arXiv subjects

Marissa L. Weichman

Publications and source records attributed to Marissa L. Weichman.

17 recordsLinked to original sources

arXiv2026

Electronic Strong Coupling of Gas-Phase Molecular Iodine

Molecular polaritons, hybrid light-matter states formed from the strong coupling of molecular transitions and discrete photonic modes, are a compelling platform for optical control of chemical reactivity. Despite the origins of the field of polaritonics in atomic gases, strong coupling of molecular gases remains underexplored. The pristine, solvent-free gas-phase environment may prove ideal for gaining mechanistic understanding of molecular behavior under strong light-matter coupling. In this work, we achieve electronic strong coupling of the B-X, $ν_1$ = 0$\rightarrow$32, J = 53$\rightarrow$52 and B-X, $ν_1$ = 0$\rightarrow$34, J = 103$\rightarrow$102 rovibronic transitions of gas-phase iodine (I$_2$) lying near 532.2 nm. We access a range of coupling strengths and detuning conditions with fine control over molecular number density and cavity length stabilization. This effort represents the first demonstration of electronic polaritons in a molecular gas and opens a new platform for polariton photochemistry and photophysics.

physics.chem-ph↗

arXiv2026

Tracking water vapor homogeneous nucleation and droplet growth with spectroscopy and holography in a free expansion cloud chamber

We use a newly commissioned rapid expansion aerosol chamber (REACh) facility to study the homogeneous nucleation of water vapor to form liquid droplets. We perform high-speed measurements to track the partitioning of water into vapor and droplets throughout the expansion process, including tunable diode laser absorption spectroscopy (TDLAS) to access the vapor concentration and in-line holography to track the size and concentration of nucleating droplets. We retrieve the peak saturation ratio achieved in each expansion from the TDLAS measurements in combination with adjusted thermocouple temperature readout. We monitor the number of nucleated droplets and their subsequent growth as a function of saturation ratio, and observe the onset of homogeneous nucleation of water vapor occurring at a threshold saturation ratio near $S=5$, in agreement with prior literature and classical nucleation theory. The trends we observe in average diameter and droplet concentration suggest that warm air pockets near the chamber walls inhomogeneously mix with cold air at the center of the chamber following expansion. Active forced mixing with fans yields more spatially uniform temperature readings across the chamber, but also significantly broadens the droplet size distribution. Our results demonstrate the capability of TDLAS and holography techniques to track both water vapor and liquid water in the high saturation ratio environments necessary for the homogeneous nucleation of droplets. Our findings also reveal that droplet nucleation and growth dynamics are highly sensitive to turbulence.

physics.flu-dyn↗

arXiv2026

Nonlinear signal enhancement of strongly-coupled molecules in pump-probe experiments

Nonlinear spectroscopy is widely used to study the transient dynamics of molecules under strong light-matter coupling, though it remains unclear to what extent uncoupled intracavity molecules obscure signals from the strongly-coupled species of interest. Pump or probe fields resonant in the strongly-coupled spectral region will preferentially interact with cavity-coupled molecules, but can exhibit severe optical artifacts due to wave interference in the cavity. On the other hand, non-resonant pump or probe fields having wavelengths at which the cavity mirrors are highly transmissive propagate as traveling waves along the cavity axis, interacting with both coupled and uncoupled intracavity molecules. Here, we quantify the contributions of signals from strongly-coupled and uncoupled populations in simulated experiments with different resonant and non-resonant pump-probe configurations. We find that while resonant schemes maximize selectivity for the signals of strongly-coupled molecules, non-resonant schemes retain surprisingly high sensitivity to these signals while remaining less susceptible to optical artifacts.

physics.chem-ph↗

arXiv2026

Long-wave mid-infrared cavity-enhanced frequency comb spectroscopy of cold, complex molecules

We report the development of a new instrument for cavity-enhanced absorption spectroscopy of the fundamental rovibrational transitions of molecules in the long-wave mid-infrared (LWIR) region from 6500 to 10000 nm. Our setup combines a LWIR frequency comb, a high-finesse optical enhancement cavity, a cryogenic buffer gas cooling cell, and a Fourier transform interferometer to obtain broadband, high-resolution, and high-sensitivity molecular absorption spectra. Here, we showcase the capabilities of this setup by presenting the gas-phase LWIR spectra of the $ν_6$ band of ethane and the $ν_{10}$ band of the gauche conformer of ethanol near 7200 nm under both room temperature and cryogenic conditions.

physics.optics↗

arXiv2025

Direct readout of excited state lifetimes in chlorin chromophores under electronic strong coupling

