Polariton chemistry: controlling molecular dynamics with optical cavities

Ribeiro, Raphael F.; Martínez-Martínez, Luis A.; Du, Matthew; Campos-González-Angulo, Jorge

doi:10.1039/c8sc01043a

Cited by 565 publications

(583 citation statements)

References 183 publications

(402 reference statements)

Supporting

Mentioning

575

Contrasting

Unclassified

Order By: Relevance

“…Figure 1 demonstrates that the coupling with the radiation field leads to the formation of three 'bright' polaritonic surfaces, and as shown in the bottom left panel, N a − 1 'dark states'. Although these 'dark states' can affect excited state dynamics [35], they usually have no significant contribution to the spectrum [3,47]. With increasing atom number the effective coupling with the field increases and the polaritonic surfaces become more pronounced.…”

Section: Numerical Resultsmentioning

confidence: 99%

Three-player polaritons: nonadiabatic fingerprints in an entangled atom–molecule–photon system

2020

View full text Add to dashboard Cite

A quantum system composed of a molecule and an atomic ensemble, confined in a microscopic cavity, is investigated theoretically. The indirect coupling between atoms and the molecule, realized by their interaction with the cavity radiation mode, leads to a coherent mixing of atomic and molecular states, and at strong enough cavity field strengths hybrid atom-molecule-photon polaritons are formed. It is shown for the Na 2 molecule that by changing the cavity wavelength and the atomic transition frequency, the potential energy landscape of the polaritonic states and the corresponding spectrum could be changed significantly. Moreover, an unforeseen intensity borrowing effect, which can be seen as a strong nonadiabatic fingerprint, is identified in the atomic transition peak, originating from the contamination of the atomic excited state with excited molecular rovibronic states.

show abstract

Section: Numerical Resultsmentioning

confidence: 99%

Three-player polaritons: nonadiabatic fingerprints in an entangled atom–molecule–photon system

2020

View full text Add to dashboard Cite

show abstract

“…Also, the effect on the kinetics has been observed to increase as the collective coupling intensifies, as a consequence of the large number of molecules present in a sample. 1 These observations are reminiscent of the description of light-matter coupling in terms of hybrid states known as polaritons, [7][8][9][10][11][12] which successfully explains the optical properties of these systems. [13][14][15][16][17] Recently, it has been suggested that a class of nonadiabatic charge transfer reactions would experience a catalytic effect from resonant collective coupling between high-frequency modes and infrared cavity modes; the mechanism relies on the formation of vibrational polaritons which feature reduced activation energies compared to the bare molecules.…”

Section: Introductionmentioning

confidence: 99%

Polaritonic normal modes in transition state theory

Campos-González-Angulo

Yuen-Zhou

2020

The Journal of Chemical Physics

Self Cite

122

137

View full text Add to dashboard Cite

A series of experiments demonstrate that strong light-matter coupling between vibrational excitations in isotropic solutions of molecules and resonant infrared optical microcavity modes leads to modified thermally-activated kinetics. However, Feist and coworkers [Phys. Rev. X., 9, 021057(2019)] have recently demonstrated that, within transition state theory, effects of strong light-matter coupling with reactive modes are electrostatic, and essentially independent of light-matter resonance or even of the formation of vibrational polaritons. To analyze this puzzling theoretical result in further detail, we revisit it under a new light, invoking a normal mode analysis of the transition state and reactant configurations for an ensemble of an arbitrary number of molecules in a cavity, obtaining simple analytical expressions that produce similar conclusions as Feist. While these effects become relevant in optical microcavities if the molecular dipoles are anisotropically aligned, or in cavities with extreme confinement of the photon modes, they become negligible for isotropic solutions in microcavities. It is concluded that further studies are necessary to track the origin of the experimentally observed kinetics.

show abstract

“…Describing the photon-matter interaction with the tool of cavity quantum electrodynamics is an emerging field. It has been successfully demonstrated both experimentally [26][27][28][29][30][31][32] and theoretically [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49], that the quantized photonic mode description of the electromagnetic field can provide an alternative solution for studying adequately the light-molecule's OPEN ACCESS RECEIVED…”

mentioning

confidence: 99%

Ultrafast dynamics in the vicinity of quantum light-induced conical intersections

et al. 2019

View full text Add to dashboard Cite

Nonadiabatic effects appear due to avoided crossings or conical intersections (CIs) that are either intrinsic properties in field-free space or induced by a classical laser field in a molecule. It was demonstrated that avoided crossings in diatomics can also be created in an optical cavity. Here, the quantized radiation field mixes the nuclear and electronic degrees of freedom creating hybrid fieldmatter states called polaritons. In the present theoretical study we go further and create CIs in diatomics by means of a radiation field in the framework of cavity quantum electrodynamics. By treating all degrees of freedom, that is the rotational, vibrational, electronic and photonic degrees of freedom on an equal footing we can control the nonadiabatic quantum light-induced dynamics by means of CIs. First, the pronounced difference between the the quantum light-induced avoided crossing and the CI with respect to the nonadiabatic dynamics of the molecule is demonstrated. Second, we discuss the similarities and differences between the classical and the quantum field description of the light for the studied scenario.The dynamics initiated in a molecule by absorbing a photon is often described in the Born-Oppenheimer (BO) or adiabatic approximation [1], where the electronic and nuclear degrees of freedom are treated separately. However, in some nuclear configurations called conical intersections (CIs) the mixing between the electronic and nuclear motions are very significant [2][3][4][5][6]. Owing to the strong nonadiabatic couplings (NACs) in the close vicinity of these CIs the BO approximation breaks down. It is well-known that these CIs have a significant impact on several important photo-dynamical processes, such as vision, photosynthesis, molecular electronics, and the photochemistry of DNA [7][8][9][10][11]. During the dynamics the CIs can serve as efficient decay channels for the ultrafast transfer of the populations. In the following we call these CIs, which originate from the field free electronic structure, natural CIs.Nonadiabatic effects can also appear when molecules are exposed to resonant laser light. The electric field can couple to two or more electronic states of the molecule via the non-vanishing transition dipole moment(s) [12][13][14][15]. This results either in a light-induced avoided crossing (LIAC) or a light-induced conical intersection (LICI) depending on how many nuclear degrees of freedom are involved in the field induced process [16]. In case of poly atomic molecules a sufficient number of vibrational degrees of freedom are always present to span a twodimensional branching space (BS), which is indispensable to the formation of LICI. In the case of diatomics one always has to find a proper second degree of freedom (DOF) which can act as a dynamical variable to form a BS. As the molecule rotates [17][18][19], the rotational angle between the molecular axis and the light polarization axis can serve as the missing DOF for establishing the BS [20].Nonadiabatic effects can arise in an optical or mi...

show abstract

Polariton chemistry: controlling molecular dynamics with optical cavities

Abstract: Strong coupling of molecules with confined electromagnetic fields provides novel strategies to control chemical reactivity and spectroscopy.

Cited by 565 publications

References 183 publications

Three-player polaritons: nonadiabatic fingerprints in an entangled atom–molecule–photon system

Three-player polaritons: nonadiabatic fingerprints in an entangled atom–molecule–photon system

Polaritonic normal modes in transition state theory

Ultrafast dynamics in the vicinity of quantum light-induced conical intersections

Contact Info

Product

Resources

About