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Significant debate surrounds the origin of nonlinear optical responses from cavity-coupled molecular vibrations. Several groups, including our own, have previously assigned portions of the nonlinear response to polariton excited-state transitions. Here, we report a new method to approximate two-dimensional infrared spectra under vibrational strong coupling, which properly accounts for inhomogeneous broadening. We find excellent agreement between this model and experimental results for prototypical systems exhibiting both homogeneous and inhomogeneous broadening. This work implies that reservoir excitation is solely responsible for all optical response measured after the polariton modes dephase and represents an important new method for predicting and interpreting the nonlinear optical response of molecular vibrational polaritons. [ABSTRACT FROM AUTHOR]

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. Comparison with recent experimental data shows good agreement upon consideration of the various vibrational anharmonicities that modulate the signals. Finally, a simple and intuitive interpretation of the data based on an effective mode-coupling theory is provided. Our work provides a solid theoretical framework to elucidate nonlinear optical properties of molecular polaritons as well as to analyze further multidimensional spectroscopy experiments on these systems.

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. Comparison with recent experimental data shows good agreement upon consideration of the various vibrational anharmonicities that modulate the signals. Finally, a simple and intuitive interpretation of the data based on an effective mode-coupling theory is provided. Our work provides a solid theoretical framework to elucidate nonlinear optical properties of molecular polaritons as well as to analyze further multidimensional spectroscopy experiments on these systems.

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. Second, 2D IR uniquely resolves excitation of hybrid light-matter polaritons and unexpected dark states in a state-selective manner, revealing otherwise hidden interactions between them. Moreover, 2D IR signals highlight the impact of molecular anharmonicities which are applicable to virtually all molecular systems. A quantum-mechanical model is developed which incorporates both nuclear and electrical anharmonicities and provides the basis for interpreting this class of 2D IR spectra. This work lays the foundation for investigating phenomena of nonlinear photonics and chemistry of molecular vibrational polaritons which cannot be probed with traditional linear spectroscopy.

Certain organophosphorus molecules are infamous due to their use as highly toxic nerve agents. The filtration materials currently in common use for protection against chemical warfare agents were designed before organophosphorus compounds were used as chemical weapons. A better understanding of the surface chemistry between simulant molecules and the individual filtration-material components is a critical precursor to the development of more effective materials for filtration, destruction, decontamination, and/or sensing of nerve agents. Here, we report on the surface adsorption and reactions of a sarin simulant molecule, dimethyl methylphosphonate (DMMP), with cupric oxide surfaces. In situ ambient pressure X-ray photoelectron and infrared spectroscopies are coupled with density functional calculations to propose mechanisms for DMMP decomposition on CuO. We find extensive room temperature decomposition of DMMP on CuO, with the majority of decomposition fragments bound to the CuO surface. We observe breaking of PO-CH3, P-OCH3, and P-CH3 bonds at room temperature. On the basis of these results, we identify specific DMMP decomposition mechanisms not seen on other metal oxides. Participation of lattice oxygen in the decomposition mechanism leads to significant changes in chemical and electronic surface environment, which are manifest in the spectroscopic and computational data. This study establishes a computational baseline for the study of highly toxic organophosphorous compounds on metal oxide surfaces.

Organophosphonates are used as chemical warfare agents, pesticides, and corrosion inhibitors. New materials for the sorption, detection, and decomposition of these compounds are urgently needed. To facilitate materials and application innovation, a better understanding of the interactions between organophosphonates and surfaces is required. To this end, we have used diffuse reflectance infrared Fourier transform spectroscopy to investigate the adsorption geometry of dimethyl methylphosphonate (DMMP) on MoO3, a material used in chemical warfare agent filtration devices. We further applied ambient pressure X-ray photoelectron spectroscopy and temperature programmed desorption to study the adsorption and desorption of DMMP. While DMMP adsorbs intact on MoO3, desorption depends on coverage and partial pressure. At low coverages under UHV conditions, the intact adsorption is reversible. Decomposition occurs with higher coverages, as evidenced by PCHx and POx decomposition products on the MoO3 surface. Heating under mTorr partial pressures of DMMP results in product accumulation.

We examine closely the differences between the densities of vibrational states of bulk, slab, and cavity polariton modes under weak and moderate inhomogeneous broadening. While existing theoretical treatments are often based on a comparative analysis of "bare" vibrations and cavity polaritons, in the strong-coupling regime, only differences between slab/bulk polaritons on the one hand and cavity polaritons on the other hand are meaningful since "bare" vibrations are not observed experimentally. We find that polaritons in cavities significantly detuned from resonance with molecular transitions at zero in-plane wavevector do not differ appreciably from bulk polaritons in their density of vibrational states. Only cavity polaritons with sufficiently weak inhomogeneous broadening and tuned to resonance near normal incidence display a pronounced density-of-state enhancement. These results shed light on the heretofore puzzling observations of modified chemical reactivity only at zero detuning and supply a new baseline for assessing the explanatory power of proposed theories of cavity-modified chemistry. [ABSTRACT FROM AUTHOR]

Photoinjecting free carriers into polar semiconductors can drastically modify the infrared (IR) optical properties of the material via coupling of the longitudinal optical phonon to the free-carrier plasma. We report a detailed description of how the IR response depends on the distribution of free carriers, which, in turn, depends on the penetration depth of the excitation. The three-dimensional spatial overlap of this distribution with a probe pulse dictates the IR response. We measure transient infrared reflectivity in the reststrahlen band region of 4H-SiC and GaN using multiple excitation wavelengths in order to show the effect of carrier spatial distributions. The sensitivity of the IR response to the carrier distribution can potentially offer an avenue for tuning that response in devices. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Steady-state and time-resolved infrared spectroscopy of the azide [(N.sub.3.sup.-]) anion is used to characterize aqueous mixtures both with the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]-[B[F.sub.4]]) and with dimethyl sulfoxide (DMSO). The small anion vibrational spectra and dynamics have shown that the differences between molecular and ionic liquids are less than those between either of the neat solvents and the corresponding mixture with water.

Existing electrochemical experiments and models of fuel oxidation postulate about the importance of different oxidation pathways and relative fuel conversion efficiencies, but specific information is often lacking. Experiments described below present the first direct, in situ measurements of relevant chemical species formed on solid oxide fuel cell (SOFC) cermet anodes operating with both butane and CO fuel feeds. Raman spectroscopy is used to acquire vibrational spectra from SOFC anodes at 715[degrees]C during operation. Both [C.sub.4][H.sub.10] and CO form graphitic intermediates. In the limit of a large oxide flux, excess butane forms ordered graphite but only transiently. At higher cell potentials (e.g., less current being drawn) ordered and disordered graphite form on the Ni cermet anode following exposure to butane, and under open circuit voltage (OCV) conditions the graphite persists indefinitely. The chemistry of CO oxidation is such that ordered graphite and a Ni-COO intermediate form only at intermediate cell potentials. Concurrent voltammetry studies show that the formation of graphite with butane at OCV leads first to decreased cell performance after exposure to 25 [cm.sup.3] butane, then recovered performance after 75 [cm.sup.3]. CO voltammetry data show that at lower potentials the oxide flux through the YSZ electrolyte is sufficient to oxidize the Ni in the anode especially near the interface with the electrolyte.

A study was conducted on the photoreactivity of the excited solvated electron with surfactant headgroups in reverse micelles (RMs) through photodetachment of ferrocyanide (Fe[(CN).sub.6][.sup.4.sup.-]) in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) RMs. The findings suggested that diffusion coefficient of the solvated electron does not appear to be significantly affected by RM confinement.