Gas phase A-band short time photodissociation dynamics of trans and gauche conformations of 1-iodopropane and comparison with the solution phase short time photodissociation dynamics

A-band resonance Raman spectra are reported for gas phase 1-iodopropane. The gas phase absorption spectrum and resonance Raman intensities were simulated using time-dependent wavepacket calculations and a simple model in order to extract the A-band short time photo-dissociation dynamics for the trans and gauche conformers of 1-iodopropane. The gas phase short time dynamics for trans and gauche are very similar to the results obtained from a reanalysis of corresponding solution phase spectra. This indicates that solvation has little effect on the A-band short time photodissociation dynamics. However, the electronic dephasing parameters for the gauche conformer increase significantly upon solvation while the trans conformer parameters are almost the same in the gas and solution phases. This suggests that the gauche conformer in the A-band excited electronic state undergoes stronger interaction with the solvent than the trans conformer to give rise to faster electronic dephasing upon solvation for the gauche conformer.     

Resonance Raman investigation of the short-time dynamics of the ultraviolet photodissociation of bromoform

We report ultraviolet resonance Raman spectra of bromoform (CHBr₃) in cyclohexane solution. The resonance Raman spectra show significant intensity in the overtones of the nominal Br-C-Br symmetric bend (v ₆), the nominal H-C-Br asymmetric bend (v3), the nominal Br-C-Br symmetric stretch (v ₂) and the nominal Br-C-Br asymmetric stretch (v ₅) vibrational modes suggesting that the short-time photodissociation dynamics have noticeable multidimensional character. The lack of strong combination bands between several of the Franck-Condon active modes suggests that more than one electronic transition contribute to the resonance Raman spectra. We briefly discuss the ultraviolet short-time photodissociation dynamics of bromoform and the potential implications for the secondary photodissociation reactions of the initially formed CHBr₂ radical.     

Indole photodissociation in the gas phase

Kinetic characteristics of the growth in delayed luminescence intensity of indole in the gas phase have been measured with excitation of the molecules in the spectral region 250–287 nm. The luminescence build-up kinetics show two components with characteristic lifetimes of about 1 and 10 μs that are associated with the formation of free radicals due to N–H bond dissociation. Two basic mechanisms for photodissociation of indole in the gas phase have been identified based on an analysis of the dependence of the kinetic characteristics for these components on the excitation radiation wavelength/intensity and the vapor pressures of indole and foreign gases. The fast component results from the dissociation of an N–H bond of vibrationally excited molecules in the ground state that is populated through internal conversion. The slow component is associated with the generation of free radicals because of annihilation of two triplet indole molecules. A dependence of the quantum yield of intersystem crossing on the excitation wavelength in the spectral region 260–287 nm has been found. It is shown that the fluorescence quantum yield drop with a decrease of the excitation radiation wavelength is caused by an increase in the internal conversion quantum yield to the electronic ground state.     

Distinguishing the monomer to cluster phase transition in concentrated lysozyme solutions by studying the temperature dependence of the short-time dynamics

Recent combined experiments by small angle neutron scattering (SANS) and neutron spin echo (NSE) have demonstrated that dynamic clusters can form in concentrated lysozyme solutions when the right combination of a short-ranged attraction and a long-ranged electrostatic repulsion exists. In this paper, we investigate the temperature effect on the dynamic cluster formation and try to pinpoint the transition concentration from a monomeric protein phase to a cluster phase. Interestingly, even at a relatively high concentration (10% mass fraction), despite the significant change in the SANS patterns that are associated with the change of the short-ranged attraction among proteins, the normalized short-time self-diffusion coefficient is not affected between 5 and 40?°C. This is interpreted as a lack of cluster formation in this condition. However, at larger concentrations such as 17.5% and 22.5% mass fraction, we show that the average hydrodynamic radius increases significantly and causes a large decrease of the normalized self-diffusion coefficient as a result of cluster formation when the temperature is changed from 25 to 5?°C.     

The effect of collisions with nitrogen on absorption by oxygen in the A-band using cavity ring-down spectroscopy.

This paper reports on the effect of collisions between nitrogen and oxygen on absorption in the A-band near 760?nm under atmospheric conditions relevant for satellite retrieval studies. We use pulsed laser cavity ring-down spectroscopy with a narrow bandwidth laser and use pressure scans to increase the accuracy of the measured oxygen extinction coefficients. We use the so-called Adjustable Branch Coupling model to describe line mixing in the magnetic allowed A-band dipole absorption and we retrieve the collision induced absorption spectrum due to N₂–O₂ collisions.     

Unraveling the solid-liquid-vapor phase transition dynamics at the atomic level with ultrafast x-ray absorption near-edge spectroscopy

X-ray absorption near-edge spectroscopy (XANES) is a powerful probe of electronic and atomic structures in various media, ranging from molecules to condensed matter. We show how ultrafast time resolution opens new possibilities to investigate highly nonequilibrium states of matter including phase transitions. Based on a tabletop laser-plasma ultrafast x-ray source, we have performed a time-resolved (～3 ps) XANES experiment that reveals the evolution of an aluminum foil at the atomic level, when undergoing ultrafast laser heating and ablation. X-ray absorption spectra highlight an ultrafast transition from the crystalline solid to the disordered liquid followed by a progressive transition of the delocalized valence electronic structure (metal) down to localized atomic orbitals (nonmetal-vapor), as the average distance between atoms increases.     

