Quasiresonant vibration–rotation transfer: A kinematic interpretation

McCaffery, A. J.

doi:10.1063/1.480107

Cited by 28 publications

(43 citation statements)

References 22 publications

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“…Using Eqs. (13) and (14) in Eq. 12, we arrive at the final polarization spectroscopy lineshape function,…”

Section: A Polarization Spectroscopy Lineshapesmentioning

confidence: 99%

“…A theoretical interpretation of these data was given by McCaffery. 14 The rate coefficients for Li 2 (A 1 u + ) + Li were measured using similar techniques. 15 In addition, rate coefficients for vibrationally inelastic Li 2 (A 1 u + )-noble gas collisions were determined systematically for a wide range of initial vibrational levels using the same experimental setup, 16,17 and these were compared to calculations using the Li 2 (A 1 u + ) + Ne ab initio potential energy surface of Ref.…”

Section: Introductionmentioning

confidence: 99%

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Collisional transfer of population and orientation in NaK

Wolfe

Ashman

Bai

et al. 2011

The Journal of Chemical Physics

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Collisional satellite lines with |ΔJ| ≤ 58 have been identified in recent polarization spectroscopy V-type optical-optical double resonance (OODR) excitation spectra of the Rb(2) molecule [H. Salami et al., Phys. Rev. A 80, 022515 (2009)]. Observation of these satellite lines clearly requires a transfer of population from the rotational level directly excited by the pump laser to a neighboring level in a collision of the molecule with an atomic perturber. However to be observed in polarization spectroscopy, the collision must also partially preserve the angular momentum orientation, which is at least somewhat surprising given the extremely large values of ΔJ that were observed. In the present work, we used the two-step OODR fluorescence and polarization spectroscopy techniques to obtain quantitative information on the transfer of population and orientation in rotationally inelastic collisions of the NaK molecules prepared in the 2(A)(1)Σ(+)(v' = 16, J' = 30) rovibrational level with argon and potassium perturbers. A rate equation model was used to study the intensities of these satellite lines as a function of argon pressure and heat pipe oven temperature, in order to separate the collisional effects of argon and potassium atoms. Using a fit of this rate equation model to the data, we found that collisions of NaK molecules with potassium atoms are more likely to transfer population and destroy orientation than collisions with argon atoms. Collisions with argon atoms show a strong propensity for population transfer with ΔJ = even. Conversely, collisions with potassium atoms do not show this ΔJ = even propensity, but do show a propensity for ΔJ = positive compared to ΔJ = negative, for this particular initial state. The density matrix equations of motion have also been solved numerically in order to test the approximations used in the rate equation model and to calculate fluorescence and polarization spectroscopy line shapes. In addition, we have measured rate coefficients for broadening of NaK 3(1)Π ← 2(A)(1)Σ(+)spectral lines due to collisions with argon and potassium atoms. Additional broadening, due to velocity changes occurring in rotationally inelastic collisions, has also been observed.

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“…Using Eqs. (13) and (14) in Eq. 12, we arrive at the final polarization spectroscopy lineshape function,…”

Section: A Polarization Spectroscopy Lineshapesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Collisional transfer of population and orientation in NaK

Wolfe

Ashman

Bai

et al. 2011

The Journal of Chemical Physics

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“…4 is reminiscent of the staircase plot for the fixed ⌬j / ⌬v ratios that was found in classical trajectory studies of QRVR transfer [29]. The structure is a consequence of the balance between energy and angular-momentum constraints [30] and appears to be a universal feature of atomdiatom collisions independent of the specific system. However, the distribution may appear differently for each system.…”

Section: Figures 1 Andmentioning

confidence: 75%

Cold collisions involving rotationally hot oxygen molecules

et al. 2004

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Cold and ultracold collisions involving rotationally hot oxygen molecules are investigated using quantummechanical, coupled-channel, coupled-states, and effective-potential scattering formulations. Quenching rate coefficients are given for initial rotational levels near the dissociation threshold. The stability of the oxygen "super rotors" against collisional decay is compared to previous investigations involving hydrogen molecules where the rotational inertia was significantly smaller. In contrast to hydrogen, all possible states of rotationally hot oxygen are quenched very rapidly during a collision with a buffer gas helium atom, and the quenching efficiency is always dominated by pure rotational transitions.

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“…4 A key objective in such an approach is to develop models for the reactive collision that allow rule-of-thumb calculations of the quantum state distributions in elementary reactions and zero order ͑or better͒ estimates of absolute cross sections using readily available data. This pragmatic view has led to the formulation of ͑qualitatively and quantita-tively͒ new approaches to the outcome of inelastic collisions [5][6][7][8] which give considerable insight into the controlling physics of the process as well as a high level of predictability based on readily available data, namely atomic masses, bond lengths, and velocity distributions.…”

Section: Introductionmentioning

confidence: 99%