Laser control strategies in full dimensional funneling dynamics: The case of pyrazine

TL;DR

This study develops laser control strategies inspired by interference and kicks to optimize population transfer in pyrazine's funneling dynamics, achieving significant population deposition in the acceptor state through a two-step process.

Contribution

It introduces a combined reduced and full-dimensional modeling approach for laser control of molecular funneling, demonstrating effective population transfer in pyrazine.

Findings

Achieved about 60% population transfer to the acceptor state.

Developed a robust control method within experimental laser field constraints.

Demonstrated potential scalability to larger molecular systems.

Abstract

Motivated by the major role funneling dynamics plays in light-harvesting processes, we built some laser control strategies inspired from basic mechanisms such as interference and kicks, and apply them to the case of pyrazine. We are studying the internal conversion between the two excited states, the highest and directly reachable from the initial ground state being considered as a donor, and the lowest as an acceptor. The ultimate control objective is the maximum population deposit in the otherwise dark acceptor, from a two-step process: radiative excitation of the donor, followed by a conical-intersection-mediated funneling towards the acceptor. The overall idea is to first obtain the control field parameters (individual pulses leading frequency and intensity, duration and inter-pulse time delay) for tractable reduced dimensional models basically describing the conical intersection branching space. Once these parameters are optimized, they are fixed and used in full dimensional dynamics describing the electronic population transfer. In the case of pyrazine, the reduced model is 4 dimensional, whereas the full dynamics involve 24 vibrational modes. Within experimentally achievable electromagnetic field requirements, we obtain a robust control with about 60 % of the ground state population deposited in the acceptor state, while about 16 % remains in the donor. Moreover, we anticipate a possible transposition to the control of even larger molecular systems, for which only a small number of normal modes are active, among all the others acting as spectators in the dynamics.