Plasma–liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on non-equilibrium plasmas.

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Plasma-liquid interactions: A review and roadmap

Dielectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological Systems

Electron Transfer Past and Future (R Marcus) Electron Transfer Reactions in Solution: A Historical Perspective (N Sutin) Electron Transfer--From Isolated Molecules to Biomolecules (M Bixon & J Jortner) Charge Transfer in Bichromophoric Molecules in the Gas Phase (D Levy) Long--Range Charge Separation in Solvent--Free Donor--Bridge--Acceptor Systems (B Wegewijs & J Verhoeven) Electron Transfer and Charge Separation in Clusters (C Dessent, et al) Control of Electron Transfer Kinetics: Models for Medium Reorganization and Donor--Acceptor Coupling (M Newton) Theories of Structure--Function Relationships for Bridge--Mediated Electron Transfer Reactions (S Skourtis & D Beratan) Fluctuations and Coherence in Long--Range and Multicenter Electron Transfer (G Iversen, et al) Lanczos Algorithm for Electron Transfer Rates in Solvents with Complex Spectral Densities (A Okada, et al) Spectroscopic Determination of Electron Transfer Barriers and Rate Constants (K Omberg, et al) Photoinduced Electron Transfer Within Donor--Spacer--Acceptor Molecular Assemblies Studied by Time--Resolved Microwave Conductivity (J Warman, et al) From Close Contact to Long--Range Intramolecular Electron Transfer (J Verhoeven) Photoinduced Electron Transfers Through sigma Bonds in Solution (N--C Yang, et al) Indexes

Electron transfer : from isolated molecules to biomolecules

Two of the more fundamental ways in which molecules change their behavior when they are dissolved are that they can begin to exchange energy with the surrounding liquid and they can induce their surroundings to rearrange so as to provide a significant stabilizing influence. The first of these is typified by the process of vibrational population relaxation of a vibrationally hot species. The second conceptcritical to solution chemistryis what is known as solvation. Both of these processes are sufficiently fundamental that one would really like to know, at the most mechanical and molecular level possible, just what events are required in order to make them happen. But how difficult is it going to be to extract such molecular detail from the complicated many-body dynamics? The most microscopic level of understanding one could ever hope to possess might seem far removed from the finely detailed dynamical information which is available routinely for individual isolated molecules and for molecule−molecule colli...

Nonreactive Dynamics in Solution: The Emerging Molecular View of Solvation Dynamics and Vibrational Relaxation

Chemical Science Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352; Department of Chemistry, ShelbyHall, University of Alabama, Box 870336, Tuscaloosa, Alabama 35487-0336; Notre Dame Radiation Laboratory, University of Notre Dame,Notre Dame, Indiana 46556; Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 0520-8107; Argonne NationalLaboratory, 9700 South Cass Avenue, Argonne, Illinois 60439; Department of Computer Science and Department of Physics, 2710 University Drive,Washington State University, Richland, Washington 99352-1671; Lawrence Berkeley National Laboratory, 1 Cyclotron Road Mailstop 1-0472,Berkeley, California 94720; Department of Chemistry and Biochemistry, University of Texas at Austin, 1 University Station A5300,Austin, Texas 78712; Office of Basic Energy Sciences, U.S. Department of Energy, SC-141/Germantown Building, 1000 Independence Avenue,S.W., Washington, D.C. 20585-1290; Department of Physics and Engineering Physics, Stevens Institute of Technology, Castle Point on Hudson,Hoboken, New Jersey 07030; Department of Chemistry, Johns Hopkins University, 34th and Charles Streets, Baltimore, Maryland 21218;Department of Chemistry, University of Southern California, Los Angeles, California 90089-1062; Department of Chemistry, The Ohio StateUniversity, 100 West 18th Avenue, Columbus, Ohio 43210-1185; Department of Chemistry, Columbia University, Box 3107, Havemeyer Hall,New York, New York 10027; Department of Chemistry, University of Pittsburgh, Parkman Avenue and University Drive,Pittsburgh, Pennsylvania 15260; Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000; Department of Physics andAstronomy, Rutgers, The State University of New Jersey, 136 Frelinghuysen Road, Piscataway, New Jersey 08854-8019; Department of Chemistry,516 Rowland Hall, University of California, Irvine, Irvine, California 92697-2025; Stanford Synchrotron Radiation Laboratory, Stanford LinearAccelerator Center, 2575 Sand Hill Road, Mail Stop 69, Menlo Park, California 94025; School of Chemistry and Biochemistry, Georgia Institute ofTechnology, 770 State Street, Atlanta, Georgia 30332-0400; Geology Department, University of California, Davis, One Shields Avenue,Davis, California 95616-8605; Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue,Cambridge, Massachusetts 02139-4307; Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084Received July 23, 2004

http://casey.brown.edu/chemistry/research/LSWang/publications/194.pdf

Role of water in electron-initiated processes and radical chemistry: issues and scientific advances.

