Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons

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

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Blackbody Radiation and Thermal Effects on Chemical Reactions and Phase Transitions in Cavities

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

An important question in polariton chemistry is whether reacting molecules are thermal equilibrium with their surroundings. If not, can experimental changes observed reaction rates of a cavity (even without optical pumping) be attributed to higher/lower temperature inside the cavity? In this work, we address by computing differences between and air outside. We found difference negligible for most reactions. On other hand, phase transitions cavities, as material actively maintained heating/cooling source experiments, show that cavities modify transition temperatures when mirrors windows ideal (nonabsorbing); however, modification vanishes real used. This conclusion relies on having low contact resistance molecules. Finally, find substantial blackbody spectral energy density free space infrared which reveal resonance effects could potentially play role explaining chemical reactivity dark.

Язык: Английский

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Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling

The Journal of Chemical Physics, Год журнала: 2023, Номер 159(16)

Опубликована: Окт. 23, 2023

Polariton chemistry may provide a new means to control molecular reactivity, permitting remote, reversible modification of reaction energetics, kinetics, and product yields. A considerable body experimental theoretical work has already demonstrated that strong coupling between vibrational mode the confined electromagnetic field an optical cavity can alter chemical reactivity without external illumination. However, mechanisms underlying cavity-altered remain unclear in large part because systems examined previously are too complex for detailed analysis their dynamics. Here, we experimentally investigate photolysis-induced reactions cyanide radicals with strongly-coupled chloroform (CHCl3) solvent molecules examine intracavity rates photofragment recombination, complexation, hydrogen abstraction. We use microfluidic fitted dichroic mirrors facilitate (VSC) C-H stretching CHCl3 while simultaneously access at visible wavelengths. Ultrafast transient absorption experiments performed cavities tuned on- off-resonance reveal VSC transition does not significantly modify any measured rate constants, including those associated abstraction reaction. This represents, best our knowledge, first study elementary bimolecular under VSC. discuss how conspicuous absence effects this system insights into modified ground state help bridge divide results predictions polariton chemistry.

Язык: Английский

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Molecular van der Waals Fluids in Cavity Quantum Electrodynamics

The Journal of Physical Chemistry Letters, Год журнала: 2023, Номер 14(40), С. 8988 - 8993

Опубликована: Сен. 29, 2023

Intermolecular van der Waals interactions are central to chemical and physical phenomena ranging from biomolecule binding soft-matter phase transitions. In this work, we demonstrate that strong light–matter coupling can be used control the thermodynamic properties of many-molecule systems. Our analyses reveal orientation dependent single molecule energies interaction for molecules. For example, find intermolecular depend on distance between molecules R as R–3 R0. Moreover, employ ab initio cavity quantum electrodynamics calculations develop machine-learning-based potentials inside optical cavities. By simulating systems 12 H2 144 molecules, observe varying degrees orientational order because cavity-modified interactions, explain how nuclear effects, strengths, number modes, molecular anisotropies, system size all impact extent order.

Язык: Английский

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Surface hopping modeling of charge and energy transfer in active environments

Physical Chemistry Chemical Physics, Год журнала: 2023, Номер 25(12), С. 8293 - 8316

Опубликована: Янв. 1, 2023

An active environment changes the photophysics of an excited chromophore. Surface hopping simulations are crucial to understanding how.

Язык: Английский

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