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Vibrational-to-translational energy transfer between the lowest vibrational levels (v′=0–4) of the A(0+u) state of Bi2 has been investigated using spectrally resolved, laser-induced fluorescence techniques. The small vibrational spacing (ω′e≃132 cm−1) leads to highly nonadiabatic conditions, particularly for the Bi2(A)–He collision pair. However, the Δv=−1 transition probabilities for collisions with the rare gases range from 0.75% to 1.75% per collision, considerably lower than would be anticipated from standard vibrational energy transfer theory. Multiquantum (Δv′=±2) transfer rates are low, consistent with the low anharmonicity of the A(0+u) state. The rates for Δv′=±1 transitions scale linearly with vibrational quantum number as expected near the bottom of this nearly harmonic potential.


© 1999 AIP Publishing LLC, published under an exclusive license with American Institute of Physics.

AFIT Scholar, as the repository of the Air Force Institute of Technology, furnishes the published Version of Record for this article in accordance with the sharing policy of the publisher, AIP Publishing. A 12-month embargo was observed.

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in The Journal of Chemical Physics, 111: 5757–5763 as fully cited below and may be found at DOI: 10.1063/1.479872.

The Part II article. published in 2002 in JCP is available at AFIT Scholar by clicking here.

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The Journal of Chemical Physics