N Huse | PubMed Health

PubMed2005

Anharmonic couplings underlying the ultrafast vibrational dynamics of hydrogen bonds in liquids.

The multilevel structure and vibrational couplings of O-H stretching transitions in intermolecular hydrogen bonds of acetic acid dimers are determined by femtosecond two-dimensional photon-echo spectroscopy in the infrared. Combining experiment and theoretical calculations, we separate Fermi resonances with combination tones of fingerprint modes from anharmonic couplings to underdamped low-frequency modes of the dimer. A multilevel density matrix approach based on density functional theory calculations reproduces the experimental results and reveals coupling strengths of both mechanisms on the order of 40-150 cm(-1).

Journal Article↗

PubMed2005

Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O.

Many of the unusual properties of liquid water are attributed to its unique structure, comprised of a random and fluctuating three-dimensional network of hydrogen bonds that link the highly polar water molecules. One of the most direct probes of the dynamics of this network is the infrared spectrum of the OH stretching vibration, which reflects the distribution of hydrogen-bonded structures and the intermolecular forces controlling the structural dynamics of the liquid. Indeed, water dynamics has been studied in detail, most recently using multi-dimensional nonlinear infrared spectroscopy for acquiring structural and dynamical information on femtosecond timescales. But owing to technical difficulties, only OH stretching vibrations in D2O or OD vibrations in H2O could be monitored. Here we show that using a specially designed, ultrathin sample cell allows us to observe OH stretching vibrations in H2O. Under these fully resonant conditions, we observe hydrogen bond network dynamics more than one order of magnitude faster than seen in earlier studies that include an extremely fast sweep in the OH frequencies on a 50-fs timescale and an equally fast disappearance of the initial inhomogeneous distribution of sites. Our results highlight the efficiency of energy redistribution within the hydrogen-bonded network, and that liquid water essentially loses the memory of persistent correlations in its structure within 50 fs.

Absorption↗

PubMed2001

Z-polarized confocal microscopy.

In light microscopy the transverse nature of the electromagnetic field precludes a strongly focused longitudinal field component, thus confining polarization spectroscopy and imaging to two dimensions (x,y). Here we describe a simple confocal microscopy arrangement that optimizes for signal from molecules with transition dipoles oriented parallel to the optic axis. In the proposed arrangement, we not only generate a predominant longitudinally (z) polarized focal field, but also engineer the detection scheme in such a way that in a bulk of randomly oriented molecules, the microscope's effective point-spread function is dominated by the contribution of those molecules that are oriented along the optic axis. Our arrangement not only implicitly allows for the determination of the orientation of transition dipoles of single molecules in three dimensions, but also highlights the contribution of z-oriented molecules in three-dimensional imaging.

Microscopy, Confocal↗

PubMed2001

Z-polarized confocal microscopy.

In light microscopy the transverse nature of the electromagnetic field precludes a strongly focused longitudinal field component, thus confining polarization spectroscopy and imaging to two dimensions (x,y). Here we describe a simple confocal microscopy arrangement that optimizes for signal from molecules with transition dipoles oriented parallel to the optic axis. In the proposed arrangement, we not only generate a predominant longitudinally (z) polarized focal field, but also engineer the detection scheme in such a way that in a bulk of randomly oriented molecules, the microscope's effective point-spread function is dominated by the contribution of those molecules that are oriented along the optic axis. Our arrangement not only implicitly allows for the determination of the orientation of transition dipoles of single molecules in three dimensions, but also highlights the contribution of z-oriented molecules in three-dimensional imaging.

Microscopy, Confocal↗