Waveform control of molecular dynamics close to a conical intersection

Abstract

Conical intersections are ubiquitous in chemical systems but, nevertheless, extraordinary points on the molecular potential energy landscape. They provide ultra-fast radiationless relaxation channels, their topography influences the product branching, and they equalize the timescales of the electron and nuclear dynamics. These properties reveal optical control possibilities in the few femtosecond regime. In this theoretical study, we aim to explore control options that rely on the carrier envelope phase of a few-cycle IR pulse. The laser interaction creates an electronic superposition just before the wave packet reaches the conical intersection. The imprinted phase information is varied by the carrier envelope phase to influence the branching ratio after the conical intersection. We test and analyze this scenario in detail for a model system and show to what extent it is possible to transfer this type of control to a realistic system like uracil.