The mechanisms governing molecular photophysics under electronic strong coupling (ESC) remain elusive to date. Here, we use ultrafast pump-probe spectroscopy to study the nonradiative excited state relaxation dynamics of chlorin e6 trimethyl ester (Ce6T) under strong coupling of its transition from the electronic ground state to the Qy band. We use dichroic Fabry-Pérot cavities to provide a transparent spectral window in which we can directly track the excited state population following optical pumping of either the strongly-coupled Qy band or the higher-lying B band. This scheme circumvents many of the optical artifacts inherent in ultrafast cavity measurements and allows for facile comparison of strongly-coupled measurements with extracavity controls. We observe no significant changes in excited state lifetimes for any optical pumping schemes or cavity coupling conditions considered herein. These results suggest that Ce6T exhibits identical photophysics under ESC and in free space, presenting a new data point for benchmarking emerging theories for cavity photochemistry.

physics.chem-ph↗

arXiv2025

Ultrafast optical modulation of vibrational strong coupling in ReCl(CO)$_3$(2,2-bipyridine)

Polaritons - hybrid light-matter states formed from the strong coupling of a bright molecular transition with a confined photonic mode - may offer new opportunities for optical control of molecular behavior. Vibrational strong coupling (VSC) has been reported to impact ground-state chemical reactivity, but its influence on electronic excited-state dynamics remains unexplored. Here, we take a first step towards excited-state VSC by demonstrating optical modulation of the ReCl(CO)$_3$(bpy), (bpy = 2,2-bipyridine) complex under VSC using femtosecond ultraviolet (UV)-pump/infrared (IR)-probe spectroscopy. We establish ground-state VSC of ReCl(CO)$_3$(bpy) in a microfluidic Fabry-Pérot cavity equipped with indium tin oxide (ITO)-coated mirrors. ITO is effectively dichroic as it is reflective in the IR and transmissive in the UV-visible and therefore minimizes optical interference. Excitation with UV pump light drives ReCl(CO)$_3$(bpy) into a manifold of electronic excited states that subsequently undergo non-radiative relaxation dynamics. We probe the transient response of the strongly-coupled system in the mid-IR, observing both Rabi contraction and cavity-filtered excited state absorption signatures. We reconstruct the intrinsic response of intracavity molecules from the transient cavity transmission spectra to enable quantitative comparison with extracavity control experiments. We report no changes in the excited-state dynamics of ReCl(CO)$_3$(bpy) under ground-state VSC. However, we do observe significant amplification of transient vibrational signals due to classical cavity-enhanced optical effects. This effort lays the groundwork to pursue direct excited-state VSC aimed at modulating photochemical reactivity.

physics.chem-ph↗

arXiv2025

A Cavity-Enhanced Spectroscopist's Lens on Molecular Polaritons

Polariton chemistry has been hailed as a potential new route to direct molecular processes with electromagnetic fields. To make further strides, it is essential for the community to clarify which unusual polaritonic phenomena are true hallmarks of cavity quantum electrodynamics and which can be rationalized with classical optical physics. Here, we provide a tutorial perspective on the formation, spectroscopy, and behavior of molecular polaritons using classical optics. Where possible, we draw connections to cavity-enhanced spectroscopy and recast open questions in terms that may be more familiar to the broader community of physical chemists.

physics.chem-ph↗

arXiv2025

When do molecular polaritons behave like optical filters?

This review outlines several linear optical effects featured by molecular polaritons arising in the collective strong light-matter coupling regime. Under weak laser irradiation and when the single-molecule light-matter coupling can be neglected (often in the limit when the number of molecules per photon mode is large), we show that the excited-state molecular dynamics under collective strong coupling can be exactly replicated without the cavity using a shaped (or ``filtered'') laser, whose field amplitude is enhanced by the cavity quality factor, shining on the bare molecules. As a consequence, the absorption within a cavity can be understood as the overlap between the polariton transmission and the bare molecular absorption, suggesting that polaritons act in part as optical filters. This framework demystifies and provides a straightforward explanation for a large class of experiments and theoretical models in molecular polaritonics, highlighting that the same effects can be achieved without the cavity with shaped laser pulses. With a few modifications, this simple conceptual picture can also be adapted to understand the incoherent nonlinear response of polaritonic systems. This review establishes a clear distinction between polaritonic phenomena that can be fully explained through classical linear optics and those that require a quantum electrodynamics approach. It also highlights the need to differentiate between effects that necessitate polaritons (i.e., hybrid light-matter states) and those that can occur in the weak coupling regime. We further discuss that certain quantum optical effects like fluorescence can be partially described as optical filtering, whereas some others like cavity-induced Raman scattering go beyond this. Further exploration in these areas is needed to uncover novel polaritonic phenomena beyond optical filtering.

