Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations DOI

Xinwei Ji,

Tao E. Li

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 5034 - 5042

Опубликована: Май 13, 2025

Vibrational polaritons, hybrid light-matter states formed between molecular vibrations and infrared (IR) cavity modes, provide a novel approach for modifying chemical reaction pathways energy transfer processes. For vibrational polaritons involving condensed-phase molecules, the short polariton lifetime raises debate over whether pumping may produce different effects on molecules compared to directly exciting in free space or under weak coupling. Here, liquid methane strong coupling, classical dynamics simulations show that upper (UP) by asymmetric bending mode of can sometimes selectively excite IR-inactive symmetric mode. This finding is validated when system described using both empirical force fields machine-learning potentials, also qualitative agreement with analytical theory rates based Fermi's golden rule calculations. Additionally, our study suggests polariton-induced modes reaches maximal efficiency UP has significant contributions from photons underscoring importance hybridization. As are generally inaccessible direct IR excitation, highlights unique role formation controlling vibrations. Since this process occurs after decays, it impact photochemistry time scale longer than lifetime, as observed experiments.

Язык: Английский

Impact of Dipole Self-Energy on Cavity-Induced Nonadiabatic Dynamics DOI
Csaba Fábri, Gábor J. Halász, Jaroslav Hofierka

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

The coupling of matter to the quantized electromagnetic field a plasmonic or optical cavity can be harnessed modify and control chemical physical properties molecules. In cavities, term known as dipole self-energy (DSE) appears in Hamiltonian ensure gauge invariance. aim this work is twofold. First, we introduce method, which has its own merits complements existing methods, compute DSE. Second, study impact DSE on cavity-induced nonadiabatic dynamics realistic system. For that purpose, various matrix elements are computed functions nuclear coordinates system after laser excitation investigated. induce conical intersections between polaritons, gives rise substantial effects. shown slightly affect these light-induced and, particular, break their symmetry.

Язык: Английский

Процитировано

3
Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons DOI
Tamás Szidarovszky

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(3)

Опубликована: Янв. 16, 2025

Accurate rovibrational molecular models are employed to gain insight in high-resolution into the collective effects and intermolecular processes arising when molecules gas phase interact with a resonant infrared (IR) radiation mode. An efficient theoretical approach is detailed, numerical results presented for HCl, H2O, CH4 confined an IR cavity. It shown that by employing rotationally resolved model molecules, revealing various cavity-mediated interactions between field-free eigenstates, it possible obtain detailed understanding of physical governing energy level structure, absorption spectra, dynamic behavior systems. Collective effects, due interaction identified shifts, intensity borrowing transfer occurring during Hermitian or non-Hermitian time propagation.

Язык: Английский

Процитировано

2
Contributions to the theoretical modeling and understanding of molecular polaritons DOI
Csaba Fábri, Tamás Szidarovszky

Advances in quantum chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations DOI

Xinwei Ji,

Tao E. Li

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 5034 - 5042

Опубликована: Май 13, 2025

Vibrational polaritons, hybrid light-matter states formed between molecular vibrations and infrared (IR) cavity modes, provide a novel approach for modifying chemical reaction pathways energy transfer processes. For vibrational polaritons involving condensed-phase molecules, the short polariton lifetime raises debate over whether pumping may produce different effects on molecules compared to directly exciting in free space or under weak coupling. Here, liquid methane strong coupling, classical dynamics simulations show that upper (UP) by asymmetric bending mode of can sometimes selectively excite IR-inactive symmetric mode. This finding is validated when system described using both empirical force fields machine-learning potentials, also qualitative agreement with analytical theory rates based Fermi's golden rule calculations. Additionally, our study suggests polariton-induced modes reaches maximal efficiency UP has significant contributions from photons underscoring importance hybridization. As are generally inaccessible direct IR excitation, highlights unique role formation controlling vibrations. Since this process occurs after decays, it impact photochemistry time scale longer than lifetime, as observed experiments.

Язык: Английский

Процитировано

0