Two-color three pulse photon echo peak shift spectroscopy

Agarwal, Ritesh; Prall, Bradley S.; Rizvi, Abbas H.; Yang, Mino; Fleming, Graham R.
April 2002
Journal of Chemical Physics;4/8/2002, Vol. 116 Issue 14, p6243
Academic Journal
Two-color three pulse photon echo peak shift spectroscopy (2C3PEPS) has been used to probe correlation in electronic transitions in two different regions of the electronic spectrum of a chromophore in the condensed phase. The 2C3PEPS can be done in an "uphill" or a "downhill" sense, where the first two interactions are of lower (higher) frequency than the final interaction with the radiation field. In both cases no correlation between the two spectral regions is observed at very short times. Different parts of the spectrum gain correlation owing to ultrafast solvent motion and the accompanying Stokes shift. We propose a model for the spectral shift that incorporates a conditional probability distribution for transition frequencies in the two spectral regions. The model qualitatively reproduces all the features of complete numerical simulations. Our results show that memory is partially conserved during the spectral diffusion process from the pump to the probe region. The downhill difference peak shift is very sensitive to the time scale of the inertial component of solvation and seems very promising for an accurate determination of this time scale.


Related Articles

  • Collective many-body resonances in condensed phase nonlinear spectroscopy. Tortschanoff, Andreas; Mukamel, Shaul // Journal of Chemical Physics;3/22/2002, Vol. 116 Issue 12, p5007 

    The optical response of assemblies of electronic and vibrational chromphores may show two types of collective resonances induced by either direct short-range coupling (multiple quantum coherence) or by long-range macroscopic local field and cascading processes. Using a unified approach for both...

  • A universal scaling law for atomic diffusion in condensed matter. Dzugutov, Mikhail // Nature;5/9/1996, Vol. 381 Issue 6578, p137 

    Presents an approach to unifying quantitative description of atomic diffusion in condensed matter. Analytic expressions for the transport coefficients of an idealized dense fluid of hard spheres; Generalizations; Evidence from molecular dynamics simulations indicating a universal relationship...

  • Self-normalized photothermal techniques for thermal diffusivity measurements. Balderas-López, J. A.; Mandelis, A. // Journal of Applied Physics;12/1/2000, Vol. 88 Issue 11, p6815 

    Two self-normalized photothermal techniques, to carry out thermal diffusivity measurements of condensed phase materials, are presented. These simple methodologies involve linear fitting procedures of the signal amplitude and phase. These procedures lead to the elimination of the usual...

  • Spectroscopy of a chromophore coupled to a lattice of dynamic two-level systems. I. Absorption line shape. Reilly, Philip D.; Skinner, J. L. // Journal of Chemical Physics;7/15/1994, Vol. 101 Issue 2, p959 

    Frequency modulation of a dilute chromophore’s transition is a common mechanism of line broadening in condensed phases. In many different physical situations this frequency modulation arises from coupling of the chromophore to a collection of flipping two-level systems. In this paper we...

  • q-Gaussian representation of non-Lorentzian M�ssbauer lineshapes. Razdan, Ashok // Hyperfine Interactions;2008, Vol. 188 Issue 1-3, p103 

    Generalized statistical physics (non-extensive/Tsallis) is being extensively used to study anomalous results in condensed matter physics. M�ssbauer line shapes for systems like proteins and glasses show non-Lorentzian behaviour. In this paper we show q-Gaussian distribution can be used to...

  • Effect of the vibrational pattern of out-of-plane vibrational modes on vibronically induced spin-orbit coupling between ππ* states involved in nonradiative intersystem crossing transitions. Gastilovich, E. A.; Korol’kova, N. V.; Serov, S. A.; Klimenko, V. G.; Nurmukhametov, R. N. // Optics & Spectroscopy;Aug2008, Vol. 105 Issue 2, p208 

    To describe nonradiative intersystem crossing between excited ππ* states, the matrix elements of the operator of spin-orbit interaction are calculated. Adiabatic electronic functions that depend on out-of-plane normal vibrational coordinates are used as a zero approximation. Using...

  • The ultrafast ground and excite state dynamics of cis-hexatriene in cyclohexane. Pullen, Stuart H.; Anderson, Neil A. // Journal of Chemical Physics;10/1/1997, Vol. 107 Issue 13, p4985 

    Presents kinetics measurements and time-resolved spectra that provide insight into the condensed-phase dynamics of cis-hexatriene in cyclohexane in the ground and excited states. Vibrational cooling results in trapping of a small amount that relaxes on a much longer time scale as the barrier to...

  • Condensed phase electron-energy-loss spectroscopy of the low-lying triplet of acetylene. Swiderek, P.; Michaud, M. // Journal of Chemical Physics;6/15/1997, Vol. 106 Issue 23, p9403 

    Examines the low-energy electron-energy-loss spectra of solid acetylene in the range of the low-lying valence excited triplet states. Spectra showing that the first band contains several overlapping single-triplet transitions; Extrapolation of the transition starting with lowest vibronic...

  • Atomic dynamics of the α-(Al,Si)CuFe alloy: A crystalline approximant of a quasicrystal... Parshin, P. P.; Zemlyanov, M. G.; Brand, R. A.; Pavlyuchkov, D.; Ollivier, J. // Physics of the Solid State;Jul2010, Vol. 52 Issue 7, p1492 

    The atomic dynamics of the Al0.550Si0.070Cu0.255Fe0.125 alloy with the structure that approximates the structure of an icosahedral quasicrystal with a similar chemical composition has been investigated using inelastic neutron scattering. The partial vibrational spectra of copper, iron, and...


Read the Article


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

Try another library?
Sign out of this library

Other Topics