Two-photon absorption ͑2PA͒ spectroscopy in the range from 7 to 10 eV provides new insight on the electronic structure of liquid water. Continuous 2PA spectra are obtained via the pump-probe technique, using broadband probe pulses to record the absorption at many wavelengths simultaneously. A preresonance enhancement of the absolute 2PA cross section is observed when the pump-photon energy increases from 4.6 to 6.2 eV. The absorption cross section also depends on the relative polarization of the pump and probe photons. The variation of the polarization ratio across the spectrum reveals a detailed picture of the 2PA and indicates that at least four different transitions play a role below 10 eV. Theoretical polarization ratios for the isolated molecule illustrate the value of the experimental polarization measurement in deciphering the 2PA spectrum and provide the framework for a simple simulation of the liquid spectrum. A more comprehensive model goes beyond the isolated molecule picture and connects the 2PA spectrum with previous one-photon absorption, photoelectron, and x-ray absorption spectroscopy measurements of liquid water. Previously unresolved, overlapping transitions are assigned for the first time. Finally, the electronic character of the vertical excited states is related to the energy-dependent ionization mechanism of liquid water.

The ICN photodissociation reaction is the prototype system for understanding energy disposal and curve crossing in small molecule bond-breaking. The wide knowledge base on this reaction in the gas phase makes it an excellent test case to explore and understand the influence of a liquid solvent on the photo-induced reaction dynamics. Molecular dynamics simulations that include surface-hopping have addressed numerous aspects of how the solvent should influence non-adiabatic transitions and energy flow and ultimately determine product branching for this reaction system. In this paper, we report femtosecond transient absorption work directly combined with new molecular dynamics simulations that make direct connection with the spectroscopic observables. The full spectral evolution after initiating ICN photodissociation at 266 nm in water and ethanol is recorded with unprecedented time resolution, fast enough to see the nascent products emerge before interacting with the solvent cage. Use of a 266 nm pump maximizes the probability of subsequent caging on the upper diabat while launching large rotational energy release for trajectories emerging on the lower diabat. The 2D dataset yields a map of the different products and how they interconvert. In particular, information on the branching ratio and spectral evolution of the product bands is revealed as the products relax their electronic and rotational degrees of freedom. An evolution from rotationally hot gas-phase like CN (sharp band, at 390 nm) to equilibrated and solvated CN radicals (broad, at 326 nm in water and 415 nm in ethanol) is clearly observed in both solvents, and signals assignable to I* are also captured. The non-adiabatic molecular dynamics simulations focus on identifying when trajectories curve cross, filtering the trajectory ensemble into spectroscopically distinct sub-populations and analyzing the rotational energy for the CN product population. The experimental results, taken together with the MD simulations, establish the initial surface crossing probability and suggest multiple passes through the curve crossing region determine the final product yields and provide a source of freshly torqued CN radicals that continues to top up the population of rotationally hot photoproduct over the first few picoseconds.

Vibrational sum-frequency generation (VSFG) has become a widely used technique for studying molecular orientation and intermolecular structure at interfaces. Due to the interfacial and vibrational selectivity of this technique, it can be used to probe molecular monolayers that are buried within bulk materials. Here, we present a critical review and examination of the assumptions that are generally used in the interpretation of VSFG spectra. This review focuses on three different aspects of VSFG spectroscopy. First, we examine the effect of dynamics (both reorientation and energy transfer) on the interpretation of VSFG spectra. Second, we consider whether (and under what circumstances) VSFG spectra cannot be interpreted solely in terms of the spectral properties of individual molecules. Third, we consider whether VSFG spectra obtained in different modes (frequency-domain, time-domain and broadband) should provide identical information. We conclude with a discussion of the challenges and opportunities provided by the revised viewpoint of VSFG that we present.

Previous experiments and simulations have shown that acetonitrile organizes into a lipid-like bilayer at the liquid/silica interface. Recent simulations have further suggested that this bilayer structure persists in mixtures of acetonitrile with water, even at low acetonitrile concentrations. This behavior is indicative of microscopic phase separation of these liquids near silica interfaces and may have important ramifications for the use of acetonitrile in chromatography and heterogeneous catalysis. To explore this phenomenon, we have used vibrational sum-frequency-generation spectroscopy to probe acetonitrile/water mixtures at a silica interface. Our spectra provide evidence that acetonitrile partitions to the hydrated silica interface even when the mole fraction of acetonitrile is as low as 10%. A blue shift is observed in the spectrum of the methyl symmetric stretch upon increasing water mole fraction, in agreement with vibrational spectra of bulk mixtures. Line shape analysis suggests that acetonitrile may exist in the form of bilayer patches at high water mole fractions.