Transition probability, nonadiabatic quantum

A and A = 0.1 eV. The adiabatic ground potential energy surface is shown in Fig. 11. The present results (solid line) are in good agreement with the quantum mechanical ones (solid circles). The minimum energy crossing point (MECP) is conventionally used as the transition state and the transition probability is represented by the value at this point. This is called the MECP approximation and does not work well, as seen in Fig. 10. This means that the coordinate dependence of the nonadiabatic transmission probability on the seam surface is important and should be taken into account as is done explicitly in Eq. (18). 

In calculating the transition probability for the nonadiabatic reactions, it is sufficient to use the lowest order of quantum mechanical perturbation theory in the operator V d. For the adiabatic reactions, we must perform the summation of the whole series of the perturbation theory.5 (It is insufficient to retain only the first term of the series that appeared in the quantum mechanical perturbation theory.) Correct calculations in both adiabatic and diabatic approaches lead to the same results, which is evidence of the equivalence of the two approaches. 

A general method for the calculation of the transition probability in the harmonic approximation developed in Ref. 44 enabled us to take into account, in a rigorous way, both the dependence of the tunneling of the quantum particles on the coordinates of other degrees of freedom of the system and the effects of the inertia and nonadiabaticity of the tunneling particle, taking into account the mixing of the normal coordinates of the system in the initial and... 

Both the initial- and the final-state wavefunctions are stationary solutions of their respective Hamiltonians. A transition between these states must be effected by a perturbation, an interaction that is not accounted for in these Hamiltonians. In our case this is the electronic interaction between the reactant and the electrode. We assume that this interaction is so small that the transition probability can be calculated from first-order perturbation theory. This limits our treatment to nonadiabatic reactions, which is a severe restriction. At present there is no satisfactory, fully quantum-mechanical theory for adiabatic electrochemical electron-transfer reactions. 

Nonadiabatic events (transition from the excited state to the ground state at the conical intersection) pose a serious challenge because the nonadiabatic transition is rigorously quantum mechanical without a well-defined classical analog. At a simple level of theory13 (we return to a better treatment subsequently), the probability of a surface hop is given as follows ... 

The simplest model is the following the diabatic potentials are constant with V2 - Vx = A > 0 and the diabatic coupling is V e R where A = 2V0. Recently, Osherov and Voronin obtained the quantum mechanically exact analytical solution for this model in terms of the Meijer function (38). In the adiabatic representation this system presents a three-channel problem at E > V2 > Vu since there is no repulsive wall at R Rx in the lower adiabatic potential. They have obtained the analytical expression of a 3 X 3 transition matrix. Adding a repulsive potential wall at R Rx for the lower adiabatic channel and using the semiclassical idea of independent events of nonadiabatic transition at Rx and adiabatic wave propagation elsewhere, they derived the overall inelastic nonadiabatic transition probability Pl2 as follows ... 

Ao and Rammer [166] obtained the same result (and more) on the basis of a fully quantum mechanical treatment. Frauenfelder and Wolynes [78] derived it from simple physical arguments. Equation (9.98) predicts a quasiadiabatic result, = h k/ v 1 and the Golden Rule result, Pk = k/ v, in the opposite limit, which is qualitatively similar to the Landau-Zener behavior of the transition probability but the implications are different. Equation (9.98) is the result of multiple nonadiabatic crossings of the delta sink although it does not depend on details of the stochastic process Xj- t). This can be understood from the following consideration. For each moment of time, the fast coordinate has a Gaussian distribution, p Xf, t) = (xy — Xj, transition region, the fast coordinate crosses it very frequently and thus forms an effective sink for the slow coordinate. 

If the interaction between the reactants leading to the reaction is weak enough (nonadiabatic processes), the transition probability per unit time may be calculated using the formula of the first order in quantum mechanical... 

Surface Hopping Model (SHM) first proposed by Tully and Preston [444] is a practical method to cope with nonadiabatic transition. It is actually not a theory but an intuitive prescription to take account of quantum coherent jump by replacing with a classical hop from one potential energy surface to another with a transition probability that is borrowed from other theories of semiclassical (or full quantum mechanical) nonadiabatic transitions state theory such as Zhu-Nakamura method. The fewest switch surface hopping method [445] and the theory of natural decay of mixing [197, 452, 509, 515] are among the most advanced methodologies so far proposed to practically resolve the critical difficulty of SET and the primitive version of SHM. 

Nonadiabatic transition probability compared with the full quantum values... 

The convergence property of the nonadiabatic transition amplitudes with respect to the number of branching generation is next studied. We here show the results only for the three-state model, since the two state model offers only an easier test. The transition probability of PSANB has been calculated with Eq. (6.78) with use of the branching paths of Fig. 6.5(a). This approximation is justified because the endpoints of the paths are generally very close to each other on the individual potential curves. To estimate the accuracy, we compare the probabilities with those obtained in the full quantum calculations described above. 

With the above simple background, we consider ET in complex systems. In this case, eqn (12.4) cannot be used straightforwardly because the nonadiabatic transition probability is explicitly dependent on the reaction coordinate and one does not know how to select this one-dimensional reaction coordinate from the multi-dimensional systems. Therefore, our strategy is to start from a generalized quantum rate expression. Miller et al. have shown that the... 

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