Cavity molecular dynamics simulations of vibrational polariton enhanced molecular nonlinear absorption

Abstract

Recent experiments have observed that the chemical and photophysical properties of molecules can be modified inside an optical Fabry-Perot microcavity under collective vibrational strong coupling (VSC) conditions, and such modification is currently not well understood by theory. In an effort to understand the origin of such cavity induced phenomena, some recent studies have focused on the effect of the cavity environment on the nonlinear optical response of the molecular subsystem. Here, we use a recently proposed protocol for classical cavity molecular dynamics (CavMD) simulations to numerically investigate the linear and nonlinear response of liquid carbon dioxide under such VSC conditions following an optical pulse excitation. We find that applying a strong pulse of excitation to the lower hybrid light-matter state, i.e., the lower polariton (LP), can lead to an overall molecular nonlinear absorption which is enhanced by up to two orders of magnitude relative to the excitation outside the cavity. This polariton-enhanced multiphoton absorption also causes an ultrashort LP lifetime (0.2 ps) under strong illumination. Unlike usual polariton relaxation processes -- whereby polaritonic energy transfers directly to the manifold of singly excited vibrational dark states -- under the present mechanism, the LP transfers energy directly to the manifold of higher vibrationally excited dark states; these highly excited dark states subsequently relax to the manifold of singly excited states with a lifetime of tens of ps. Because the present mechanism is generic in nature, we expect these numerical predictions to be experimentally observed in different molecular systems and in cavities with different volumes.

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Cited by in corpus (17)

• Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
• Theoretical Challenges in Polaritonic Chemistry
• Molecular orbital theory in cavity QED environments
• Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations
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• i-PI 3.0: a flexible and efficient framework for advanced atomistic simulations
• Enhanced optical nonlinearities under strong light-matter coupling
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• Generalization of the Tavis-Cummings model for multi-level anharmonic systems: insights on the second excitation manifold
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• When do molecular polaritons behave like optical filters?
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