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Title: Non-adiabatic dynamics of molecules in optical cavities

Strong coupling of molecules to the vacuum field of micro cavities can modify the potential energy surfaces thereby opening new photophysical and photochemical reaction pathways. While the influence of laser fields is usually described in terms of classical field, coupling to the vacuum state of a cavity has to be described in terms of dressed photon-matter states (polaritons) which require quantized fields. We present a derivation of the non-adiabatic couplings for single molecules in the strong coupling regime suitable for the calculation of the dressed state dynamics. The formalism allows to use quantities readily accessible from quantum chemistry codes like the adiabatic potential energy surfaces and dipole moments to carry out wave packet simulations in the dressed basis. In conclusion, the implications for photochemistry are demonstrated for a set of model systems representing typical situations found in molecules.
Authors:
ORCiD logo [1] ;  [1] ;  [1]
  1. Univ. of California, Irvine, CA (United States)
Publication Date:
Grant/Contract Number:
FG02-04ER15571
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 5; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of California, Irvine, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1469202
Alternate Identifier(s):
OSTI ID: 1236993

Kowalewski, Markus, Bennett, Kochise, and Mukamel, Shaul. Non-adiabatic dynamics of molecules in optical cavities. United States: N. p., Web. doi:10.1063/1.4941053.
Kowalewski, Markus, Bennett, Kochise, & Mukamel, Shaul. Non-adiabatic dynamics of molecules in optical cavities. United States. doi:10.1063/1.4941053.
Kowalewski, Markus, Bennett, Kochise, and Mukamel, Shaul. 2016. "Non-adiabatic dynamics of molecules in optical cavities". United States. doi:10.1063/1.4941053. https://www.osti.gov/servlets/purl/1469202.
@article{osti_1469202,
title = {Non-adiabatic dynamics of molecules in optical cavities},
author = {Kowalewski, Markus and Bennett, Kochise and Mukamel, Shaul},
abstractNote = {Strong coupling of molecules to the vacuum field of micro cavities can modify the potential energy surfaces thereby opening new photophysical and photochemical reaction pathways. While the influence of laser fields is usually described in terms of classical field, coupling to the vacuum state of a cavity has to be described in terms of dressed photon-matter states (polaritons) which require quantized fields. We present a derivation of the non-adiabatic couplings for single molecules in the strong coupling regime suitable for the calculation of the dressed state dynamics. The formalism allows to use quantities readily accessible from quantum chemistry codes like the adiabatic potential energy surfaces and dipole moments to carry out wave packet simulations in the dressed basis. In conclusion, the implications for photochemistry are demonstrated for a set of model systems representing typical situations found in molecules.},
doi = {10.1063/1.4941053},
journal = {Journal of Chemical Physics},
number = 5,
volume = 144,
place = {United States},
year = {2016},
month = {2}
}