physics.chem-ph↗

arXiv2024

Droplet Nucleation In a Rapid Expansion Aerosol Chamber

We present a new experimental facility to investigate the nucleation and growth of liquid droplets and ice particles under controlled conditions and characterize processes relevant to cloud microphysics: the rapid expansion aerosol chamber (REACh). REACh is an intermediate size chamber (~0.14 m$^3$) combining the principle of an expansion chamber with the ability to probe the influence of turbulent flows. Nucleation is achieved via a sudden pressure drop accompanied by a temperature drop, which can cause humid air to condense into a cloud of droplets under the appropriate thermodynamic conditions. REACh features tight control and monitoring of the initial saturation ratio of water vapor, identity and concentration of seeding aerosol particles, temperature, pressure, and air flow mixing, together with high speed real time measurements of aerosol and droplet size and number. Here, we demonstrate that the minimum temperature reached during each expansion can be reasonably described by the thermodynamics of dry or moist adiabats, for a wide range of initial relative humidity. The size and number of droplets formed, and the overall lifetime of the cloud, are characterized as a function of the aerosol concentration and initial water vapor saturation ratio. The total droplet concentration scales linearly with the seeding aerosol concentration, suggesting that all injected aerosol particles serve as condensation nuclei. While the total number of droplets formed increases with aerosol concentration, the mean droplet size decreases with the concentration of seeding aerosols as a result of competition for the available water vapor. Theoretical considerations provide a quantitative prediction for the mean droplet size for a wide range of conditions.

physics.flu-dyn↗

arXiv2024

More than just smoke and mirrors: Gas-phase polaritons for optical control of chemistry

Gas-phase molecules are a promising platform through which to elucidate the mechanisms of action and scope of polaritons for optical control of chemistry. Polaritons arise from the strong coupling of a dipole-allowed molecular transition with the photonic mode of an optical cavity. There is mounting evidence of modified reactivity under polaritonic conditions; however, the complex condensed-phase environment of most experimental demonstrations impedes mechanistic understanding of this phenomenon. While the gas phase was the playground of early efforts in atomic cavity quantum electrodynamics, we have only recently demonstrated the formation of molecular polaritons under these conditions. Studying the reactivity of isolated gas-phase molecules under strong coupling would eliminate solvent interactions and enable quantum state resolution of reaction progress. In this Perspective, we contextualize recent gas-phase efforts in the field of polariton chemistry and offer a practical guide for experiment design moving forward.

physics.chem-ph↗

arXiv2024

Exploring the impact of vibrational cavity coupling strength on ultrafast CN + $c$-C$_6$H$_{12}$ reaction dynamics

Molecular polaritons, hybrid light-matter states resulting from strong cavity coupling of optical transitions, may provide a new route to guide chemical reactions. However, demonstrations of cavity-modified reactivity in clean benchmark systems are still needed to clarify the mechanisms and scope of polariton chemistry. Here, we use transient absorption to observe the ultrafast dynamics of CN radicals interacting with a cyclohexane ($c$-C$_6$H$_{12}$) and chloroform (CHCl$_3$) solvent mixture under vibrational strong coupling of the brightest C$-$H stretching mode of $c$-C$_6$H$_{12}$. By modulating the $c$-C$_6$H$_{12}$:CHCl$_3$ ratio, we explore how solvent complexation and hydrogen (H)-abstraction processes proceed under collective cavity coupling strengths ranging from 55$-$85 cm$^{-1}$. Reaction rates remain unchanged for all extracavity, on resonance, and off-resonance cavity coupling conditions, regardless of coupling strength. These results suggest that insufficient vibrational cavity coupling strength may not be the determining factor for the negligible cavity effects observed previously in H-abstraction reactions of CN with CHCl$_3$.

physics.chem-ph↗

arXiv2023

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

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 of experimental and theoretical work has already demonstrated that strong coupling between a molecular vibrational mode and the confined electromagnetic field of an optical cavity can alter chemical reactivity without external illumination. However, the mechanisms underlying cavity-altered chemistry remain unclear in large part because the experimental systems examined previously are too complex for detailed analysis of their reaction dynamics. Here, we experimentally investigate photolysis-induced reactions of cyanide (CN) radicals with strongly-coupled chloroform (CHCl$_3$) solvent molecules and examine the intracavity rates of photofragment recombination, solvent complexation, and hydrogen abstraction. We use a microfluidic optical cavity fitted with dichroic mirrors to facilitate vibrational strong coupling (VSC) of the C-H stretching mode of CHCl$_3$ while simultaneously permitting optical access at visible wavelengths. Ultrafast transient absorption experiments performed with cavities tuned on- and off-resonance reveal that VSC of the CHCl$_3$ C-H stretching transition does not significantly modify any measured rate constants, including those associated with the hydrogen abstraction reaction. This work represents, to the best of our knowledge, the first experimental study of an elementary bimolecular reaction under VSC. We discuss how the conspicuous absence of cavity-altered effects in this system may provide insights into the mechanisms of modified ground state reactivity under VSC and help bridge the divide between experimental results and theoretical predictions in vibrational polariton chemistry.

