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Recent breakthroughs in high repetition-rate extreme ultraviolet (XUV) light sources and photoelectron analyzers have led to dramatic advances in the performance of time-resolved photoemission experiments. In this perspective article, we discuss the application of cavity-enhanced high-order harmonic generation (CE-HHG), with repetition rates exceeding 10 MHz, to photoemission experiments using advanced endstations incorporating time-of-flight photoelectron analyzers. We discuss recent results, perspective on future areas for further technological improvement, and the wide array of science enabled by ultrafast XUV photoemission experiments, now in a qualitatively new regime., Comment: 14 pages, 9 figures

Transient absorption spectroscopy (TAS) is among the most common ultrafast photochemical experiments, but its interpretation remains challenging. In this work, we present an efficient and robust method for simulating TAS signals from first principles. Excited-state absorption and stimulated emission (SE) signals are computed using time-dependent complete active space configuration interaction (TD-CASCI) simulations, leveraging the robustness of time-domain simulation to minimize electronic structure failure. We demonstrate our approach by simulating the TAS signal of 1$^\prime$-hydroxy-2$^\prime$-acetonapthone (HAN) from ab initio multiple spawning nonadiabatic molecular dynamics simulations. Our results are compared to gas-phase TAS data recorded from both jet-cooled ($T\sim$ 40 K) and hot ($\sim$ 403 K) molecules via cavity-enhanced transient absorption spectroscopy (CE-TAS). Decomposition of the computed spectrum allows us to assign a rise in the SE signal to excited-state proton transfer and the ultimate decay of the signal to relaxation through a twisted conical intersection. The total cost of computing the observable signal ($\sim$1700 graphics processing unit hours for $\sim$4 ns of electron dynamics) was markedly less than that of the ab initio multiple spawning calculations used to compute the underlying nonadiabatic dynamics., Comment: Supplementary materials available upon request

The unique optical properties of graphene, with broadband absorption and ultrafast response, make it a critical component of optoelectronic and spintronic devices. Using time-resolved momentum microscopy with high data rate and high dynamic range, we report momentum-space measurements of electrons promoted to the graphene conduction band with visible light, and their subsequent relaxation. We observe a pronounced non-thermal distribution of nascent photoexcited electrons with lattice pseudospin polarization in remarkable agreement with results of simple tight-binding theory. By varying the excitation fluence, we vary the relative importance of electron-electron vs. electron-phonon scattering in the relaxation of the initial distribution. Increasing the excitation fluence results in increased noncollinear electron-electron scattering and reduced pseudospin polarization, although up-scattered electrons retain a degree of polarization. These detailed momentum-resolved electron dynamics in graphene demonstrate the capabilities of high-performance time-resolved momentum microscopy in the study of 2D materials and can inform the design of graphene devices., Comment: 19 pages, 5 figures

Salicylidenaniline (SA) is an archetypal system for excited-state intramolecular proton transfer (ESIPT) in non-planar systems. Multiple channels for relaxation involving both the keto and enol forms have been proposed after excitation to S$_1$ with near-UV light. Here we present transient absorption measurements of hot gas-phase SA, jet-cooled SA, and SA in Ar clusters using cavity-enhanced transient absorption spectroscopy (CE-TAS). Assignment of the spectra is aided by simulated TAS spectra, computed by applying time-dependent complete active space configuration interaction (TD-CASCI) to structures drawn from nonadiabatic molecular dynamics simulations. We find prompt ESIPT in all conditions followed by the rapid parallel generation of the trans-keto metastable photochrome state and fluorescent keto state in parallel. Increasing the internal energy increases the photochrome yield and decreases the fluorescent yield and fluorescent state lifetime observed in TAS. In Ar clusters, internal conversion of SA is severely hindered but the photochrome yield is unchanged. Taken together, these results are consistent with the photochrome being produced via the vibrationally excited keto population after ESIPT.

