## Rate constants for the photodissociation of the *b* ^{3}Σ^{+} state as a function of the temperature *T*_{*} of the blackbody, for different Maxwell–Boltzmann distribution temperatures *T*_{M − B}

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**Figure 8.** Rate constants for the photodissociation of the *b* ^{3}Σ^{+} state as a function of the temperature *T*_{*} of the blackbody, for different Maxwell–Boltzmann distribution temperatures *T*_{M − B}. The *T _{MB}* = 2 result, for which only the

*v*'' = 0,

*J*'' = 0 level is populated, is obtained for all Maxwell–Boltzmann distribution temperatures if the vibrational dependence of the cross section is neglected, as the photodissociation cross sections for all

*v*'',

*J*'' levels are then assumed to be equal to the cross section for the

*v*'' = 0,

*J*'' = 0'' level.

**Abstract**

We illustrate some of the difficulties that may be encountered when computing photodissociation and radiative association cross sections from the same time-dependent approach based on wavepacket propagation. The total and partial photodissociation cross sections from the 33 vibrational levels of the *b* ^{3}Σ^{+} state of HeH^{+} towards the nine other ^{3}Σ^{+} and 6 ^{3}Π *n* = 2, 3 higher lying electronic states are calculated, using the autocorrelation method introduced by Heller (1978 *J. Chem. Phys.* **68** 3891) and the method based on the asymptotic behaviour of wavepackets introduced by Balint-Kurti *et al* (1990 *J. Chem. Soc. Faraday Trans.* **86** 1741). The corresponding radiative association cross sections are extracted from the same calculations, and the photodissociation and radiative association rate constants are determined.