physics.chem-ph↗

arXiv2023

A versatile platform for gas-phase molecular polaritonics

Strong cavity coupling of gas-phase molecules will enable studies of benchmark chemical processes under strong light-matter interactions with a high level of experimental control and no solvent effects. We recently demonstrated the formation of gas-phase molecular polaritons by strongly coupling the bright $ν_3$, $J=3 \rightarrow 4$ rovibrational transitions of methane (CH$_4$) to a Fabry-Pérot optical cavity mode inside a cryogenic buffer gas cell. Here, we further explore the flexible capabilities of this infrastructure. We show that we can greatly increase the collective coupling strength of the molecular ensemble to the cavity by increasing the intracavity CH$_4$ number density. In doing so, we can tune from the single-mode coupling regime to the multimode coupling regime in which many nested polaritonic states arise as the Rabi splitting approaches the cavity mode spacing. We explore polariton formation for cavity geometries of varying length, finesse, and mirror radius of curvature. We also report a proof-of-principle demonstration of rovibrational gas-phase polariton formation at room temperature. This experimental flexibility affords a great degree of control over the properties of molecular polaritons and opens up a wider range of simple molecular processes to future interrogation under strong cavity-coupling. We anticipate that ongoing work in gas-phase polaritonics will facilitate convergence between experimental results and theoretical models of cavity-altered chemistry and physics.

physics.chem-ph↗

arXiv2023

Rovibrational Polaritons in Gas-Phase Methane

Polaritonic states arise when a bright optical transition of a molecular ensemble is resonantly matched to an optical cavity mode frequency. Here, we lay the groundwork to study the behavior of polaritons in clean, isolated systems by establishing a new platform for vibrational strong coupling in gas-phase molecules. We access the strong coupling regime in an intracavity cryogenic buffer gas cell optimized for the preparation of simultaneously cold and dense ensembles, and report a proof-of-principle demonstration in gas-phase methane. We strongly cavity-couple individual rovibrational transitions and probe a range of coupling strengths and detunings. We reproduce our findings with classical cavity transmission simulations in the presence of strong intracavity absorbers. This infrastructure provides a new testbed for benchmark studies of cavity-altered chemistry.

physics.chem-ph↗

arXiv2022

Collision-induced C_60 rovibrational relaxation probed by state-resolved nonlinear spectroscopy

Quantum state-resolved spectroscopy was recently achieved for C60 molecules when cooled by buffer gas collisions and probed with a midinfrared frequency comb. This rovibrational quantum state resolution for the largest molecule on record is facilitated by the remarkable symmetry and rigidity of C60, which also present new opportunities and challenges to explore energy transfer between quantum states in this many-atom system. Here we combine state-specific optical pumping, buffer gas collisions, and ultrasensitive intracavity nonlinear spectroscopy to initiate and probe the rotation-vibration energy transfer and relaxation. This approach provides the first detailed characterization of C60 collisional energy transfer for a variety of collision partners, and determines the rotational and vibrational inelastic collision cross sections. These results compare well with our theoretical modeling of the collisions, and establish a route towards quantum state control of a new class of unprecedentedly large molecules.

physics.atom-ph↗

arXiv2018

Quantum state resolution of the C$_{60}$ fullerene

The remarkable physical properties of buckminsterfullerene, C$_{60}$, have attracted intense research activity since its original discovery. Total quantum state resolved measurements of isolated C$_{60}$ molecules have been of particularly long-standing interest. However, such observations have to date been unsuccessful due to the difficulty in preparing cold, gas-phase C$_{60}$ in sufficiently high densities. Here we report high resolution infrared absorption spectroscopy of C$_{60}$ in the 8.5 $μ$m spectral region. A combination of cryogenic buffer gas cooling and cavity-enhanced direct frequency comb spectroscopy has enabled the observation of quantum state resolved rovibrational transitions. Characteristic nuclear spin statistical intensity patterns provide striking confirmation of the indistinguishability of the sixty $^{12}$C atoms, while rovibrational fine structure encodes further details of the molecule's rare icosahedral symmetry. These observations establish new possibilities in the study and control of emergent complexity in finite-sized quantum systems such as fullerenes.

physics.chem-ph↗

arXiv2007

The Forgotten Night: The Number Devil Explores Spherical Geometry

This is a missing chapter from Hans Magnus Enzensberger's mathematical adventure The Number Devil (Henry Holt and Company, New York, 1997). In the book, a math-hating boy named Robert is visited in his dreams by the clever Number Devil, who teaches him to love all things numerical. However, we all forget our dreams from time to time. Here is one adventure that Enzensberger overlooked, where the Number Devil introduces Robert to geometry not-of-Euclid, great circles, parallel transport, the pendulum of Foucault, and the genius of Euler.

math.HO↗