Recent advancements in infrared frequency combs will enable recording of coherent two-dimensional infrared spectra of gas-phase molecules with rotational resolution (RR2DIR). We describe how RR2DIR spectra can be controlled with polarization to enhance or suppress certain features of the spectrum, with new polarization conditions unique to freely rotating molecules and absent in the condensed-phase. With the polarization control methods described here, RR2DIR spectroscopy can be a powerful tool for studying complex gas mixtures of polyatomic molecules., Comment: updated references, minor clarification; 6 pages, 4 figures

Two-dimensional infrared (2DIR) spectroscopy is widely used to study molecular dynamics but it is typically restricted to solid and liquid phase samples and modest spectral resolution. Only recently, its potential to study gas-phase dynamics is beginning to be realized. Moreover, the recently proposed technique of cavity-enhanced 2D spectroscopy using frequency combs and developments in multi-comb spectroscopy are expected to dramatically advance capabilities for acquisition of rotationally-resolved 2DIR spectra. This demonstrates the need for rigorous and quantitative treatment of rotationally-resolved, polarization-dependent third-order response of gas-phase samples. In this article, we provide a rigorous and quantitative description of rotationally-resolved 2DIR spectroscopy using density-matrix, time-dependent perturbation theory and angular momentum algebra techniques. We describe the band and branch structure of 2D spectra, decompose the molecular response into polarization-dependence classes, use this decomposition to derive and explain special polarization conditions and relate the liquid-phase polarization conditions to gas-phase ones. Furthermore, we discuss the rotational coherence dynamics during waiting time., Comment: accepted, pre-proof version; 19 pages + 8 supplementary, 10 figures + 4 supplementary

Coupling between exciton states across the Brillouin zone in monolayer transition metal dichalcogenides can lead to ultrafast valley depolarization. Using time- and angle-resolved photoemission, we present momentum- and energy-resolved measurements of exciton coupling in monolayer WS$_2$. By comparing full 4D ($k_x, k_y, E, t$) data sets after both linearly and circularly polarized excitation, we are able to disentangle intervalley and intravalley exciton coupling dynamics. Recording in the exciton binding energy basis instead of excitation energy, we observe strong mixing between the B$_{1s}$ exciton and A$_{n>1}$ states. The photoelectron energy and momentum distributions observed from excitons populated via intervalley coupling (e.g. K$^-$ $\rightarrow$ K$^+$) indicate that the dominant valley depolarization mechanism conserves the exciton binding energy and center-of-mass momentum, consistent with intervalley Coulomb exchange. On longer timescales, exciton relaxation is accompanied by contraction of the momentum space distribution., Comment: 16 pages: 8 pages main text with 5 figures, 8 pages SI with 6 figures

Broadband ultrafast optical spectroscopy methods, such as transient absorption spectroscopy and 2D spectroscopy, are widely used to study molecular dynamics. However, these techniques are typically restricted to optically thick samples, such as solids and liquid solutions. In this article we discuss a cavity-enhanced ultrafast transient absorption spectrometer covering almost the entire visible range with a detection limit of $\Delta$OD $ < 1 \times 10^{-9}$, extending broadband all-optical ultrafast spectroscopy techniques to dilute beams of gas-phase molecules and clusters. We describe the technical innovations behind the spectrometer and present transient absorption data on two archetypical molecular systems for excited-state intramolecular proton transfer, 1'-hydroxy-2'-acetonapthone and salicylideneaniline, under jet-cooled and Ar cluster conditions.

High-harmonic generation (HHG) provides short-wavelength light that is useful for precision spectroscopy and probing ultrafast dynamics. We report efficient, phase-coherent harmonic generation up to 9th-order (333 nm) in chirped periodically poled lithium niobate waveguides driven by phase-stable $\leq$12-nJ, 100 fs pulses at 3 $\mu$m with 100 MHz repetition rate. A mid-infrared to ultraviolet-visible conversion efficiency as high as 10% is observed, amongst an overall 23% conversion of the fundamental to all harmonics. We verify the coherence of the harmonic frequency combs despite the complex highly nonlinear process. Numerical simulations based on a single broadband envelope equation with quadratic nonlinearity give estimates for the conversion efficiency within approximately 1 order of magnitude over a wide range of experimental parameters. From this comparison we identify a dimensionless parameter capturing the competition between three-wave mixing and group-velocity walk-off of the harmonics that governs the cascaded HHG physics. These results can inform cascaded HHG in a range of different platforms., Comment: 10 pages, 7 figures

We describe the cavity-enhancement of frequency combs over a wide tuning range of 450-700 nm (> 7900 cm$^{-1}$), covering nearly the entire visible spectrum. Tunable visible frequency combs from a synchronously-pumped optical parametric oscillator are coupled into a 4-mirror, dispersion-managed cavity with a finesse of 600 to 1400. An intracavity absorption path length enhancement greater than 190 is obtained over the entire tuning range, while preserving intracavity spectral bandwidths capable of supporting sub-200 fs pulse durations. These tunable cavity-enhanced frequency combs can find many applications in nonlinear optics and spectroscopy.

