Non-adiabatic dynamics of molecules in optical cavities
Abstract
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:
-
- Univ. of California, Irvine, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Irvine, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1469202
- Alternate Identifier(s):
- OSTI ID: 1236993
- Grant/Contract Number:
- FG02-04ER15571
- Resource 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)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Kowalewski, Markus, Bennett, Kochise, and Mukamel, Shaul. Non-adiabatic dynamics of molecules in optical cavities. United States: N. p., 2016.
Web. doi:10.1063/1.4941053.
Kowalewski, Markus, Bennett, Kochise, & Mukamel, Shaul. Non-adiabatic dynamics of molecules in optical cavities. United States. https://doi.org/10.1063/1.4941053
Kowalewski, Markus, Bennett, Kochise, and Mukamel, Shaul. Fri .
"Non-adiabatic dynamics of molecules in optical cavities". United States. https://doi.org/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 = {Fri Feb 05 00:00:00 EST 2016},
month = {Fri Feb 05 00:00:00 EST 2016}
}
Web of Science
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