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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′-hydroxy-2′-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 ∼ 40 K) and hot (∼ 403 K) molecules via cavity-enhanced TAS (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 (∼1700 graphics processing unit hours for ∼4 ns of electron dynamics) was markedly less than that of performing the ab initio multiple spawning calculations used to compute the underlying nonadiabatic dynamics. [ABSTRACT FROM AUTHOR]

Salicylideneaniline (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 S1 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 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. [ABSTRACT FROM AUTHOR]

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 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 >1011 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 × 100 μm2. 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 strong space charge distortions of the photoelectron spectra, and excellent isolation of individual harmonic orders allow us to observe laser-induced modifications of the photoelectron spectra at the 10−4 level, enabling time-resolved XUV photoemission experiments in a qualitatively new regime. [ABSTRACT FROM AUTHOR]

We present a detailed description of the design, construction, and performance of high-power ultrafast Yb:fiber laser frequency combs in operation in our laboratory. We discuss two such laser systems: an 87 MHz, 9 W, 85 fs laser operating at 1060 nm and an 87 MHz, 80 W, 155 fs laser operating at 1035 nm. Both are constructed using low-cost, commercially available components, and can be assembled using only basic tools for cleaving and splicing single-mode fibers. We describe practical methods for achieving and characterizing low-noise single-pulse operation and long-term stability from Yb:fiber oscillators based on nonlinear polarization evolution. Stabilization of the combs using a variety of transducers, including a new method for tuning the carrier-envelope offset frequency, is discussed. High average power is achieved through chirped-pulse amplification in simple fiber amplifiers based on double-clad photonic crystal fibers. We describe the use of these combs in several applications, including ultrasensitive femtosecond time-resolved spectroscopy and cavity-enhanced high-order harmonic generation. [ABSTRACT FROM AUTHOR]

We present a detailed description of the design, construction, and performance of high-power ultrafast Yb:fiber laser frequency combs in operation in our laboratory. We discuss two such laser systems: an 87 MHz, 9 W, 85 fs laser operating at 1060 nm and an 87 MHz, 80 W, 155 fs laser operating at 1035 nm. Both are constructed using low-cost, commercially available components, and can be assembled using only basic tools for cleaving and splicing single-mode fibers. We describe practical methods for achieving and characterizing low-noise single-pulse operation and long-term stability from Yb:fiber oscillators based on nonlinear polarization evolution. Stabilization of the combs using a variety of transducers, including a new method for tuning the carrier-envelope offset frequency, is discussed. High average power is achieved through chirped-pulse amplification in simple fiber amplifiers based on double-clad photonic crystal fibers. We describe the use of these combs in several applications, including ultrasensitive femtosecond time-resolved spectroscopy and cavity-enhanced high-order harmonic generation.