We report on the development of a high-power mid-infrared frequency comb with 100 MHz repetition rate and 100 fs pulse duration. Difference frequency generation is realized between two branches derived from an Er:fiber comb, amplified separately in Yb:fiber and Er:fiber amplifiers. Average powers of 6.7 W and 14.9 W are generated in the 2.9 $\mu$m idler and 1.6 $\mu$m signal, respectively. With high average power, excellent beam quality, and passive carrier-envelope phase stabilization, this light source is a promising platform for generating broadband frequency combs in the far infrared, visible, and deep ultraviolet.

We present a 100 MHz repetition rate Yb-fiber-laser-pumped synchronously pumped optical parametric oscillator (SPOPO) delivering tunable frequency combs covering almost the entire visible spectral range. By intracavity doubling both the signal and idler combs and using collinear residual pump light, nearly continuous tuning over the range of 420-700 nm is achieved with only small gaps near the OPO degeneracy condition. Output powers range from 10 mW to 200 mW, depending on wavelength, with pulse durations below 150 fs without external compression. Frequency locking of all three collinearly outcoupled combs (pump, doubled signal, and doubled idler) to a femtosecond enhancement cavity facilitates direct comparison of their optical phase noise and phase modulation transfer functions. In the singly-resonant OPO, optical phase modulation of the pump comb is transferred nearly completely to the non-resonant idler comb. This results in a resonant signal comb with reduced optical phase noise and also enables high-bandwidth modulation on the idler comb via phase modulation of the pump.

Mid-infrared laser frequency combs are compelling sources for precise and sensitive metrology with applications in molecular spectroscopy and spectro-imaging. The infrared atmospheric window between 3-5.5 $\mu$m in particular provides vital information regarding molecular composition. Using a robust, fiber-optic source of few-cycle pulses in the near-infrared, we experimentally demonstrate ultra-broad bandwidth nonlinear phenomena including harmonic and difference frequency generation in a single pass through periodically poled lithium niobate (PPLN). These $\chi^{(2)}$ nonlinear optical processes result in the generation of frequency combs across the mid-infrared atmospheric window which we employ for dual-comb spectroscopy of acetone and carbonyl sulfide with resolution as high as 0.003 cm$^{-1}$. Moreover, cascaded $\chi^{(2)}$ nonlinearities in the same PPLN directly provide the carrier-envelope offset frequency of the near-infrared driving pulse train in a compact geometry.

Time- and Angle-resolved photoelectron spectroscopy from surfaces can be used to record the dynamics of electrons and holes in condensed matter on ultrafast time scales. However, ultrafast photoemission experiments using extreme-ultraviolet (XUV) light have previously been limited by either space-charge effects, low photon flux, or limited tuning range. In this article, we describe space-charge-free XUV photoelectron spectroscopy experiments with up to 5 nA of average sample current using a tunable cavity-enhanced high-harmonic source operating at 88 MHz repetition rate. The source delivers $ > 10^{11}$ photons/s in isolated harmonics to the sample over a broad photon energy range from 18 to 37 eV with a spot size of $58 \times 100 \; \mu$m$^2$. From photoelectron spectroscopy data, we place conservative upper limits on the XUV pulse duration and photon energy bandwidth of 93 fs and 65 meV, respectively. The high photocurrent, lack of space charge distortions of the photoelectron spectra, and excellent isolation of individual harmonic orders allow us to observe the laser-assisted photoelectric effect with sideband amplitudes as low as $6 \times 10^{-4}$, enabling time-resolved XUV photoemission experiments in a qualitatively new regime.

Spectroscopy in the molecular fingerprint spectral region (6.5-20 $\mu$m) yields critical information on material structure for physical, chemical and biological sciences. Despite decades of interest and effort, this portion of the electromagnetic spectrum remains challenging to cover with conventional laser technologies. In this report, we present a simple and robust method for generating super-octave, optical frequency combs in the fingerprint region through intra-pulse difference frequency generation in an orientation-patterned gallium phosphide crystal. We demonstrate the utility of this unique coherent light source for high-precision, dual-comb spectroscopy in methanol and ethanol vapor. These results highlight the potential of laser frequency combs for a wide range of molecular sensing applications, from basic molecular spectroscopy to nanoscopic imaging.

