Multidimensional Coherent Spectroscopy of Molecular Polaritons: Langevin Approach

Zhedong Zhang, Xiaoyu Nie, Dangyuan Lei, and Shaul Mukamel

Phys. Rev. Lett. 130, 103001 – Published 10 March 2023

Abstract

We present a microscopic theory for nonlinear optical spectroscopy of $N$ molecules in an optical cavity. Using the Heisenberg-Langevin equation, an analytical expression is derived for the time- and frequency-resolved signals accounting for arbitrary numbers of vibrational excitations. We identify clear signatures of the polariton-polaron interaction from multidimensional projections of the signal, e.g., pathways and timescales. Cooperative dynamics of cavity polaritons against intramolecular vibrations is revealed, along with a crosstalk between long-range coherence and vibronic coupling that may lead to localization effects. Our results further characterize the polaritonic coherence and the population transfer that is slower.

Received 8 August 2022
Accepted 3 January 2023

DOI:https://doi.org/10.1103/PhysRevLett.130.103001

Physics Subject Headings (PhySH)

Atoms, ions, & molecules in cavities Chemical Physics & Physical Chemistry Light-matter interaction Polaritons

Molecules Organic microcavities

Atomic, Molecular & Optical

Authors & Affiliations

Zhedong Zhang ^1,2,*, Xiaoyu Nie ³, Dangyuan Lei⁴, and Shaul Mukamel^5,†

¹Department of Physics, City University of Hong Kong, Kowloon, Hong Kong SAR
²City University of Hong Kong, Shenzhen Research Institute, Shenzhen, Guangdong 518057, China
³School of Physics, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China
⁴Department of Materials Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong SAR
⁵Department of Chemistry, Department of Physics and Astronomy, University of California Irvine, Irvine, California 92697, USA