Adiabatic transition dipole moment

The mixing parameter Ae makes the CT free energy surfaces dependent on the gas-phase, adiabatic transition dipole moment. The standard extension... 

The mixing parameter Ae makes the CT free energy surfaces dependent on the gas-phase, adiabatic transition dipole moment. The standard extension of the MH theory on the case of strong electronic overlap85 assumes a nonzero ET matrix element Hab, but neglects the diabatic transition dipole (or eliminates... 

Because of difficulties in calculating the non-adiabatic conpling terms, this method did not become very popular. Nevertheless, this approach, was employed extensively in particular to simulate spectroscopic measurements, with a modification introduced by Macias and Riera [47,48]. They suggested looking for a symmetric operator that behaves violently at the vicinity of the conical intersection and use it, instead of the non-adiabatic coupling term, as the integrand to calculate the adiabatic-to-diabatic transformation. Consequently, a series of operators such as the electronic dipole moment operator, the transition dipole moment operator, the quadrupole moment operator, and so on, were employed for this purpose [49,52,53,105]. However, it has to be emphasized that immaterial to the success of this approach, it is still an ad hoc procedure. 

Taylor series 260 torque, correlation functions 28 transfer time, rotational relaxation 51 transitions dipole moment 30 forbidden 30 non-adiabatic 130 translational velocity v 6... 

The potential energy curves (Fig. 1), the non-adiabatic coupling, transition dipole moments and other system parameters are same as those used in our previous work (18,19,23,27). The excited states 1 B(0 ) and 2 B( rio) are non-adiabatically coupled and their potential energy curves cross at R = 6.08 a.u. The ground 0 X( Eo) state is optically coupled to both the and the 2 R( nJ) states with the transition dipole moment /ioi = 0.25/xo2-The results to be presented are for the cw field e(t) = A Yll=o cos (w - u pfi)t described earlier. However, for IBr, we have shown (18) that similar selectivity and yield may be obtained using Gaussian pulses too. 

The GMH method of Cave and Newton [39, 40] is based on the assumption that the transition dipole moment between the diabatic donor and acceptor states vanishes, i.e., the off-diagonal element of the corresponding dipole moment matrix is zero. Thus, in the localization transformation one diagonalizes the dipole moment matrix of the adiabatic states ij/i and ij/z. For a two-state model, the rotation angle ft) can be expressed with the help of the transition dipole moment and the difference of the dipole mo-... 

Here inv stands for an invariant in respect to transformation consistent with the symmetry of the system. For quantum mechanical operators, this means unitary transformations. The parameter Ae in Eq. [107] quantifies the extent of mixing between two adiabatic gas-phase states induced by the interaction with the solvent. For a dipolar solute, it is determined through the adiabatic differential and the transition dipole moments... 

Here, [in is the transition dipole moment for the transition between V22 and Vn. In the adiabatic approximation (see, e.g.. Ret. [Stenholm 1994]), the coupled bare potentials V22 and V33 can be replaced by uncoupled adiabatic potentials. Using the rotating-wave approximation, the dynamics of the system is then described by the Schrodinger equation... 

Fig. 3. x-component of the adiabatic (a) and diabatic (b) transition dipole moment for the So — S transition of pyrazine in the Qoa — QlOa space, taken from Ref. 38. 

It should be stressed that for multidimensional curve crossing problems the low-order Taylor expansions (8), (9) and (19) are justified only in the diabatic electronic representation. In the adiabatic representation, curve crossings generally lead to rapid variations of potential-energy functions and transition dipole moments, rendering a low-order Taylor expansion of these functions in terms of nuclear coordinates meaningless. 

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