Beyond a single solvated electron: Hybrid quantum Monte Carlo and molecular mechanics approach

Submitted for the MAR10 Meeting of The American Physical Society Beyond a single solvated electron: Hybrid quantum Monte Carlo and molecular mechanics approach DMITRY ZUBAREV, UC Berkeley, Department of Chemistry, GARY CLARK, TERESA HEAD-GORDON, UC Berkeley, Department of Bioengineering, WILLIAM LESTER, UC Berkeley, Department of Chemistry — A hybrid computational approach combining quantum Monte Carlo and molecular mechanics (QMC/MM) has been recently developed for an accurate treatment of electron correlation in systems that require a large number of explicit solvent molecules. Here, QMC/MM is utilized to address the issue of binding of two excess electrons to water clusters of medium-to-large size. Such systems are relevant to the studies of interaction of excess electrons with solvent molecules during electron-energy transfer in medium. A modeling strategy is proposed that combines polarizable force field simulations and density functional theoretical calculations for geometries and binding energies of dianionic clusters, and QMC/MM calculations for refined binding energies. The possibility of stable doubly charged anionic water clusters is demonstrated. The study explores binding properties of various structural motifs and how stability towards spontaneous electron detachment depends on cluster size. Applicability of QMC/MM to the studies of metastable systems is discussed. William Lester UC Berkeley, Department of Chemistry Date submitted: 19 Nov 2009 Electronic form version 1.4

[1]  W. Lester,et al.  Explicit Solvent Model for Quantum Monte Carlo , 2010 .

[2]  J. Herbert,et al.  Polarization-bound quasi-continuum states are responsible for the "blue tail" in the optical absorption spectrum of the aqueous electron. , 2010, Journal of the American Chemical Society.

[3]  B. Schwartz,et al.  Does the Hydrated Electron Occupy a Cavity? , 2010, Science.

[4]  C. Bain,et al.  Hydrated electrons at the water/air interface. , 2010, Journal of the American Chemical Society.

[5]  O. Link,et al.  Binding energies, lifetimes and implications of bulk and interface solvated electrons in water. , 2010, Nature chemistry.

[6]  Toshinori Suzuki,et al.  Direct measurement of vertical binding energy of a hydrated electron. , 2010, Physical chemistry chemical physics : PCCP.

[7]  K. Jordan,et al.  Application of the diffusion Monte Carlo method to the binding of excess electrons to water clusters. , 2010, The journal of physical chemistry. A.

[8]  K. Jordan,et al.  Model potential approaches for describing the interaction of excess electrons with water clusters: incorporation of long-range correlation effects. , 2008, The journal of physical chemistry. A.

[9]  C Filippi,et al.  Energy-consistent pseudopotentials for quantum Monte Carlo calculations. , 2007, The Journal of chemical physics.

[10]  M. Head‐Gordon,et al.  Accuracy and limitations of second-order many-body perturbation theory for predicting vertical detachment energies of solvated-electron clusters. , 2006, Physical chemistry chemical physics : PCCP.

[11]  M. Head‐Gordon,et al.  First-principles, quantum-mechanical simulations of electron solvation by a water cluster , 2006, Proceedings of the National Academy of Sciences.

[12]  B. Schwartz,et al.  Nonadiabatic molecular dynamics simulations of correlated electrons in solution. 1. Full configuration interaction (CI) excited-state relaxation dynamics of hydrated dielectrons. , 2006, The journal of physical chemistry. B.

[13]  B. Schwartz,et al.  Nonadiabatic molecular dynamics simulations of correlated electrons in solution. 2. A prediction for the observation of hydrated dielectrons with pump-probe spectroscopy. , 2006, The journal of physical chemistry. B.

[14]  B. Schwartz,et al.  Full configuration interaction computer simulation study of the thermodynamic and kinetic stability of hydrated dielectrons. , 2006, The journal of physical chemistry. B.

[15]  D. Neumark,et al.  Comment on "Characterization of Excess Electrons in Water-Cluster Anions by Quantum Simulations" , 2005, Science.

