Targeted energy transfer dynamics and chemical reactions

TL;DR

This paper investigates how vibrational degrees of freedom influence ultrafast energy transfer and chemical reactions, revealing conditions for resonant electron transfer and unique non-Arrhenius behavior under noise.

Contribution

It demonstrates that vibrational effects preserve resonant energy transfer dynamics and identifies conditions for efficient transfer in nonlinear oscillator models.

Findings

Vibrations assist resonant electron transfer.

Non-Arrhenius behavior emerges with noise.

Resonant dynamics survive vibrational considerations.

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 on 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.