Quantum simulation of solution phase intramolecular electron transfer rates in betaine-30

Mixed quantum-classical atomistic simulations have been carried out to investigate the mechanistic details of excited state intramolecular electron transfer in a betaine-30 molecule in acetonitrile. The key electronic degrees of freedom of the solute molecule are treated quantum mechanically using the semiempirical Pariser-Parr-Pople Hamiltonian, including the solvent influence on electronic structure. The intramolecular vibrational modes are also treated explicitly at a quantum level, with the remaining elements treated classically using empirical potentials. The electron-transfer rate, corresponding to S-1 -> S-0 relaxation, is evaluated via time-dependent perturbation theory with the explicit inclusion of the dynamics of solvation and intramolecular conformation. The calculations reveal that, while solvation dynamics is critical to the rate, the intramolecular torsional dynamics also plays an important role. The importance of the use of multiple high-frequency quantum modes is also discussed.