Non-adiabatic transfer

Larsson, S. (1981) Electron transfer in chemical and biological systems orbital rules for non-adiabatic transfer. Journal of the American Chemical Society, 103, 4034 4040. 

Larsson S. Electron-Transfer in Chemical and Biological Systems - Orbital Rules for Non-Adiabatic Transfer. J. Am. Chem. Soc. 1981 103 4034-4040. 

The ultimate approach to simulate non-adiabatic effects is tln-ough the use of a fiill Scln-ddinger wavefunction for both the nuclei and the electrons, using the adiabatic-diabatic transfomiation methods discussed above. The whole machinery of approaches to solving the Scln-ddinger wavefiinction for adiabatic problems can be used, except that the size of the wavefiinction is now essentially doubled (for problems involving two-electronic states, to account for both states). The first application of these methods for molecular dynamical problems was for the charge-transfer system... 

To add non-adiabatic effects to semiclassical methods, it is necessary to allow the trajectories to sample the different surfaces in a way that simulates the population transfer between electronic states. This sampling is most commonly done by using surface hopping techniques or Ehrenfest dynamics. Recent reviews of these methods are found in [30-32]. Gaussian wavepacket methods have also been extended to include non-adiabatic effects [33,34]. Of particular interest here is the spawning method of Martinez, Ben-Nun, and Levine [35,36], which has been used already in a number of direct dynamics studies. 

The original semiclassical version of the centrifugal sudden approximation (SCS) developed by Strekalov [198, 199] consistently takes into account adiabatic corrections to IOS. Since the orbital angular momentum transfer is supposed to be small, scattering occurs in the collision plane. The body-fixed correspondence principle method (BFCP) [200] was used to write the S-matrix for f — jf Massey parameter a>xc. At low quantum numbers, when 0)zc —> 0, it reduces to the usual non-adiabatic expression, which is valid for any Though more complicated, this method is the necessary extension of the previous one adapted to account for adiabatic corrections at higher excitation... 

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... 

Figure 2.2 Adiabatic and non-adiabatic electron transfer (schematic). The splitting at the intersection has been exaggerated.

Ab initio thermodynamics, 129-155 Acetaldehyde oxidation, 196-197, 624 Acetic acid, 192-198, 394-395 Active sites in electrocatalysis, 93-124, 159-198, 237,250,253 Adiabatic and non-adiabatic electron transfer, 34... 

The effects of deviations from the Born-Oppenheimer approximation (BOA) due to the interaction of the electron in the sub-barrier region with the local vibrations of the donor or the acceptor were considered for electron transfer processes in Ref. 68. It was shown that these effects are of importance for long-distance electron transfer since in this case the time when the electron is in the sub-barrier region may be long as compared to the period of the local vibration.68 A similar approach has been used in Ref. 65 to treat non-adiabatic effects in the sub-barrier region in atom transfer processes. However, nonadiabatic effects in the classically attainable region may also be of importance in atom transfer processes. In the harmonic approximation, when these effects are taken into account exactly, they manifest themselves in the noncoincidence of the... 

In this section, we switch gears slightly to address another contemporary topic, solvation dynamics coupled into the ESPT reaction. One relevant, important issue of current interest is the ESPT coupled excited-state charge transfer (ESCT) reaction. Seminal theoretical approaches applied by Hynes and coworkers revealed the key features, with descriptions of dynamics and electronic structures of non-adiabatic [119, 120] and adiabatic [121-123] proton transfer reactions. The most recent theoretical advancement has incorporated both solvent reorganization and proton tunneling and made the framework similar to electron transfer reaction, [119-126] such that the proton transfer rate kpt can be categorized into two regimes (a) For nonadiabatic limit [120] ... 

Expressions for the transition between adiabatic and non-adiabatic dissociative electron transfers have also recently been derived.54... 

In total, the situation is less favorable in terms of quantum yields than in the preceding case. Indeed, even if the cleavage rate constant is large enough to overcome back electron transfer from the ion pair (kc k act), the maximal value of the quantum yield is 1/(1 + P), which would reach unity only in the unlikely case where the ground-state electron transfer was entirely non-adiabatic (H = 0). 

Thus, from equation (63), the magnitude of the electronic coupling matrix element may finally be estimated, leading to values of 21 and 24 meV for EDA and perylene, respectively. That these values are quite reasonable derives from the observation that they correspond to moderately non-adiabatic electron transfer at the ground state (with electronic factors of 2 /(1 + P) - 0.5 and 0.6 with EDA and perylene, respectively). 

Fig. 5 Potential energy hypersurfaces as a function of the reaction coordinate for adiabatic (A, single-minimum potential B, double-minimum potential) and non-adiabatic (C) electron-transfer reactions.

The picture here is of uncoupled Gaussian functions roaming over the PES, driven by classical mechanics. The coefficients then add the quantum mechanics, building up the nuclear wavepacket from the Gaussian basis set. This makes the treatment of non-adiabatic effects simple, as the coefficients are driven by the Hamiltonian matrices, and these elements couple basis functions on different surfaces, allowing transfer of population between the states. As a variational principle was used to derive these equations, the coefficients describe the time dependence of the wavepacket as accurately as possible using the given... 

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