Center line slope (CLS) analysis in 2D infrared spectroscopy has been extensively used to extract frequency-frequency correlation functions of vibrational transitions. We apply this concept to 2D electronic spectroscopy, where CLS is a measure of electronic gap fluctuations. The two domains, infrared and electronic, possess differences: In the infrared, the frequency fluctuations are classical,...

We observe vibrational states by photoassociation spectroscopy of cold He(2 ^{3}S) atoms. Photoassociation resonances are detected as peaks in the Penning ionization rate over a frequency range of 20 GHz below the atomic 2 ^{3}S_{1}-2 ^{3}P_{2} transition frequency. We have observed three vibrational series, of which two can be identified. A possible mechanism to explain the observed increase o...

Enantioenriched square-pyramidal oxo- and sulfidorhenium(v) complexes have been prepared and their stereochemistry studied by vibrational circular dichroism (VCD) spectroscopy.

The vibrational configuration interaction method used to obtain static vibrational (hyper)polarizabilities is extended to dynamic nonlinear optical properties in the infinite optical frequency approximation. Illustrative calculations are carried out on H(2)O and NH(3). The former molecule is weakly anharmonic while the latter contains a strongly anharmonic umbrella mode. The effect on vibration...

The vibrational Stark effect measures the effect of an external electric field on the vibrational (IR) spectrum of a molecule. This technique gives quantitative information on the sensitivity of a vibrational peak position to an electric field. This calibration can be used to evaluate shifts in the vibrational frequency caused by changes in the local electric field in the organized electrostati...

A molecular theory of time-resolved sum-frequency generation (SFG) has been developed. The theoretical framework is constructed using the coupled-oscillator model in the adiabatic approximation. This theory can treat not only the vibrational spectroscopy but also vibrational dynamics. An application of this theory is also provided for estimation of the time constants of the intermolecular vibra...

The electrical and spectral characteristics of a dielectric barrier discharge (DBD) are experimentally investigated in a sealed off coaxial cylinder filled with nitrogen at a pressure of 10 mbar. The discharge is a transient diffused glow at low frequency alternating voltage (60 Hz) and changes to a filamentary mode at high frequency alternating voltage (35 kHz). In case of pulsed voltage, the ...

We study the vibrational properties near a free surface of disordered spring networks derived from jammed sphere packings. In bulk systems, without surfaces, it is well understood that such systems have a plateau in the density of vibrational modes extending down to a frequency scale ω*. This frequency is controlled by ΔZ = 〈Z〉 - 2d, the difference between the average coordination of the sphere...

Excited-state vibrational coherence of solution-phase polyatomic molecules was studied by two different timedomain spectroscopic methods. Raman-active low-frequency vibrations in the excited state of trans-stilbene were observed by transient impulsive stimulated Raman scattering spectroscopy. In transient absorption spectroscopy with a 40-fs resolution, a different vibrational mode of the same ...

Vibrational excitations of low frequency collective modes are essential for functionally important conformational transitions in proteins. Here we report the first direct measurement on the lifetime of vibrational excitations of the collective modes at 87 pm (115 cm(-1)) in bacteriorhodopsin, a transmembrane protein. The data show that these modes have extremely long lifetime of vibrational exc...