑+ -X 2II1/2 system were then recorded at delays corresponding to a fraction of a collision. From the relative line intensities, rate coefficients were determined for transfer of the excited NO molecule from the level X 2II1/2, ν = 3, Ji to different final rotational levels (Jf) in the X 2II1/2, ν=2 state. Results are reported for Ji=3.5, 4.5, 7.5, 10.5, and 15.5. The data show a significant, though not strong, propensity for J to decrease by one; i.e., for ΔJ=Jf-Ji= -1, especially for the higher Ji levels. This result is interpreted as arising from a combination of (a) the tendency to minimize the energy that has to be accommodated in the relative translation of the collision partners, and (b) the favoring of ΔJ = ±1 changes when V- V intermolecular exchange occurs under the influence of dipole-dipole interactions.

AB - Infrared ultraviolet double resonance (IRUVDR) experiments have been performed to investigate the rotational specificity of the vibrational-vibrational (V-V) exchange process, NO(X 2II1/2,ν = 3,Ji) + NO(ν = 0)→NO(X 2II1/2,ν = 2,Jf) + NO(ν=1), for which the vibrational energy discrepancy corresponds to 55.9 cm-1. Radiation from an optical parametric oscillator was used to excite NO molecules into a specific rotational level (Ji) in the X2II, Ω=1/2, ν=3 state. Laser-induced fluorescence (LIF) spectra of the (0,2) band of the A 2∑+ -X 2II1/2 system were then recorded at delays corresponding to a fraction of a collision. From the relative line intensities, rate coefficients were determined for transfer of the excited NO molecule from the level X 2II1/2, ν = 3, Ji to different final rotational levels (Jf) in the X 2II1/2, ν=2 state. Results are reported for Ji=3.5, 4.5, 7.5, 10.5, and 15.5. The data show a significant, though not strong, propensity for J to decrease by one; i.e., for ΔJ=Jf-Ji= -1, especially for the higher Ji levels. This result is interpreted as arising from a combination of (a) the tendency to minimize the energy that has to be accommodated in the relative translation of the collision partners, and (b) the favoring of ΔJ = ±1 changes when V- V intermolecular exchange occurs under the influence of dipole-dipole interactions.

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