Sum-frequency generation spectro-microscopy in the reststrahlen band of wurtzite-type aluminum nitride.

Nonlinear-optical microscopy and spectroscopy provide detailed spatial and spectroscopic contrast, specifically sensitive to structural symmetry and order. Ferroics, in particular, have been widely studied using second harmonic generation imaging, which provides detailed information on domain structures but typically lacks spectroscopic detail. In contrast, infrared-visible sum-frequency generation (SFG) spectroscopy reveals details of the atomic structure and bonding via vibrational resonances, but conventionally lacks spatial information. In this work, we combine the benefits of nonlinear optical imaging and SFG spectroscopy by employing SFG spectro-microscopy using an infrared free-electron laser. In particular, we demonstrate the feasibility of SFG spectro-microscopy for spectroscopy using in-plane anisotropic wurtzite-type aluminum nitride as a model system. We find the experimental spectra to agree well with our theoretical calculations, and we show the potential of our microscope to provide spatially resolved spectroscopic information in inhomogeneous systems such as ferroics and their domains in the near future.

Ultrafast Relaxation Dynamics of the Antiferrodistortive Phase in Ca Doped SrTiO_{3}.

The ultrafast dynamics of the octahedral rotation in Ca:SrTiO_{3} is studied by time-resolved x-ray diffraction after photoexcitation over the band gap. By monitoring the diffraction intensity of a superlattice reflection that is directly related to the structural order parameter of the soft-mode driven antiferrodistortive phase in Ca:SrTiO_{3}, we observe an ultrafast relaxation on a 0.2 ps timescale of the rotation of the oxygen octahedron, which is found to be independent of the initial temperature despite large changes in the corresponding soft-mode frequency. A further, much smaller reduction on a slower picosecond timescale is attributed to thermal effects. Time-dependent density-functional-theory calculations show that the fast response can be ascribed to an ultrafast displacive modification of the soft-mode potential towards the normal state induced by holes created in the oxygen 2p states.

Temperature dependence of the two-dimensional infrared spectrum of liquid H2O.

Two-dimensional infrared photon-echo measurements of the OH stretching vibration in liquid H2O are performed at various temperatures. Spectral diffusion and resonant energy transfer occur on a time scale much shorter than the average hydrogen bond lifetime of approximately 1 ps. Room temperature measurements show a loss of frequency and, thus, structural correlations on a 50-fs time scale. Weakly hydrogen-bonded OH stretching oscillators absorbing at high frequencies undergo slower spectral diffusion than strongly bonded oscillators. In the temperature range from 340 to 274 K, the loss in memory slows down with decreasing temperature. At 274 K, frequency correlations in the OH stretch vibration persist beyond approximately 200 fs, pointing to a reduction in dephasing by librational excitations. Polarization-resolved pump-probe studies give a resonant intermolecular energy transfer time of 80 fs, which is unaffected by temperature. At low temperature, structural correlations persist longer than the energy transfer time, suggesting a delocalization of OH stretching excitations over several water molecules.

Nonlinear response of vibrational excitons: simulating the two-dimensional infrared spectrum of liquid water.

A simulation formalism for the nonlinear response of vibrational excitons is presented and applied to the OH stretching vibrations of neat liquid H(2)O. The method employs numerical integration of the Schrodinger equation and allows explicit treatment of fluctuating transition frequencies, vibrational couplings, dipole moments, and the anharmonicities of all these quantities, as well as nonadiabatic effects. The split operator technique greatly increases computational feasibility and performance. The electrostatic map for the OH stretching vibrations in liquid water employed in our previous study [A. Paarmann et al., J. Chem. Phys. 128, 191103 (2008)] is presented. The two-dimensional spectra are in close agreement with experiment. The fast 100 fs dynamics are primarily attributed to intramolecular mixing between states in the two-dimensional OH stretching potential. Small intermolecular couplings are sufficient to reproduce the experimental energy transfer time scales. Interference effects between Liouville pathways in excitonic systems and their impact on the analysis of the nonlinear response are discussed.

Probing intermolecular couplings in liquid water with two-dimensional infrared photon echo spectroscopy.

Two-dimensional infrared photon echo and pump probe studies of the OH stretch vibration provide a sensitive probe of the correlations and couplings in the hydrogen bond network of liquid water. The nonlinear response is simulated using numerical integration of the Schrodinger equation with a Hamiltonian constructed to explicitly treat intermolecular coupling and nonadiabatic effects in the highly disordered singly and doubly excited vibrational exciton manifolds. The simulated two-dimensional spectra are in close agreement with our recent experimental results. The high sensitivity of the OH stretch vibration to the bath dynamics is found to arise from intramolecular mixing between states in the two-dimensional anharmonic OH stretch potential. Surprisingly small intermolecular couplings reproduce the experimentally observed intermolecular energy transfer times.

Hemiretinal stimuli elicit different amplitudes in the pattern electroretinogram.

Pattern electroretinograms were elicited in 13 normal eyes by half-field checkerboard stimulation of nasal-temporal and upper-lower retinal areas. With nasal-temporal visual half-field stimulation the p-q component amplitude of the nasal hemiretina was significantly larger than that of the temporal hemiretina. With upper-lower visual half-field stimulation the amplitude was significantly larger for the upper than for the lower hemiretina. No significant differences were found with respect to the component latency. Finding the p-q amplitude of the pattern electroretinogram to be closely related to the distribution of nerve cells in the innermost retinal layer supports the conclusion that the pattern response is generated in the more proximal retinal layers including the retinal ganglion cells.

Cone interaction and color substitution as revealed by pattern ERG.

Transient electroretinograms to a reversing color-contrast checkerboard pattern (P-ERG) were recorded in a protanomalous, a deuteranomalous, and a normal observer. Alternate monochromatic checks were of constant wavelength (630 nm red-531 nm green), while the relative energies were varied systematically. When changing the radiance ratio 630 nm-531 nm of the stimulus, the normal subject exhibited a P-ERG to all stimuli with only a relative amplitude minimum at a distinct radiance ratio, whereas the color-deficient observers failed to show a P-ERG at some color contrast 630 nm-531 nm, the radiance ratio of which was different in the protan and deutan. From the radiance ratio of color contrast for the smallest potential in the normal observer, we conclude that the green- and red-sensitive cone mechanism provides a difference signal which generates the response. The data from the color-deficient observer support the view that color discrimination in protans and deutans is reduced because the input of one type of photoreceptor is missing.