Curve crossing adiabatic

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. 

Zhu and Nakamura proved that the intriguing phenomenon of complete reflection occurs in the ID NT type potential curve crossing [1, 14]. At certain discrete energies higher than the bottom of the upper adiabatic potential, the particle cannot transmit through the potential from right to left or vice versa. The overall transmission probability P (see Fig. 45) is given by... 

In this section, we introduce the model Hamiltonian pertaining to the molecular systems under consideration. As is well known, a curve-crossing problem can be formulated in the adiabatic as well as in a diabatic electronic representation. Depending on the system under consideration and on the specific method used, both representations have been employed in mixed quantum-classical approaches. While the diabatic representation is advantageous to model potential-energy surfaces in the vicinity of an intersection and has been used in mean-field type approaches, other mixed quantum-classical approaches such as the surfacehopping method usually employ the adiabatic representation. 

To summarize, it has been found that the SH method is able to at least qualitatively describe the complex photoinduced electronic and vibrational relaxation dynamics exhibited by the model problems under consideration. The overall quality of SH calculations is typically somewhat better than the quality of the mean-field trajectory results. In particular, this holds in the case of several curve crossings (see Fig. 2) as well as when the dynamics and the observables of interest are essentially of adiabatic nature— for example, for the calculation of the adiabatic population dynamics associated with a conical intersection (see Figs. 3 and 12). Furthermore, we have briefly discussed various consistency problems of a simple quasi-classical SH description. It has been shown that binned electronic population probabilities and no momentum adjustment for classically forbidden transitions help us to improve this matter. There have been numerous suggestions to further improve the hopping algorithm [70-74] however, the performance of all these variants seems to depend largely on the problem under consideration. 

Figure 1. Diabatic potential energy curves for Nal with an expanded view of the adiabatic potential curves, e, and Ej, near the diabatic curve crossing.

In principle, excitation transfer at curve crossings may also occur at thermal collision energies, but only under rather restricted conditions, because at low collision energies the system will usually follow the adiabatic curve V (R)- The following two exceptions may arise ... 

Formulated in another way, the metal (M)-level is suddenly pulled down from well above to well below the ligand (L) valence levels a distance larger than the exchange splitting 2H]2 as a consequence, the system cannot follow adiabatically but undergoes a diabatic (curve crossing) transition to an excited state of the ionic system. 

Fig. 14.4 A schematic display of a curve crossing reaction in the diabatic and adiabatic representations. See Section 2.4 for further details. (Note This is same as Fig. 2.3).

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