We describe methods using frequency combs and optical resonators for recording two-dimensional (2D) ultrafast spectroscopy signals with high sensitivity. By coupling multiple frequency combs to higher-order modes of one or more optical cavities, background-free, cavity-enhanced 2D spectroscopy signals are naturally generated via phase cycling. As in cavity-enhanced ultrafast transient absorption spectroscopy (CE-TAS), the signal to noise is enhanced by a factor proportional to the cavity finesse squared, so even using cavities of modest finesse, a very high sensitivity is expected, enabling ultrafast 2D spectroscopy experiments in dilute molecular beams.

We present a new technique using a frequency comb laser and optical cavities for performing ultrafast transient absorption spectroscopy with improved sensitivity. Resonantly enhancing the probe pulses, we demonstrate a sensitivity of $\Delta$OD $ = 1 \times 10^{-9}/\sqrt{\mbox{Hz}}$ for averaging times as long as 30 s per delay point ($\Delta$OD$_{min} = 2 \times 10^{-10}$). Resonantly enhancing the pump pulses allows us to produce a high excitation fraction at high repetition-rate, so that signals can be recorded from samples with optical densities as low as OD $\approx 10^{-8}$, or column densities $< 10^{10}$ molecules/cm$^2$. This high sensitivity enables new directions for ultrafast spectroscopy.

Extreme ultraviolet frequency combs are a versatile tool with applications including precision measurement, strong-field physics, and solid-state physics. Here we report on an application of extreme ultraviolet frequency combs and their driving lasers for studying strong-field effects in molecular systems. We perform field-free molecular alignment and high-order harmonic generation with aligned molecules in a gas jet at a repetition rate of 154 MHz using a high-powered optical frequency comb inside a femtosecond enhancement cavity. The cavity-enhanced system provides a means to reach suitable intensities to study field-free molecular alignment and enhance the observable effects of the molecule-field interaction. We observe modulations of the driving field, arising from the nature of impulsive stimulated Raman scattering responsible for coherent molecular rotations. We foresee the impact of this work on the study of molecule-based strong-field physics, with improved precision and a more fundamental understanding of the interaction effects on both the field and molecules., Comment: 5 pages, 5 figures

Many atomic and molecular systems of fundamental interest possess resonance frequencies in the extreme ultraviolet (XUV) where laser technology is limited and radiation sources have traditionally lacked long-term phase coherence. Recent breakthroughs in XUV frequency comb technology have demonstrated spectroscopy with unprecedented resolution at the megahertz level, but even higher resolutions are desired for future applications in precision measurement. By characterizing heterodyne beats between two XUV comb sources, we demonstrate the capability for sub-hertz spectral resolution. This corresponds to coherence times >1 s at photon energies up to 20 eV, more than six orders of magnitude longer than previously reported. This work establishes the ability of creating highly phase-stable radiation in the XUV with performance rivaling that of visible light. Furthermore, by direct sampling of the phase of the XUV light originating from high-harmonic generation, we demonstrate precise measurements of attosecond strong-field physics.

Development of the optical frequency comb has revolutionised metrology and precision spectroscopy due to its ability to provide a precise and direct link between microwave and optical frequencies. A novel application of frequency comb technology that leverages both the ultrashort duration of each laser pulse and the exquisite phase coherence of a train of pulses is the generation of frequency combs in the extreme ultraviolet (XUV) via high harmonic generation (HHG) in a femtosecond enhancement cavity. Until now, this method has lacked sufficient average power for applications, which has also hampered efforts to observe phase coherence of the high-repetition rate pulse train produced in the extremely nonlinear HHG process. Hence, the existence of a frequency comb in the XUV has not been confirmed. We have overcome both challenges. Here, we present generation of >200 {\mu}W per harmonic reaching 50 nm, and the observation of single-photon spectroscopy signals for both an argon transition at 82 nm and a neon transition at 63 nm. The absolute frequency of the argon transition has been determined via direct frequency comb spectroscopy. The resolved 10-MHz linewidth of the transition, limited by the transverse temperature of the argon atoms, is unprecedented in this spectral region and places a stringent upper limit on the linewidth of individual comb teeth. Due to the lack of cw lasers, these frequency combs are currently the only promising avenue towards extending ultrahigh precision spectroscopy to below the 100-nm spectral region with a wide range of applications that include spectroscopy of electronic transitions in molecules, experimental tests of bound state and many body quantum electrodynamics in He+ and He, development of next-generation "nuclear" clocks, and searches for spatial and temporal variation of fundamental constants using the enhanced sensitivity of highly charged ions.