Theoretical Quantum Control of Fluctuating Molecular Energy Levels in Complex Chemical Environments

Abstract

AbstractIn the present study, quantum control simulations are performed to explore the theoretical and practical limits of controlling applied synthetic chemistry in solution. To this extent a reactive model coordinate is used which captures the essential features of an atomistic and dynamic solvent environment during a picosecond control scenario. The time‐resolved influence of a molecular environment is revealed to fluctuate on a time‐scale of few hundred femtoseconds. Laser pulse optimizations are performed for different control scenarios, giving general experimental guidelines on how to find a reasonable tradeoff between pulse complexity and population yield. Few‐cycle flexible terahertz pulses are found to be capable of handling the complexities which are introduced by a fluctuating environment to the quantum properties of the molecular system. Besides the practical limitations in pulse generation and shaping, there seem to be no theoretical limits to controlling the investigated process with its environmental fluctuations. As the chosen model system involves a methyl group transfer and carbon–carbon formation, it stands representative for other commonly performed synthetic schemes in modern organic and pharmaceutical chemistry.