Calculation of the short-time dynamics of the hot-electron distribution in noble and transition metals

Received: 23 October 1998     

Role of the gouy phase in the coherent phase control of the photoionization and photodissociation of vinyl chloride

We demonstrate theoretically and experimentally that the Gouy phase of a focused laser beam may be used to control the photoinduced reactions of a polyatomic molecule. Quantum mechanical interference between one- and three-photon excitation of vinyl chloride produces a small phase lag between the dissociation and ionization channels on the axis of the molecular beam. Away from the axis, the Gouy phase introduces a much larger phase lag that agrees quantitatively with theory without any adjustable parameters.     

Spontaneous-search method and short-time dynamics: applications to the Domany-Kinzel cellular automaton

The one-dimensional Domany-Kinzel cellular automaton is investigated by two numerical approaches: (i) the spontaneous-search method, which is a method appropriated for a search of criticality; (ii) short-time dynamics. Both critical frontiers of the system are investigated, namely, the one separating the frozen and active phases, as well as the critical line determined by damage spreading between two cellular automata, that splits the active phase into the nonchaotic and chaotic phases. The efficiency of the spontaneous-search method is established herein through a precise estimate of both critical frontiers, and in addition to that, it is shown that this method may also be used in the determination of the critical exponent ν_⊥. Using the critical frontiers obtained, other exponents are estimated through short-time dynamics. It is verified that the critical exponents of both critical frontiers fall in the universality class of directed percolation.     

Polarized fluorescence of radicals in photodissociation of disulfides in the gas phase

The polarization of the fluorescence of radicals formed in laser-induced photodissociation of some disulfides in the gas phase is measured. Experimental data obtained in the study are interpreted within the free recoil model. It is shown that polarization experiments carried out to investigate photodecay in vapors allow researchers to uniquely the intramolecular direction of the dipole moments of transitions with absorption and emission. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 54–59, January–February, 1999.     

Laser-driven switching dynamics in phase change materials investigated by time-resolved X-ray absorption spectroscopy

Time-dependent X-ray absorption spectroscopy at the Ge L₃ edge is used to study the optical switching dynamics of epitaxial phase change materials grown on Si(111) membranes. Small differences between the static absorption spectra of the crystalline and laser-amorphized phase of GeTe are observed. Furthermore, a new approach for pump-probe studies on phase change materials is presented. However, no time-dependent change in the X-ray absorption > 0.1% has been detected so far. This is mainly attributed to sample deterioration at 3 kHz pump-probe rates.     

Berry phase effects on the dynamics of quasiparticles in a superfluid with a vortex

We study quasiparticle dynamics in a Bose-Einstein condensate with a vortex by following the center of mass motion of a Bogoliubov wave packet, and find important Berry-phase effects due to the background flow. We show that the Berry phase invalidates the usual canonical relation between the mechanical momentum and position variables, leading to important modifications of quasiparticle statistics and thermodynamic properties of the condensates. Applying these results to a vortex in an infinite uniform superfluid, we find that the total transverse force acting on the vortex is proportional to the superfluid density. We propose an experimental setup to directly observe Berry phase effects through measuring local thermal atoms' momentum distribution around a vortex.     

Test of a Fokker-Planck-Kramers equation treatment for short-time dynamics of diffusion-controlled reactions by molecular dynamics simulation in Lennard-Jones fluids

We test the extended Harris (EXH) theory for the dynamics of diffusion-controlled reactions using the molecular dynamics simulations in Lennard-Jones fluids. The EXH theory is based on the Fokker-Planck-Kramers equation in which the inertia effect on the molecular migration is taken into account. The time dependence of the theoretical survival probabilities of the reactant agrees with the simulation results if the potential of mean force and the initial equilibrium distribution are appropriately taken into account. The position dependence of the diffusion coefficient is not necessary in explaining the simulation results. On the other hand, the simulation results cannot be reproduced if the two-body or the uniform potentials are employed in the theoretical calculations.     

Infrared photodissociation spectroscopy of protonated neurotransmitters in the gas phase – ARTICLE WITHDRAWN

WITHDRAWN TO APPEAR IN SPECIAL ISSUE IN 2007     

Sound absorption in a colloidal solution of interacting particles

The absorption of sound in a colloidal solution is studied with allowance for interaction between microparticles or nanoparticles. It is shown that electrostatic repulsion, which is typical of charged colloids used in science and engineering, leads to an increase in absorption, all other factors being the same. This is related to the fact that the effective correlation length characterizing the motion of particles increases when the interparticle interaction becomes stronger.     

Polarization dynamics of a monochromatic laser with linear phase anisotropy

We analyse this laser's phase diagram: the properties of its steady states when varying the linear phase anisotropy, the intensity coupling asymmetry, or the pump rate. Most interesting is a parameter window in which the laser output is a limit cycle, and not only the intensity but also the electric field polarization varies periodically. The dependence of the polarization on the laser parameters is evaluated for various states.