Hydrophobic Molecules Slow Down the Hydrogen-Bond Dynamics of Water

We study the spectral and orientational dynamics of HDO molecules in solutions of tertiary-butyl-alcohol (TBA), trimethyl-amine-oxide (TMAO), and tetramethylurea (TMU) in isotopically diluted water (HDO:D2O and HDO:H2O). The spectral dynamics are studied with femtosecond two-dimensional infrared spectroscopy and the orientational dynamics with femtosecond polarization-resolved vibrational pump-probe spectroscopy. We observe a strong slowing down of the spectral diffusion around the central part of the absorption line that increases with increasing solute concentration. At low concentrations, the fraction of water showing slow spectral dynamics is observed to scale with the number of methyl groups, indicating that this effect is due to slow hydrogen-bond dynamics in the hydration shell of the methyl groups of the solute molecules. The slowing down of the vibrational frequency dynamics is strongly correlated with the slowing down of the orientational mobility of the water molecules. This correlation indicates that these effects have a common origin in the effect of hydrophobic molecular groups on the hydrogen-bond dynamics of water.

Water-Mediated Ion Pairing: Occurrence and Relevance

We present an overview of the studies of ion pairing in aqueous media of the past decade. In these studies, interactions between ions, and between ions and water, are investigated with relatively novel approaches, including dielectric relaxation spectroscopy, far-infrared (terahertz) absorption spectroscopy, femtosecond mid-infrared spectroscopy, and X-ray spectroscopy and scattering, as well as molecular dynamics simulation methods. With these methods, it is found that ion pairing is not a rare phenomenon only occurring for very particular, strongly interacting cations and anions. Instead, for many salt solutions and their interfaces, the measured and calculated structure and dynamics reveal the presence of a distinct concentration of contact ion pairs (CIPs), solvent shared ion pairs (SIPs), and solvent-separated ion pairs (2SIPs). We discuss the importance of specific ion-pairing interactions between cations like Li+ and Na+ and anionic carboxylate and phosphate groups for the structure and functioning of large (bio)molecular systems

Orientational relaxation of liquid water molecules as an activated process

Femtosecond mid-infrared pump-probe spectroscopy is used to study the orientational relaxation of HDO molecules dissolved in liquid D2O. In this technique, the excitation of the O-H stretch vibration is used as a label in order to follow the orientational motion of the HDO molecules. The decay of the anisotropy is nonexponential with a typical time scale of 1 ps and can be described with a model in which the reorientation time depends on frequency and in which the previously observed spectral diffusion is incorporated. From the frequency and temperature dependence of the anisotropy decay, the activation energy for reorientation can be derived. This activation energy is found to increase with increasing hydrogen bond strength. (C) 2000 American Institute of Physics. [S0021-9606(00)52019- 4

Research of the Power Plant Operational Modes

In this article the algorithm of the power plant operational modes research is offered. According to this algorithm the program for the modes analysis and connection power transformers choice is developed. The program can be used as educational means for studying of the power plant electric part, at the same time basic data are provided. Also the program can be used for the analysis of the working power plants modes. Checks of the entered data completeness and a choice correctness of the operational modes are provided in the program; in all cases of a deviation from the correct decisions to the user the relevant information is given

Dynamics of water molecules in an alkaline environment

We report on a two-color mid-infrared pump-probe spectroscopic study of the dynamics of the OH stretch vibrations of HDO molecules dissolved in a concentrated (10 M) solution of NaOD in D2O. We observe that spectral holes can be created in the broad OH stretch absorption band that change neither position nor width on a picosecond time scale. This behavior differs strongly from that of pure HDO:D2O where rapid spectral diffusion (tau(c)approximate to600 fs) occurs. The long-living inhomogeneity indicates that a concentrated aqueous NaOX (X=H,D) solution has a very static hydrogen-bond network. The results also show that the absorption band of the OH stretch vibration consists of two separate classes of OH groups with very different vibrational lifetimes. For component I, the lifetime of the OH stretch vibration is similar to600 fs and increases with OH frequency, which can be explained from the accompanying decrease in the strength of the hydrogen-bond interaction. This component represents HDO molecules of which the OH group is bonded to a D2O molecule via a DO-H.OD2 hydrogen bond. For component II, the lifetime is similar to160 fs, and does not show a significant frequency dependence. This component represents HDO molecules that are hydrogen bonded to a D2O molecule or an OD- ion. The short, frequency-independent vibrational lifetime of component II can be explained from the participation of the HDO molecule and its hydrogen-bonded partner in deuteron and/or proton-transfer processes. (C) 2002 American Institute of Physic

Observation of a stronger-than-adiabatic change of light trapped in an ultrafast switched GaAs-AlAs microcavity

We study the time-resolved reflectivity spectrum of a switched planar GaAs-AlAs microcavity. Between 5 and 40 ps after the switching (pump) pulse we observe a strong excess probe reflectivity and a change of the frequency of light trapped in the cavity up to 5 linewidths away from the cavity resonance. This frequency change does not adiabatically follow the fast-changing cavity resonance. The frequency change is attributed to an accumulated phase change due to the time-dependent refractive index. An analytical model predicts dynamics in qualitative agreement with the experiments, and points to crucial parameters that control future applications.Comment: Discussed effect of probe bandwidth. Included functional forms of n(z) and R(z