Entangled Photonic-Nuclear Molecular Dynamics of LiF in Quantum Optical Cavities

Triana, Johan F.; Peláez, Daniel; Sanz-Vicario, José Luis

doi:10.1021/acs.jpca.7b11833

Cited by 56 publications

(72 citation statements)

References 24 publications

(84 reference statements)

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“…The number of active electrons and molecular orbitals in the individual irreducible representations of the C 2v point group were A 1 → 2/5, B 1 → 2/3, B 2 → 2/3, A 2 → 0/1. With these parameters, we achieved a good agreement with the results of other studies [49][50][51].…”

Section: The Physical Situation and Methodssupporting

confidence: 87%

Control of photodissociation with the dynamic Stark effect induced by THz pulses

Tóth

Csehi

Halász

et al. 2020

Phys. Rev. Research

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We demonstrate how dynamic Stark control (DSC) can be achieved on molecular photodissociation in the dipole limit, using single-cycle (FWHM) laser pulses in the terahertz (THz) regime. As the laser-molecule interaction follows the instantaneous electric field through the permanent dipoles, the molecular potentials dynamically oscillate and so does the crossings between them. In this paper, we consider rotating-vibrating diatomic molecules (2D description) and reveal the interplay between the dissociating wave packet and the dynamically fluctuating crossing seam located in the configuration space of the molecules spanned by the R vibrational and θ rotational coordinates. Our showcase example is the widely studied lithium-fluoride (LiF) molecule for which the two lowest Σ states are nonadiabatically coupled at an avoided crossing (AC), furthermore a low-lying pure repulsive Π state is energetically close. Optical pumping of the system in the ground state thus results in two dissociation channels: one indirect route via the AC in the ground Σ state and one direct path in the Π state. We show that applying THz control pulses with specific time delays relative to the pumping, can significantly alter the population dynamics, as well as, the kinetic energy and angular distribution of the photofragments.

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Section: The Physical Situation and Methodssupporting

confidence: 87%

Control of photodissociation with the dynamic Stark effect induced by THz pulses

Tóth

Csehi

Halász

et al. 2020

Phys. Rev. Research

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show abstract

“…Another problem where a collaboration between theory and experiments can be fruitful is strong coupling in the gas phase. Detailed theoretical predictions about spontaneous generation of infrared light with diatomic molecules under conditions of electronic strong coupling [184,185] represent a challenge for experimental verification, as achieving the strong coupling regime with gas-phase cavities is comparably difficult, although in principle possible.…”

Section: Discussionmentioning

confidence: 99%

Molecular polaritons for controlling chemistry with quantum optics

Herrera

Owrutsky

2020

The Journal of Chemical Physics

260

248

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This is a tutorial-style introduction to the field of molecular polaritons. We describe the basic physical principles and consequences of strong light-matter coupling common to molecular ensembles embedded in UV-visible or infrared cavities. Using a microscopic quantum electrodynamics formulation, we discuss the competition between the collective cooperative dipolar response of a molecular ensemble and local dynamical processes that molecules typically undergo, including chemical reactions. We highlight some of the observable consequences of this competition between local and collective effects in linear transmission spectroscopy, including the formal equivalence between quantum mechanical theory and the classical transfer matrix method, under specific conditions of molecular density and indistinguishability. We also overview recent experimental and theoretical developments on strong and ultrastrong coupling with electronic and vibrational transitions, with a special focus on cavity-modified chemistry and infrared spectroscopy under vibrational strong coupling. We finally suggest several opportunities for further studies that may lead to novel applications in chemical and electromagnetic sensing, energy conversion, optoelectronics, quantum control and quantum technology.

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“…Phase-space representations of the photon state follow directly from the QED formulation of the model [61]. Such phase-space analysis would be closely related to previous coordinate-only treatments of photon-nuclei coupling [28,39,62], although a systematic comparison has yet to be done.…”

Section: Discussionmentioning

confidence: 99%

Multi-level quantum Rabi model for anharmonic vibrational polaritons

Hernández

Herrera

2019

The Journal of Chemical Physics

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We propose a cavity QED approach to describe light-matter interaction between an individual anharmonic molecular vibration and an infrared cavity field. Starting from a generic Morse oscillator with quantized nuclear motion, we derive a multi-level quantum Rabi model to study vibrational polaritons beyond the rotating-wave approximation. We analyze the spectrum of vibrational polaritons in detail and compare with available experiments. For high excitation energies, the spectrum exhibits a dense manifold of true and avoided level crossings as the light-matter coupling strength and cavity frequency are tuned. These crossings are governed by a pseudo parity selection rule imposed by the cavity field. We also analyze polariton eigenstates in nuclear coordinate space. We show that the bond length of a vibrational polariton at a given energy is never greater than the bond length of a bare Morse oscillator with the same energy. This type of bond hardening of vibrational polaritons occurs at the expense of the creation of virtual infrared cavity photons, and may have implications in chemical reactivity.Cavity quantum electrodynamics (QED) has been intensely studied for the development of quantum technology over the last decade [1,2]. Precision experiments under carefully controlled conditions have been implemented to reach the regime where quantum optical effects become relevant for applications [3][4][5]. Chemical systems and molecular materials at ambient conditions for long have been considered to be unnecessarily complex and uncontrollable to enable useful quantum optical effects. In recent years, the demonstration of reversible modifications of chemical properties in molecular materials via strong coupling to confined light has stimulated the study of cavity QED as an emerging research direction in chemical physics [6]. Light-matter interaction in the strong coupling (SC) and ultrastrong coupling (USC) regimes opens the possibility of creating novel hybrid photon-molecule states whose unique properties may enable novel applications in chemistry and material science.In the infrared regime, the coupling of an intramolecular vibration to the quantized electromagnetic vacuum of a Fabry-Pérot cavity can lead to the formation of vibrational polaritons [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. These hybrid light-matter states exhibit fundamentally novel properties in comparison with free-space vibrations. For instance, vibrational polaritons may enable the selective control of chemical reactions [21-23], a long-standing goal in physical chemistry [24]. Strong light-matter coupling provides a reversible way of modifying reactive processes without changing the chemical composition of materials, and also modify the radiative and non-radiative dynamics of molecular vibrations [25][26][27][28][29][30][31]. Several recent studies on vibrational strong coupling (VSC) within the ground electronic state have shown that chemical reactions can proceed through novel pathways in comparison with free space. Under VSC, r...

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Entangled Photonic-Nuclear Molecular Dynamics of LiF in Quantum Optical Cavities

Cited by 56 publications

References 24 publications

Control of photodissociation with the dynamic Stark effect induced by THz pulses

Control of photodissociation with the dynamic Stark effect induced by THz pulses

Molecular polaritons for controlling chemistry with quantum optics

Multi-level quantum Rabi model for anharmonic vibrational polaritons

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