Transformation from adiabatic diabatic basis

Sadygov R G and Yarkony D R 1998 On the adiabatic to diabatic states transformation in the presence of a conical intersection a most diabatic basis from the solution to a Poisson s equation. I J. Chem. Rhys. 109 20... 

Formally, we can write the unitary transformation from the adiabatic to the diabatic basis as... 

The unitary transformation from a basis of adiabatic electronic states to a basis of diabatic electronic states is given by... 

While both populations are equivalent in principle, being related by a unitary transformation, one of them may be more clo.sely related to experiment than the other. For example, if there are dipole. selection rules forbidding the optical transition to or from a subset of the interacting electronic states, these selection rules are usually obeyed to a much larger extent in the diabatic basis than in the adiabatic ba.si.s. Then the diabatic electronic populations are monitored via the intensities of spontaneous and induced emission (the adiabatic populations may be more relevant if the optical transition takes place within the interacting manifold). More specifically, in the limit of ideally short pump and probe pulses the time-resolved pump-probe signal as a function of the delay time has been shown to be proportional to the diabatic population, equation (51). For the more realistic case of finite pulse durations the situation is more complex. In the present article we leave these problems aside and focus on the purely intramolecular aspects of the vibronic dynamics. The various aspects associated with their detection in real time have been surveyed in a recent review article. ... 

In this section, diabatization is formed employing the adiabatic-to-diabatic transformation matrix A, which is a solution of Eq. (19). Once A is calculated, the diabatic potential matiix W is obtained from Eq. (22). Thus Eqs. (19) and (22) form the basis for the procedure to obtain the diabatic potential matrix elements. 

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