Non-linear response and hydrogen bond dynamics for electron solvation in methanol

Abstract Non-equilibrium and equilibrium adiabatic mixed quantum-classical molecular dynamics computer simulations of the solvation dynamics of an excess electron in methanol are reported. We develop the connection between the multiple time scales reflected in solvent response and individual physical phenomena, such as the radial collapse of the electron and structural relaxation of the hydrogen-bonding network of the solvent. The significant role of the latter aspect appears responsible for the breakdown of the linear response approximation for the relaxation of the adiabatic ground state energy of the excess electron.

[1]  R. Cukier,et al.  A quantum molecular dynamics simulation of an excess electron in methanol , 1993 .

[2]  Martin,et al.  Excess electrons in liquid water: First evidence of a prehydrated state with femtosecond lifetime. , 1987, Physical review letters.

[3]  H. Callen,et al.  THE IRREVERSIBLE THERMODYNAMICS OF NONLINEAR PROCESSES AND NOISE IN DRIVEN SYSTEMS , 1959 .

[4]  F. H. Long,et al.  Femtosecond studies of electron photodetachment of simple ions in liquid water: Solvation and geminate recombination dynamics , 1989 .

[5]  B. Ladanyi,et al.  Breakdown of linear response for solvation dynamics in methanol , 1991 .

[6]  Benjamin J. Schwartz,et al.  Aqueous solvation dynamics with a quantum mechanical Solute: Computer simulation studies of the photoexcited hydrated electron , 1994 .

[7]  P. Rossky,et al.  Equilibrium structure, fluctuations, and spectroscopy of a solvated electron in methanol , 1997 .

[8]  P. Barbara,et al.  Direct pump/probe spectroscopy of the near-IR band of the solvated electron in alcohols , 1995 .

[9]  M. Maroncelli,et al.  Computer simulation of the dynamics of aqueous solvation , 1988 .

[10]  P. Rossky,et al.  Dynamics of chemical processes in polar solvents , 1994, Nature.

[11]  Mauro Ferrario,et al.  Molecular-dynamics simulation of liquid methanol , 1987 .

[12]  J. Banavar,et al.  Computer Simulation of Liquids , 1988 .

[13]  P. Rossky,et al.  Solvation dynamics of an excess electron in methanol and water , 1998 .

[14]  Solvent Mode Participation in the Nonradiative Relaxation of the Hydrated Electron , 1996, chem-ph/9604003.

[15]  T. Goulet,et al.  Femtosecond Kinetic Measurements of Excess Electrons in Methanol: Substantiation for a Hybrid Solvation Mechanism , 1994 .

[16]  H. Ohtaki,et al.  Structure and dynamics of hydrated ions , 1993 .

[17]  Friedrichs,et al.  Solvation dynamics of the hydrated electron: A nonadiabatic quantum simulation. , 1991, Physical review letters.

[18]  P. Rossky,et al.  On the nature of pre-existing states for an excess electron in water , 1989 .

[19]  M. Maroncelli,et al.  Nonreactive Dynamics in Solution: The Emerging Molecular View of Solvation Dynamics and Vibrational Relaxation , 1996 .

[20]  Richard A. Friesner,et al.  Nonadiabatic processes in condensed matter: semi-classical theory and implementation , 1991 .

[21]  P. Rossky,et al.  Nonadiabatic molecular dynamics simulation of photoexcitation experiments for the solvated electron in methanol , 1999 .

[22]  Gábor Pálinkás,et al.  A molecular dynamics study of liquid methanol with a flexible three-site model , 1987 .

[23]  P. Rossky,et al.  The role of solvent intramolecular modes in excess electron solvation dynamics , 1993 .

[24]  M. Maroncelli Computer simulations of solvation dynamics in acetonitrile , 1991 .

[25]  Schnitker,et al.  A priori calculation of the optical absorption spectrum of the hydrated electron. , 1988, Physical review letters.

[26]  P. Barbara,et al.  Ultrafast Transient Absorption Spectroscopy of the Solvated Electron in Water , 1994 .

[27]  P. Rossky,et al.  A dynamical analysis of energy level fluctuations for an excess electron in methanol , 1998 .