Abstract
The precise determination of the excitation energies in condensed-phase molecular systems is important for understanding system-environment interactions as well as for the prerequisite input data of theoretical models used to study the dynamics of the system. The excitation energies are usually determined by fitting of the measured optical spectra that contain broad and unresolved peaks as a result of the thermally random dynamics of the environment. Herein, we propose a method for precise energy determination by strongly coupling the molecular system to an optical cavity and measuring the energy of the resulting polariton. The effect of thermal fluctuations induced by the environment on the polariton is also investigated, from which a power scaling law relating the polariton's linewidth to the number of molecules is obtained. The power exponent gives important information about the environmental dynamics.
Highlights
Embedded in the high density of environmental particles, the excitation energies of molecules in the condensed phase can be modified from their values in the gas phase by the static influence of various kinds of system-environment interactions [1,2] including electrostatic interaction and hydrogen bonding [3,4,5,6,7,8], as well as the effects of molecular conformation [9,10]
We have demonstrated that the sharp and isolated peak of lower polariton (LP) appears in the molecularabsorption spectrum, which can be used for precise determination of molecular excitation energies
We have demonstrated that a precise determination of the excitation energies of condensed-phase molecular systems is possible by strongly coupling the molecules to an optical cavity and measuring the energy of the LP, which is a mixture of light and matter degrees of freedom
Summary
Embedded in the high density of environmental particles, the excitation energies of molecules in the condensed phase can be modified from their values in the gas phase by the static influence of various kinds of system-environment interactions [1,2] including electrostatic interaction and hydrogen bonding [3,4,5,6,7,8], as well as the effects of molecular conformation [9,10]. In this paper we propose a method for the precise determination of the excitation energies of condensed-phase molecular systems by strongly coupling the molecules to an optical cavity and measuring the energy of the polariton that results from the hybridization of the degrees of freedom of light and matter. The underlying mechanism that allows a precise determination of the excitation energies of condensed-phase molecular systems is that the polariton appears as a sharp peak in optical spectra under the strong coupling between the cavity mode and the electronic excitations of molecules. The molecular-absorption and cavitytransmission spectroscopies are calculated for molecular systems with different types of orientations
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