TITLE

Condensed phase spectroscopy from mixed-order semiclassical molecular dynamics: Absorption, emission, and resonant Raman spectra of I2 isolated in solid Kr

AUTHOR(S)
Ovchinnikov, M.; Apkarian, V. A.
PUB. DATE
December 1996
SOURCE
Journal of Chemical Physics;12/15/1996, Vol. 105 Issue 23, p10312
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
A method for spectral simulations in systems of very large dimensionality via semiclassical molecular dynamics is introduced and applied to the spectroscopy of iodine isolated in solid Kr, as a prototype of spectroscopy in condensed media in general. The method relies on constructing quantum correlation functions, C(t), using initial value propagators which correspond to the zeroth- and second-order approximations in stationary phase of the exact quantum propagator. The first is used for treating modes with high thermal occupation numbers, the lattice modes, while the second is used for treating the guest mode. The limits of validity of the bare propagators are tested vs exact treatments of gas phase I2, and shown to be quite broad. The mixed order simulations are then used to reproduce the structured A→X emission, the structureless B←X absorption, and the intensities in resonant Raman (RR) progressions of matrix isolated I2, connecting spectroscopic observables to molecular motions. Decompositions of the supersystem correlations into system and bath are used to provide perspectives about condensed phase spectroscopy. The system correlation can be regarded as the sampling function for the decaying bath correlation, which in turn is a summary of the many-body dynamics. The B←X absorption spectrum is determined by the coherent ballistic motion of the excited state density: Upon stretching, I2 pushes the cage atoms out of overlap in position density, and C(t) never recovers. Due to the compressive nature of the cage coordinate in the A→X transition, C(t) decays more gently, after being sampled three times. RR spectra, which are reproduced with adiabatic dynamics, sample the complete history of the many-body correlations, however, due to the breadth in space-time of scattering into high overtones, the sampling is coarse grained. The specific dynamics that control C(t) cannot be described as dissipative. © 1996 American Institute of...
ACCESSION #
7629839

 

Related Articles

  • Femtosecond coherent anti-Stokes Raman-scattering polarization beat spectroscopy of I2–Xe complex in solid krypton. Kiviniemi, Tiina; Kiljunen, Toni; Pettersson, Mika // Journal of Chemical Physics;10/28/2006, Vol. 125 Issue 16, p164302 

    Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out to study the interaction between xenon atom and iodine molecule in a solid krypton matrix. Interference between the CARS polarizations of the “free” and complexed iodine molecules is observed,...

  • Two-dimensional Raman spectra of atomic solids and liquids. Nagata, Yuki; Tanimura, Yoshitaka // Journal of Chemical Physics;1/14/2006, Vol. 124 Issue 2, p024508 

    We calculate third- and fifth-order Raman spectra of simple atoms interacting through a soft-core potential by means of molecular-dynamics (MD) simulations. The total polarizability of molecules is treated by the dipole-induced dipole model. Two- and three-body correlation functions of the...

  • Volume properties and spectroscopy: A terahertz Raman investigation of hen egg white lysozyme. Sassi, Paola; Perticaroli, Stefania; Comez, Lucia; Giugliarelli, Alessandra; Paolantoni, Marco; Fioretto, Daniele; Morresi, Assunta // Journal of Chemical Physics;Dec2013, Vol. 139 Issue 22, p225101 

    The low frequency depolarized Raman spectra of 100 mg/ml aqueous solutions of hen egg white lysozyme (HEWL) have been collected in the 25-85 °C range. Short and long exposures to high temperatures have been used to modulate the competition between the thermally induced reversible and...

  • Tetrahedral order in homologous disaccharide-water mixtures. Branca, C.; Maccarrone, S.; Magazù, S.; Maisano, G.; Bennington, S. M.; Taylor, J. // Journal of Chemical Physics;5/1/2005, Vol. 122 Issue 17, p174513 

    The present work aims at evidencing the “kosmotrope” nature of trehalose through the analysis of inelastic neutron scattering measurements on trehalose and sucrose water solutions at different temperatures. Neutron spectra were collected by using the spectrometer MARI at the ISIS...

  • Time- and frequency-resolved coherent anti-Stokes Raman scattering spectroscopy with sub-25 fs laser pulses. Lausten, Rune; Smirnova, Olga; Sussman, Benjamin J.; Gräfe, Stefanie; Mouritzen, Anders S.; Stolow, Albert // Journal of Chemical Physics;6/28/2008, Vol. 128 Issue 24, p244310 

    In general, many different diagrams can contribute to the signal measured in broadband four-wave mixing experiments. Care must therefore be taken when designing an experiment to be sensitive to only the desired diagram by taking advantage of phase matching, pulse timing, sequence, and the...

  • Theoretical study of the local structure and Raman spectra of CaO-SiO2 binary melts. Wu, Yong Quan; Jiang, Guo Chang; You, Jing Lin; Hou, Huai Yu; Chen, Hui; Xu, Kuang Di // Journal of Chemical Physics;10/22/2004, Vol. 121 Issue 16, p7883 

    A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson’s GF matrix method for the calculations of eigenfrequencies and corresponding...

  • Low-frequency Raman spectra of paradichlorobenzene thin films. Korshunov, M. A. // Optics & Spectroscopy;Mar2009, Vol. 106 Issue 3, p347 

    The low-frequency Raman spectra of paradichlorobenzene nanofilms with a thickness of about 30 μm, 1 μm, and 400 nm are experimentally measured. With decreasing film thickness, the spectral lines shift to lower frequencies and broaden and some additional lines appear, the intensity of which...

  • Mode Selective Excitation Using Coherent Control Spectroscopy. Singh, Ajay K.; Konradi, Jakow; Sarkar, Sisir K.; Materny, Arnulf // AIP Conference Proceedings;11/14/2008, Vol. 1075 Issue 1, p64 

    Femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) gives access to ultrafast molecular dynamics. However, femtosecond laser pulses are spectrally broad and therefore coherently excite several molecular modes. While the temporal resolution is high, usually no mode-selective...

  • Nonlinear Raman Techniques in Femtosecond Time Resolved Spectroscopy for the Analysis and Control of Molecular Dynamics. Materny, Arnulf; Konradi, Jakow; Namboodiri, Vinu; Namboodiri, Mahesh; Scaria, Abraham // AIP Conference Proceedings;11/14/2008, Vol. 1075 Issue 1, p43 

    The use of four-wave mixing techniques in femtosecond time-resolved spectroscopy has considerable advantages. Due to the many degrees of freedom offered e.g. by coherent anti-Stokes Raman scattering (CARS), the dynamics even of complex systems can be analyzed in detail. Using pulse shaping...

Share

Read the Article

Courtesy of THE LIBRARY OF VIRGINIA

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics