Coherent transient exciton transport in disordered polaritonic wires.

Excitation energy transport can be significantly enhanced by strong light-matter interactions. In the present work, we explore intriguing features of coherent transient exciton wave packet dynamics on a lossless disordered polaritonic wire. Our main results can be understood in terms of the effective exciton group velocity, a new quantity we obtain from the polariton dispersion.

Theoretical formulation of chemical equilibrium under vibrational strong coupling.

Experiments have suggested that strong interactions between molecular ensembles and infrared microcavities can be employed to control chemical equilibria. Nevertheless, the primary mechanism and key features of the effect remain largely unexplored. In this work, we develop a theory of chemical equilibrium in optical microcavities, which allows us to relate the equilibrium composition of a mixture in different electromagnetic environments.

Vibrational polariton transport in disordered media.

Chemical reactions and energy transport phenomena have been experimentally reported to be significantly affected by strong light-matter interactions and vibrational polariton formation. These quasiparticles exhibit nontrivial transport phenomena due to the long-range correlations induced by the photonic system and elastic and inelastic scattering processes driven by matter disorder. In this article, we employ the Ioffe-Regel criterion to obtain vibrational polariton mobility edges and to identify distinct regimes of delocalization and transport under variable experimental conditions of light-matter detuning, disorder, and interaction strength.

Theoretical Analysis of Exciton Wave Packet Dynamics in Polaritonic Wires.

We present a comprehensive study of the exciton wave packet evolution in disordered lossless polaritonic wires. Our simulations reveal signatures of ballistic, diffusive, and subdiffusive exciton dynamics under strong light-matter coupling and identify the typical time scales associated with the transitions between these qualitatively distinct transport phenomena. We determine optimal truncations of the matter and radiation subsystems required for generating reliable time-dependent data from computational simulations at an affordable cost.

Multimode polariton effects on molecular energy transport and spectral fluctuations.

Despite the potential paradigm breaking capability of microcavities to control chemical processes, the extent to which photonic devices change properties of molecular materials is still unclear, in part due to challenges in modeling hybrid light-matter excitations delocalized over many length scales. We overcome these challenges for a photonic wire under strong coupling with a molecular ensemble. Our simulations provide a detailed picture of the effect of photonic wires on spectral and transport properties of a disordered molecular material.

Correction: Polariton chemistry: controlling molecular dynamics with optical cavities.

[This corrects the article DOI: 10.1039/C8SC01043A.].

Computational method for highly constrained molecular dynamics of rigid bodies: Coarse-grained simulation of auxetic two-dimensional protein crystals.

The increasing number of protein-based metamaterials demands reliable and efficient theoretical and computational methods to study the physicochemical properties they may display. In this regard, we develop a simulation strategy based on Molecular Dynamics (MD) that addresses the geometric degrees of freedom of an auxetic two-dimensional protein crystal. This model consists of a network of impenetrable rigid squares linked through massless rigid rods.

Intermolecular vibrational energy transfer enabled by microcavity strong light-matter coupling.

Selective vibrational energy transfer between molecules in the liquid phase, a difficult process hampered by weak intermolecular forces, is achieved through polaritons formed by strong coupling between cavity photon modes and donor and acceptor molecules. Using pump-probe and two-dimensional infrared spectroscopy, we found that the excitation of the upper polariton, which is composed mostly of donors, can efficiently relax to the acceptors within ~5 picoseconds. The energy-transfer efficiency can be further enhanced by increasing the cavity lifetime, suggesting that the energy transfer is a polaritonic process.

Manipulating optical nonlinearities of molecular polaritons by delocalization.

Optical nonlinearities are key resources in the contemporary photonics toolbox, relevant to quantum gate operations and all-optical switches. Chemical modification is often used to control the nonlinear response of materials at the microscopic level, but on-the-fly manipulation of such response is challenging. Tunability of optical nonlinearities in the mid-infrared (IR) is even less developed, hindering its applications in chemical sensing or IR photonic circuitry.

Correction: Theory for polariton-assisted remote energy transfer.

[This corrects the article DOI: 10.1039/C8SC00171E.].

Resonant catalysis of thermally activated chemical reactions with vibrational polaritons.

Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics. In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number [Formula: see text] of molecular transitions couple to each resonant cavity mode, yielding two hybrid light-matter (polariton) modes and a reservoir of [Formula: see text] dark states whose chemical dynamics are essentially those of the bare molecules. This fact is seemingly in opposition to the recently reported modification of thermally activated ground electronic state reactions under VSC.

State-Selective Polariton to Dark State Relaxation Dynamics.

The modification of vibrational dynamics is essential for controlling chemical reactions and IR photonic applications. The hybridization between cavity modes and molecular vibrational modes provides a new way to control molecular dynamics. In this work, we study the dynamics of molecular vibrational polaritons in various solvent environments.

Theory for polariton-assisted remote energy transfer.

Strong-coupling between light and matter produces hybridized states (polaritons) whose delocalization and electromagnetic character allow for novel modifications in spectroscopy and chemical reactivity of molecular systems. Recent experiments have demonstrated remarkable distance-independent long-range energy transfer between molecules strongly coupled to optical microcavity modes. To shed light on the mechanism of this phenomenon, we present the first comprehensive theory of polariton-assisted remote energy transfer (PARET) based on strong-coupling of donor and/or acceptor chromophores to surface plasmons.

Polariton chemistry: controlling molecular dynamics with optical cavities.

Molecular polaritons are the optical excitations which emerge when molecular transitions interact strongly with confined electromagnetic fields. Increasing interest in the hybrid molecular-photonic materials that host these excitations stems from recent observations of their novel and tunable chemistry. Some of the remarkable functionalities exhibited by polaritons include the ability to induce long-range excitation energy transfer, enhance charge conductivity, and inhibit or accelerate chemical reactions.

Deriving uniform semiclassical approximations for one-dimensional fermionic systems.

A complete derivation is provided of the uniform semiclassical approximations to the particle and kinetic energy densities of noninteracting bounded fermions in one dimension. The employed methodology allows the inclusion of non-perturbative quantum effects, including tunneling and quantum oscillations, via an infinite resummation of the Poisson summation formula. We explore the analytic behavior, physical meaning, and the relationship between the semiclassical uniform approximations for the fermionic kinetic energy and particle densities.

Theory for Nonlinear Spectroscopy of Vibrational Polaritons.

Molecular polaritons have gained considerable attention due to their potential to control nanoscale molecular processes by harnessing electromagnetic coherence. Although recent experiments with liquid-phase vibrational polaritons have shown great promise for exploiting these effects, significant challenges remain in interpreting their spectroscopic signatures. We develop a quantum-mechanical theory of pump-probe spectroscopy for this class of polaritons based on the quantum Langevin equation and the input-output theory.

Continuous vibronic symmetries in Jahn-Teller models.

Explorations of the consequences of the Jahn-Teller (JT) effect remain active in solid-state and chemical physics. In this topical review we revisit the class of JT models which exhibit continuous vibronic symmetries. A treatment of these systems is given in terms of their algebraic properties.

Two-dimensional infrared spectroscopy of vibrational polaritons.

We report experimental 2D infrared (2D IR) spectra of coherent light-matter excitations--molecular vibrational polaritons. The application of advanced 2D IR spectroscopy to vibrational polaritons challenges and advances our understanding in both fields. First, the 2D IR spectra of polaritons differ drastically from free uncoupled excitations and a new interpretation is needed.

Polariton-Assisted Singlet Fission in Acene Aggregates.

Singlet fission is an important candidate to increase energy conversion efficiency in organic photovoltaics by providing a pathway to increase the quantum yield of excitons per photon absorbed in select materials. We investigate the dependence of exciton quantum yield for acenes in the strong light-matter interaction (polariton) regime, where the materials are embedded in optical microcavities. Starting from an open-quantum-systems approach, we build a kinetic model for time-evolution of species of interest in the presence of singlet quenchers and show that polaritons can decrease or increase exciton quantum yields compared to the cavity-free case.

Vibronic Ground-State Degeneracies and the Berry Phase: A Continuous Symmetry Perspective.

