Stark absorption and Stark fluorescence spectroscopies: Theory and simulations

Stark spectroscopy experiments are widely used to study the properties of molecular systems, particularly those containing charge-transfer (CT) states. However, due to the small transition dipole moments and large static dipole moments of the CT states, the standard interpretation of the Stark absorption and Stark fluorescence spectra in terms of the Liptay model may be inadequate. In this work, we provide a theoretical framework for calculations of Stark absorption and Stark fluorescence spectra and propose new methods of simulations that are based on the quantum-classical theory. In particular, we use the forward-backward trajectory solution and a variant of the Poisson bracket mapping equation, which have been recently adapted for the calculation of conventional (field-free) absorption and fluorescence spectra. For comparison, we also apply the recently proposed complex time-dependent Redfield theory, while exact results are obtained using the hierarchical equations of motion approach. We show that the quantum-classical methods produce accurate results for a wide range of systems, including those containing CT states. The CT states contribute significantly to the Stark spectra, and the standard Liptay formalism is shown to be inapplicable for the analysis of spectroscopic data in those cases. We demonstrate that states with large static dipole moments may cause a pronounced change in the total fluorescence yield of the system in the presence of an external electric field. This effect is correctly captured by the quantum-classical methods, which should therefore prove useful for further studies of Stark spectra of real molecular systems. As an example, we calculate the Stark spectra for the Fenna-Matthews-Olson complex of green sulfur bacteria.