Manipulating the Dynamics of a Fermi Resonance with Light. A Direct Optimal Control Theory Approach

TL;DR

This paper applies direct optimal control theory to manipulate Fermi resonance dynamics in molecules, enabling precise control of vibrational energy redistribution without the need for complex derivative calculations.

Contribution

It extends direct optimal control theory to exact wavepacket propagation in Fermi resonance models, allowing for optimized population control of vibrational states.

Findings

Successfully applied to a Fermi-resonance model

Enabled control of overtone state populations

Reduced intramolecular vibrational energy redistribution

Abstract

Direct optimal control theory for quantum dynamical problems presents itself as an interesting alternative to the traditional indirect optimal control. The method relies on the first discretize and then optimize paradigm, where a discretization of the dynamical equations leads to a nonlinear optimization problem. It has been applied successfully to the control of a bistable system where the wavepacket had been approximated by a parameterized Gaussian, leading to a semiclassical set of equations of motion (A. R. Ramos Ramos, O. K\"uhn, Front. Phys. 9 (2021) 615168). Motivated by these results, in the present paper we extend the application of the method to the case of exact wavepacket propagation using the example of a generic Fermi-resonance model. In particular we address the question how population of the involved overtone state can be avoided such as to reduce the effect of intramolecular vibrational energy redistribution. A methodological advantage is that direct optimal control theory offers flexibility when choosing the running cost, since there is no need to compute functional derivatives and coupling terms as in the case of indirect optimal control. We exploit this fact to include state populations in the running cost, which allows their optimization.