Abstract
Strong light-matter coupling provides a new strategy to manipulate the non-adiabatic dynamics of molecules by modifying potential energy surfaces. The vacuum field of nanocavities can couple strongly with the molecular degrees of freedom and form hybrid light-matter states, termed as polaritons or dressed states. The photochemistry of molecules possessing intrinsic conical intersections can be significantly altered by introducing cavity couplings to create new conical intersections or avoided crossings. Here, we explore the effects of optical cavities on the photo-induced hydrogen elimination reaction of pyrrole. Wave packet dynamics simulations have been performed on the two-state, two-mode model of pyrrole, combined with the cavity photon mode. Our results show how the optical cavities assist in controlling the photostability of pyrrole and influence the reaction mechanism by providing alternative dissociation pathways. The cavity effects have been found to be intensely dependent on the resonance frequency. We further demonstrate the importance of the vibrational cavity couplings and dipole-self interaction terms in describing the cavity-modified non-adiabatic dynamics.
Highlights
Photochemistry involves the interaction of matter with light and plays an important role in synthetic chemistry, biology, and material sciences.[1−3] Photochemical reactions are crucial in processes such as photosynthesis,[4] vision,[5] and storage of solar energy,[6] but they can possess detrimental effects such as DNA damage[7] and modification of the efficiency of solar cells.[8]
The optical cavity can either accelerate or inhibit the photodissociation reaction of pyrrole depending on their frequency and coupling strength
The longest lifetime (1.5 ps) has been observed for a cavity frequency of 1.56 eV, which we found to be an optimum for stabilizing the photodissociation dynamics of pyrrole
Summary
Photochemistry involves the interaction of matter with light and plays an important role in synthetic chemistry, biology, and material sciences.[1−3] Photochemical reactions are crucial in processes such as photosynthesis,[4] vision,[5] and storage of solar energy,[6] but they can possess detrimental effects such as DNA damage[7] and modification of the efficiency of solar cells.[8] photochemical reactions need to be either accelerated or suppressed depending on their applications These manipulations can be achieved by chemical modifications and classical laser fields.[9−12] In recent times, strong light-matter coupling introduced by the optical cavities has evolved as a new tool to control the photochemical processes.[13−17] The lightmatter interaction can be considered to be strong when the energy exchange rate between matter and the cavity mode outpaces all incoherent decay processes. These modified PESs correspond to the polaritonic states and determine the dynamics of the coupled cavity-molecular system
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