Biomedical subjects

P Jungwirth

Publications and source records attributed to P Jungwirth.

5 recordsLinked to original sources

PubMed2005

Ultrafast far-infrared dynamics probed by terahertz pulses: a frequency domain approach. I. Model systems.

Time-resolved terahertz spectroscopy has become a widely used experimental tool for the investigation of ultrafast dynamics of polar systems in the far infrared. We have recently proposed an analytical method for the extraction of a transient two-dimensional susceptibility from the experimental data [Nĕmec, Kadlec, and Kuzel, J. Chem. Phys. 117, 8454 (2002)]. In the present paper the methodology of optical pump-terahertz probe experiments is further developed for direct application in realistic experimental situations. The expected two-dimensional transient response function is calculated for a number of model cases (including Drude dynamics of free carriers, harmonic and anharmonic oscillator modes); these results serve as a basis for the interpretation of experimental results. We discuss also the cases where only partial (one-dimensional) information about the system dynamics can be experimentally obtained.

Journal Article↗

PubMed2005

Ultrafast far-infrared dynamics probed by terahertz pulses: a frequency-domain approach. II. Applications.

We present data obtained by time-resolved terahertz spectroscopy in selected semiconducting and molecular systems exhibiting subpicosecond far-infrared dynamics. We use a frequency-domain method which eliminates the influence of instrumental functions and artifacts due to frequency mixing and yields a two-dimensional transient conductivity of the photoexcited sample. This technique enables improving the attainable experimental time resolution and allows a simple qualitative interpretation of the results without a priori modeling. The quantitative interpretation is based on the time-dependent Drude and damped harmonic oscillator models.

Journal Article↗

PubMed2004

Calculation of the photodetachment cross sections of the HCN- and HNC- dipole-bound anions as described by a one-electron Drude model.

The Drude model for treating the interaction of excess electrons with polar molecules is extended to calculate continuum functions and to evaluate photodetachment cross sections. The approach is applied to calculate the cross sections for photodetachment of dipole-bound electrons from HCN(-) and HNC(-). In addition, an adiabatic model separating the angular and radial degrees of freedom of the excess electron is introduced and shown to account in a qualitative manner for the cross sections.

Journal Article↗

PubMed2000

Experiments and simulations of ion-enhanced interfacial chemistry on aqueous NaCl aerosols

A combination of experimental, molecular dynamics, and kinetics modeling studies is applied to a system of concentrated aqueous sodium chloride particles suspended in air at room temperature with ozone, irradiated at 254 nanometers to generate hydroxyl radicals. Measurements of the observed gaseous molecular chlorine product are explainable only if reactions at the air-water interface are dominant. Molecular dynamics simulations show the availability of substantial amounts of chloride ions for reaction at the interface, and quantum chemical calculations predict that in the gas phase chloride ions will strongly attract hydroxl radicals. Model extrapolation to the marine boundary layer yields daytime chlorine atom concentrations that are in good agreement with estimates based on field measurements of the decay of selected organics over the Southern Ocean and the North Atlantic. Thus, ion-enhanced interactions with gases at aqueous interfaces may play a more generalized and important role in the chemistry of concentrated inorganic salt solutions than was previously recognized.

Journal Article↗

PubMed2000

Double tunneling: An overlooked quantum effect in anionic molecular clusters

Simultaneous tunneling of an electron and nuclei in hydrogen-bonded molecular clusters which support a dipole bound electron is reported. A whole class of systems including hydrogen halide and water dimer anions is predicted to exhibit this effect. A measurable signature of double tunneling is a strong reduction of the tunneling splitting compared to the neutral cluster. Quantum mechanical calculations give for the hydrogen fluoride dimer anion a ground-state tunneling splitting of 114 MHz, while for the first excited vibrational state the tunneling splitting reaches 4.20 GHz.

Journal Article↗