[16]  Peter J Rossky,et al.  Characterization of Excess Electrons in Water-Cluster Anions by Quantum Simulations , 2005, Science.

[17]  Alán Aspuru-Guzik,et al.  Zori 1.0: A parallel quantum Monte Carlo electronic structure package , 2005, J. Comput. Chem..

[18]  M. Head‐Gordon,et al.  Calculation of electron detachment energies for water cluster anions: an appraisal of electronic structure methods, with application to (H2O)20- AND (H2O)24-. , 2005, The journal of physical chemistry. A.

[19]  D. Neumark,et al.  Observation of Large Water-Cluster Anions with Surface-Bound Excess Electrons , 2005, Science.

[20]  Gennady N. Chuev,et al.  Density functional method based on wavelets for quantum classical systems , 2004 .

[21]  Mark A. Johnson,et al.  How Do Small Water Clusters Bind an Excess Electron? , 2004, Science.

[22]  D. Neumark,et al.  Hydrated Electron Dynamics: From Clusters to Bulk , 2004, Science.

[23]  B. Schwartz,et al.  Mixed Quantum/Classical Molecular Dynamics Simulations of the Hydrated Dielectron: The Role of Exchange in Condensed-Phase Structure, Dynamics, and Spectroscopy , 2004 .

[24]  David A. Dixon,et al.  The Nature and Absolute Hydration Free Energy of the Solvated Electron in Water , 2003 .

[25]  R. Mathies,et al.  Structure of the aqueous solvated electron from resonance Raman spectroscopy: lessons from isotopic mixtures. , 2003, Journal of the American Chemical Society.

[26]  D. Borgis,et al.  Analytical investigations of an electron–water molecule pseudopotential. II. Development of a new pair potential and molecular dynamics simulations , 2002 .

[27]  Carlos Silva,et al.  Femtosecond Solvation Dynamics of the Hydrated Electron , 1998 .

[28]  A. Staib,et al.  Molecular dynamics simulation of an excess charge in water using mobile Gaussian orbitals , 1995 .

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

[30]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[31]  A. Becke.  A New Mixing of Hartree-Fock and Local Density-Functional Theories , 1993 .

[32]  U. Landman,et al.  Dielectrons in water clusters , 1992 .

[33]  Jules W. Moskowitz,et al.  Correlated Monte Carlo wave functions for the atoms He through Ne , 1990 .

[34]  Lu,et al.  Femtosecond studies of the presolvated electron: An excited state of the solvated electron? , 1990, Physical review letters.

[35]  H. W. Sarkas,et al.  Photoelectron spectroscopy of hydrated electron cluster anions, (H2O)−n=2–69 , 1990 .

[36]  U. Landman,et al.  Excess electrons in polar molecular clusters , 1988 .

[37]  B. Berne,et al.  Behavior of the hydrated electron at different temperatures: structure and absorption spectrum , 1988 .

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

[39]  W. L. Jorgensen,et al.  Comparison of simple potential functions for simulating liquid water , 1983 .

[40]  L. Kevan,et al.  Solvated electron structure in glassy matrixes , 1981 .

[41]  L. Kevan,et al.  Semicontinuum model for the trapped dielectron in polar liquids and solids , 1973 .

[42]  G. Kenney-Wallace,et al.  A Transient Intermediate in the Bimolecular Reaction of Hydrated Electrons , 1972 .

[43]  N. Handy,et al.  A calculation for the energies and wavefunctions for states of neon with full electronic correlation accuracy , 1969, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[44]  J. Boag,et al.  ABSORPTION SPECTRUM OF THE HYDRATED ELECTRON IN WATER AND IN AQUEOUS SOLUTIONS , 1962 .

[45]  D. Bartels,et al.  Lack of ionic strength effect in the recombination of hydrated electrons: (e−)aq + (e−)aq → 2(OH−) + H2 , 1995 .

[46]  P. Rossky,et al.  The hydrated electron: quantum simulation of structure, spectroscopy, and dynamics , 1988 .