The effect of Wigner singularities on low-temperature vibrational relaxation rates

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Abstract
We have applied the vibrational-close-coupling, rotational-infinite-order-sudden (VCC-RIOS) and vibrational-rotational close coupling (CC) methods to collisions between He and I2(X 1Σ+g) to study the threshold dependence of vibrational deexcitation cross sections and rates on energy and temperature, respectively, for the v=1→0 and v=16→15 processes, where v is the vibrational quantum number. The long-range attraction causes the cross sections to be decreasing functions of energy below about 10 cm−1 and causes the thermally averaged deexcitation rate constants to have a minimum at about 1 K, but the Wigner threshold law holds only within 10−3 cm−1 of threshold and the Wigner singularity causes the rate constant to assume a nonzero temperature-independent value only below about 10−4 K. We also observe low-energy resonances in the CC calculations and these lead to additional structure in the rate constants but do not change the important conclusions.