Reorientation-induced spectral diffusion in vibrational sum-frequency-generation spectroscopy.

There is a growing appreciation that dynamic processes play an important role in determining the line shape in surface-selective, nonlinear spectroscopies such as vibrational sum-frequency-generation (VSFG). Here we analyze the influence that reorientation can have on VSFG spectra when the vibrational transition frequency is a function of orientation. Under these circumstances, reorientation-induced spectral diffusion (RISD) causes the underlying spectral line shape to become time dependent.

Persistence of acetonitrile bilayers at the interface of acetonitrile/water mixtures with silica.

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.

The dynamical role of solvent on the ICN photodissociation reaction: connecting experimental observables directly with molecular dynamics simulations.

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.

Gires-Tournois interferometer type negative dispersion mirrors for deep ultraviolet pulse compression.

Typical femtosecond pulse compression of deep ultraviolet radiation consists of prism or diffraction grating pair chirp compensation but, both techniques introduce higher-order dispersion, spatial-spectral beam distortion and poor transmission. While negatively chirped dielectric mirrors have been used to compress near infrared and visible pulses to <10 fs, there has been no extension of this technique below 300 nm. We demonstrate the use of Gires-Tournois interferometer (GTI) negative dispersion multilayer dielectric mirrors designed for pulse compression in the deep ultraviolet region.

Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy.

Two-photon absorption (2PA) 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.