Ab-Initio Vibro-Polaritonic Spectra in Strongly Coupled Cavity-Molecule Systems
arXiv:2310.01871 · doi:10.1021/acs.jctc.3c01135
Abstract
Recent experiments have revealed the profound effect of strong light-matter interactions in optical cavities on the electronic ground state of molecular systems. This phenomenon, known as vibrational strong coupling (VSC), can modify reaction rates and induce the formation of molecular vibrational polaritons, hybrid states involving both photon modes and vibrational modes of molecules. We present an ab-initio methodology, based on the cavity Born-Oppenheimer Hartree-Fock ansatz, which is specifically powerful for ensembles of molecules, to calculate vibro-polaritonic IR spectra. This method allows a comprehensive analysis of these hybrid states. Our semi-classical approach, validated against full quantum simulations, reproduces key features of the vibro-polaritonic spectra. The underlying analytic gradients also pave the way for optimizing cavity-coupled molecular systems and performing semi-classical dynamics simulations
References in corpus (11)
- Multiple Rabi Splittings under Ultra-Strong Vibrational Coupling
- Quantum Dynamics of Vibrational Polariton Chemistry
- Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
- Cavity-Born-Oppenheimer Hartree-Fock Ansatz: Light-matter Properties of Strongly Coupled Molecular Ensembles
- Unraveling a cavity induced molecular polarization mechanism from collective vibrational strong coupling
- Beyond Cavity Born-Oppenheimer: On Non-Adiabatic Coupling and Effective Ground State Hamiltonians in Vibro-Polaritonic Chemistry
- The role of dephasing for dark state coupling in a molecular Tavis-Cummings model
- Multidimensional quantum calculation of the infrared spectra under polaritonic vibrational strong and ultrastrong coupling
- Understanding the polaritonic ground state in cavity quantum electrodynamics
- Extraordinary electrical conductance through amorphous non-conducting polymers under vibrational strong coupling
- Non-perturbative Mass Renormalization Effects in Non-relativistic Quantum Electrodynamics
Cited by in corpus (11)
- Unraveling a cavity induced molecular polarization mechanism from collective vibrational strong coupling
- Do Molecular Geometries Change Under Vibrational Strong Coupling?
- A quantum chemistry approach to linear vibro-polaritonic IR spectra with perturbative electron-photon correlation
- Molecular Polarizability under Vibrational Strong Coupling
- Extending the Tavis-Cummings model for molecular ensembles -- Exploring the effects of dipole self energies and static dipole moments
- Disentangling collective coupling in vibrational polaritons with double quantum coherence spectroscopy
- Impact of dipole self-energy on cavity-induced nonadiabatic dynamics
- Cavity-Born Oppenheimer Approximation for Molecules and Materials via Electric Field Response
- Cavity Born-Oppenheimer Coupled Cluster Theory: Towards Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime
- Indirect probing of light-induced nonadiabatic dynamics in lossy nanocavities
- Coherent nonlinear optical probe for cavity-dressed vibrational mode mixing: Multidimensional double-quantum coherence and photon-echo spectroscopy