Affiliation:
1. Institute of Theoretical and Computational Physics, Department of Physics, University of Crete, 71003 Heraklion, Greece
Abstract
Ultrafast reaction processes take place when resonant features of nonlinear model systems are taken into account. In the targeted energy or electron transfer dimer model this is accomplished through the implementation of nonlinear oscillators with opposing types of nonlinearities, one attractive while the second repulsive. In the present work, we show that this resonant behavior survives if we take into account the vibrational degrees of freedom as well. After giving a summary of the basic formalism of chemical reactions we show that resonant electron transfer can be assisted by vibrations. We find the condition for this efficient transfer and show that in the case of additional interaction with noise, a distinct non-Arrhenius behavior develops that is markedly different from the usual Kramers-like activated transfer.
Funder
Stavros Niarchos Foundation
Reference49 articles.
1. Brownian motion in a field of force and the diffusion model of chemical reactions;Kramers;Physica,1940
2. Lindenberg, K., and West, B.J. (1996). The Nonequilibrium Statistical Mechanics of Open and Closed Systems, Wiley-VCH.
3. Malgaretti, P., Pagonabarraga, I., and Rubi, J.M. (2016). Rectification and Non-Gaussian Diffusion in Heterogeneous Media. Entropy, 18.
4. Understanding entropic barriers;Zeradjanin;Nat. Energy,2024
5. Schlawin, F., Gessner, M., Buchleitner, A., Schätz, T., and Skourtis, S.S. (2021). Continuously Parametrized Quantum Simulation of Molecular Electron-Transfer Reactions. PRX Quantum, 2.