Abstract:A general theory and calculation framework for the prediction of frequency-resolved single molecule photon counting statistics is presented. Expressions for the generating function of photon counts are derived, both for the case of naive "detection" based solely on photon emission from the molecule and also for experimentally realizable detection of emitted photons, and are used to explicitly calculate low-order photon-counting moments. The two cases of naive detection versus physical detection are compared to… Show more
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.
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.
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