Femtosecond pump-probe spectroscopy of the equilibrated hydrated electron has been recorded with 35fs resolution, revealing unprecedented transient features on the 30{endash}80fs time scales that have been assigned to inertial solvation dynamics of the hydrated electron. These data allow for a rigorous experimental evaluation of the recently published nonadiabatic quantum molecular dynamics simulations of the adiabatic and nonadiabatic dynamics of the hydrated electron. {copyright} {ital 1998 } {ital The American Physical Society}

Femtosecond Solvation Dynamics of the Hydrated Electron

Ultrafast near-infrared (NIR)-pump/variable wavelength probe transient absorption spectroscopy has been performed on the aqueous solvated electron. The photodynamics of the solvated electron excited to its p-state are qualitatively similar to previous measurements of the dynamics of photoinjected electrons at high energy. This result confirms the previous interpretation of photoinjected electron dynamics as having a rate-limiting bottleneck at low energies presumably involving the p-state. The absorption transients of our NIR-pump experiments obtained probing between 540 and 1060 nm reveal complicated dynamics that cannot be strictly reproduced using a two-state kinetic model, necessitating modification of the two-state model to include ground-state transient solvation and local heating following electronic relaxation. This modified kinetic model was found to quantitatively reproduce the observed spectral dynamics, yielding an excited-state lifetime of 310 [+-] 80 fs and a 1.1 [+-] 0.2 ps time scale for ground-state cooling and solvation. This model preserves a two-state electronic relaxation but adds ground-state relaxation dynamics. Excited-state solvation has been neglected in the model, and it remains to be proven whether the observed relaxation processes result from solvation in the ground state, the excited state, or both. 83 refs., 8 figs., 1 tab.

Ultrafast Transient Absorption Spectroscopy of the Solvated Electron in Water

We have performed the first direct pump‐probe transient‐absorption measurements on the near‐infrared (IR) band of the equilibrated aqueous solvated electron. The pump pulse was centered at 780 nm. The absorption spectrum of the excited state is observed to be red‐shifted relative to the ground‐state absorption. The radiationless transition from the excited state to the ground state occurs with an average time constant of 550±170 fs. In observing a subpicosecond lifetime and red‐shifted absorption for the excited p‐states, these experiments are in accord with a growing body of experimental and theoretical work, serving to provide a consistent picture of the photophysics of the solvated electron.

Ultrafast transient-absorption spectroscopy of the aqueous solvated electron

We recently reported the first pump−probe measurements on the hydrated electron with sufficient time resolution (∼35 fs) to directly observe the initial processes in the solvation dynamics of this key prototype for condensed-phase dynamics [Silva, C.; Walhout, P. K.; Yokoyama, K.; Barbara, P. F. Phys. Rev. Lett. 1998, 80, 1086]. An unprecedented relaxation process for the hydrated electron was observed that occurs on the 35−80 fs time scale and exhibits a solvent isotope effect (τ(D2O)/τ(H2O) ∼ 1.4). The new process was assigned to inertial/librational motion of the water surrounding the excess electron. The present paper reports a more extensive study of the ∼35 fs resolved dynamics of the hydrated electron in H2O and D2O at more probe wavelengths and as a function of pump-pulse intensity. The results are in agreement with the preliminary report and support the importance of librational water motion in the relaxation dynamics of the hydrated electron. New high excitation pulse intensity measurements reve...

Peter K. Walhout

Papers

Femtosecond Solvation Dynamics of the Hydrated Electron

Ultrafast Transient Absorption Spectroscopy of the Solvated Electron in Water

Ultrafast transient-absorption spectroscopy of the aqueous solvated electron

Detailed Investigation of the Femtosecond Pump-Probe Spectroscopy of the Hydrated Electron

Ultrafast experiments on the photodissociation, recombination, and vibrational relaxation of i2- : role of solvent-induced solute charge flow