Energy transfer selection rules

If no transfer of translational energy occurs, then the charge exchange process probably takes place when the distance between the ion and the molecule is large. This means, however, that the ion and the molecule can be considered as isolated from each other, and therefore, the recombination process of the ion and the ionization process of the molecule must obey the spectroscopic transition laws. On the other hand, if a large transfer of translational energy takes place, then the process probably takes place when the distance is small, and possibly then all selection rules break down. 

If a charge exchange process, A + + B- A -f- B +, occurs when the distance between the two particles is large, we expect that no transfer of translational energy takes place in the reaction and that the same selection rules govern the ionization as in spectroscopic transitions. This means that if the molecule B is in a singlet state before the ionization, the ion B + will be formed in a doublet state after ionization of one electron without rearrangements of any other electrons, at least for small molecules. 

A further technique exists for the determination of triplet energy levels. This technique, called electron impact spectroscopy, involves the use of inelastic scattering of low-energy electrons by collision with molecules. The inelastic collisions of the electrons with the molecules result in transfer of the electron energy to the molecule and the consequent excitation of the latter. Unlike electronic excitation by photons, excitation by electron impact is subject to no spin selection rule. Thus transitions that are spin and/or orbitally forbidden for photon excitation are totally allowed for electron impact excitation. 

As a consequence of the quantum-mechanical selection rules for resonance energy transfer involving the spin wave functions of the donor and acceptor,... 

Selection rules for the electronic energy transfer by dipole-dipole interactions are the same as those for corresponding electric dipole transitions in the isolated molecules. The spin selection rule requires that the total multiplicity of the donor arid the acceptor, prior to and after the act of transfer, must be preserved. This implies that M0. - Mq and MA — MA where M s denote the multiplicity of the states (Section 2.5.1). 

A number of techniques have been used previously for the study of state-selected ion-molecule reactions. In particular, the use of resonance-enhanced multiphoton ionization (REMPI) [21] and threshold photoelectron photoion coincidence (TPEPICO) [22] has allowed the detailed study of effects of vibrational state selection of ions on reaction cross sections. Neither of these methods, however, are intrinsically capable of complete selection of the rotational states of the molecular ions. The TPEPICO technique or related methods do not have sufficient electron energy resolution to achieve this, while REMPI methods are dependent on the selection rules for angular momentum transfer when a well-selected intermediate rotational state is ionized in the most favorable cases only a partial selection of a few ionic rotational states is achieved [23], There can also be problems in REMPI state-selective experiments with vibrational contamination, because the vibrational selectivity is dependent on a combination of energetic restrictions and Franck-Condon factors. 

Insufficient experimental data is available to demonstrate either the occurrence or lack of selection rules. In Table 15, some of the fastest reactions do correspond to transitions allowed for both atoms. Singlet helium transfers to Ne at a rate consistent with the data in Fig. 26, whereas triplet helium transfers comparatively slowly neither of the He transitions is allowed. However, there appear to be other cases, discussed earlier, where a forbidden transition is preferred to an allowed transition. Stepp and Anderson146 have suggested that there is partial conservation of electronic angular momentum accompanying energy transfer between atoms, and interpreted experiments on mercury fluorescence by means of the steps... 

Ewing, G.E. (1987). Selection rules for vibrational energy transfer Vibrational predissociation of van der Waals molecules, J. Phys. Chem. 91, 4662-4671. 

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