We develop a geometric construction to prove the inevitability of the electronic ground-state (adiabatic) Berry phase for a class of Jahn-Teller (JT) models with maximal continuous symmetries and N > 2 intersecting electronic states. Given that vibronic ground-state degeneracy in JT models may be seen as a consequence of the electronic Berry phase and that any JT problem may be obtained from the subset that we investigate in this Letter by symmetry-breaking, our arguments reveal the fundamental origin of the vibronic ground-state degeneracy of JT models.

Corrections to Thomas-Fermi densities at turning points and beyond.

Uniform semiclassical approximations for the number and kinetic-energy densities are derived for many noninteracting fermions in one-dimensional potentials with two turning points. The resulting simple, closed-form expressions contain the leading corrections to Thomas-Fermi theory, involve neither sums nor derivatives, are spatially uniform approximations, and are exceedingly accurate.

Use of solution-phase vibrational frequencies in continuum models for the free energy of solvation.

We find that vibrational contributions to a solute's free energy are in general insensitive to whether the solute vibrational frequencies are computed in the gas phase or in solution. In most cases, the difference is smaller than the intrinsic error in solvation free energies associated with the continuum approximation to solvation modeling, although care must be taken to avoid spurious results associated with limitations in the quantum-mechanical harmonic-oscillator approximation for very low-frequency molecular vibrations. We compute solute vibrational partition functions in aqueous and carbon tetrachloride solution and compare them to gas-phase molecular partition functions computed with the same level of theory and the same quasiharmonic approximation for the diverse and extensive set of molecules and ions included in the training set of the SMD continuum solvation model, and we find mean unsigned differences in vibrational contributions to the solute free energy of only about 0.

The solvation, partitioning, hydrogen bonding, and dimerization of nucleotide bases: a multifaceted challenge for quantum chemistry.

We present M06-2X density functional calculations of the chloroform/water partition coefficients of cytosine, thymine, uracil, adenine, and guanine and calculations of the free energies of association of selected unsubstituted and alkylated nucleotide base pairs in chloroform and water. Both hydrogen bonding and π-π stacking interactions are considered. Solvation effects are treated using the continuum solvent models SM8, SM8AD, and SMD, including geometry optimization in solution.

Prediction of SAMPL2 aqueous solvation free energies and tautomeric ratios using the SM8, SM8AD, and SMD solvation models.

We applied the solvation models SM8, SM8AD, and SMD in combination with the Minnesota M06-2X density functional to predict vacuum-water transfer free energies (Task 1) and tautomeric ratios in aqueous solution (Task 2) for the SAMPL2 test set. The bulk-electrostatic contribution to the free energy of solvation is treated as follows: SM8 employs the generalized Born model with the Coulomb field approximation, SM8AD employs the generalized Born approximation with asymmetric descreening, and SMD solves the nonhomogeneous Poisson equation. The non-bulk-electrostatic contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell is treated as a sum of terms that are products of geometry-dependent atomic surface tensions and solvent-accessible surface areas of the individual atoms of the solute.

Solvent Dependence of (14)N Nuclear Magnetic Resonance Chemical Shielding Constants as a Test of the Accuracy of the Computed Polarization of Solute Electron Densities by the Solvent.

Although continuum solvation models have now been shown to provide good quantitative accuracy for calculating free energies of solvation, questions remain about the accuracy of the perturbed solute electron densities and properties computed from them. Here we examine those questions by applying the SM8, SM8AD, SMD, and IEF-PCM continuum solvation models in combination with the M06-L density functional to compute the (14)N magnetic resonance nuclear shieldings of CH3CN, CH3NO2, CH3NCS, and CH3ONO2 in multiple solvents, and we analyze the dependence of the chemical shifts on solvent dielectric constant. We examine the dependence of the computed chemical shifts on the definition of the molecular cavity (both united-atom models and models based on superposed individual atomic spheres) and three kinds of treatments of the electrostatics, namely the generalized Born approximation with the Coulomb field approximation, the generalized Born model with asymmetric descreening, and models based on approximate numerical solution schemes for the nonhomogeneous Poisson equation.