Ab initio polaritonic potential-energy surfaces for excited-state nanophotonics and polaritonic chemistry
Abstract
Advances in nanophotonics, quantum optics, and low-dimensional materials have enabled precise control of light–matter interactions down to the nanoscale. Combining concepts from each of these fields, there is now an opportunity to create and manipulate photonic matter via strong coupling of molecules to the electromagnetic field. Toward this goal, here we demonstrate a first principles framework to calculate polaritonic excited-state potential-energy surfaces, transition dipole moments, and transition densities for strongly coupled light–matter systems. In particular, we demonstrate the applicability of our methodology by calculating the polaritonic excited-state manifold of a formaldehyde molecule strongly coupled to an optical cavity. This proof-of-concept calculation shows how strong coupling can be exploited to alter photochemical reaction pathways by influencing avoided crossings with tuning of the cavity frequency and coupling strength. Therefore, by introducing an ab initio method to calculate excited-state potential-energy surfaces, our work opens a new avenue for the field of polaritonic chemistry.
- Authors:
-
[1];
[2]
- Harvard University, Cambridge, Massachusetts (United States). John A. Paulson School of Engineering and Applied Sciences; Flatiron Institute, New York (United States). Center for Computational Quantum Physics
- Harvard University, Cambridge, Massachusetts (United States). John A. Paulson School of Engineering and Applied Sciences
- Publication Date:
- Research Org.:
- Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); German Research Foundation (DFG); USDOE Advanced Research Projects Agency - Energy (ARPA-E)
- OSTI Identifier:
- 1803588
- Alternate Identifier(s):
- OSTI ID: 1657878
- Grant/Contract Number:
- SC0019140; FL997/1-1
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 153; Journal Issue: 9; 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; Photochemical reactions; Quantum optics; Optical resonators; Ab-initio methods; Nano optics; Transition moment; Potential energy surfaces; Electromagnetism; Time dependent density functional theory; Photon scattering
Citation Formats
Flick, Johannes, and Narang, Prineha. Ab initio polaritonic potential-energy surfaces for excited-state nanophotonics and polaritonic chemistry. United States: N. p., 2020.
Web. doi:10.1063/5.0021033.
Flick, Johannes, & Narang, Prineha. Ab initio polaritonic potential-energy surfaces for excited-state nanophotonics and polaritonic chemistry. United States. https://doi.org/10.1063/5.0021033
Flick, Johannes, and Narang, Prineha. Fri .
"Ab initio polaritonic potential-energy surfaces for excited-state nanophotonics and polaritonic chemistry". United States. https://doi.org/10.1063/5.0021033. https://www.osti.gov/servlets/purl/1803588.
@article{osti_1803588,
title = {Ab initio polaritonic potential-energy surfaces for excited-state nanophotonics and polaritonic chemistry},
author = {Flick, Johannes and Narang, Prineha},
abstractNote = {Advances in nanophotonics, quantum optics, and low-dimensional materials have enabled precise control of light–matter interactions down to the nanoscale. Combining concepts from each of these fields, there is now an opportunity to create and manipulate photonic matter via strong coupling of molecules to the electromagnetic field. Toward this goal, here we demonstrate a first principles framework to calculate polaritonic excited-state potential-energy surfaces, transition dipole moments, and transition densities for strongly coupled light–matter systems. In particular, we demonstrate the applicability of our methodology by calculating the polaritonic excited-state manifold of a formaldehyde molecule strongly coupled to an optical cavity. This proof-of-concept calculation shows how strong coupling can be exploited to alter photochemical reaction pathways by influencing avoided crossings with tuning of the cavity frequency and coupling strength. Therefore, by introducing an ab initio method to calculate excited-state potential-energy surfaces, our work opens a new avenue for the field of polaritonic chemistry.},
doi = {10.1063/5.0021033},
journal = {Journal of Chemical Physics},
number = 9,
volume = 153,
place = {United States},
year = {Fri Sep 04 00:00:00 EDT 2020},
month = {Fri Sep 04 00:00:00 EDT 2020}
}
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