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Title: On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

Abstract

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is then computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Authors:
 [1];  [1];  [1];  [1]
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1416960
Report Number(s):
PNNL-SA-130814
Journal ID: ISSN 0009-2614; PII: S0009261417311260; TRN: US1800977
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Physics Letters
Additional Journal Information:
Journal Volume: 692; Journal ID: ISSN 0009-2614
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; marcus theory; Landau-Zener transmission coefficient; AIMD; Classical MD; solvent exchange; 2DIR

Citation Formats

Roy, Santanu, Galib, Mirza, Schenter, Gregory K., and Mundy, Christopher J. On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics. United States: N. p., 2017. Web. doi:10.1016/j.cplett.2017.12.041.
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Roy, Santanu, Galib, Mirza, Schenter, Gregory K., & Mundy, Christopher J. On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics. United States. https://doi.org/10.1016/j.cplett.2017.12.041
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Roy, Santanu, Galib, Mirza, Schenter, Gregory K., and Mundy, Christopher J. Sun . "On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics". United States. https://doi.org/10.1016/j.cplett.2017.12.041. https://www.osti.gov/servlets/purl/1416960.
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@article{osti_1416960,
title = {On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics},
author = {Roy, Santanu and Galib, Mirza and Schenter, Gregory K. and Mundy, Christopher J.},
abstractNote = {The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is then computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.},
doi = {10.1016/j.cplett.2017.12.041},
journal = {Chemical Physics Letters},
number = ,
volume = 692,
place = {United States},
year = {Sun Dec 24 00:00:00 EST 2017},
month = {Sun Dec 24 00:00:00 EST 2017}
}
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Journal Article:
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https://doi.org/10.1016/j.cplett.2017.12.041
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Figures / Tables:

Figure 1 Figure 1: Proposed mechanism for ultrafast water exchange around BF-4 ion: Coordination number of an ion-bound water (a) has to increase to form an activated complex (b) that leads to the solvent-bound state (c). In the ion-bound state weak hydrogen bonds between the ion and water hydrogens result in amore » high frequency peak (ha01), whereas in the water-bound state strong hydrogen bonds among water molecules result in a low frequency peak (hw01) in the OD stretch 2DIR spectrum of isotope-diluted water (HOD in H2O) at zero waiting time; ha01 and hw01 indicate the transitions between the vibrational ground (0) and singly excited states (1), while the transitions between the singly (1) and doubly (2) excited states are represented by ha12 and hw12 (d). At an increased waiting time, the cross peak A arises due to the transitions between the water-bound and ion-bound states of water hydrogens, describing the water exchange phenomenon around the ion (e). 2DIR spectra were adopted from Ref. [44] with the permission from Proceedings of the National Academy of Sciences, USA.« less
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Works referenced in this record:

On a novel rate theory for transport in narrow ion channels and its application to the study of flux optimization via geometric effects
journal, February 2009

  • Abad, E.; Reingruber, J.; Sansom, M. S. P.
  • The Journal of Chemical Physics, Vol. 130, Issue 8
  • DOI: 10.1063/1.3077205

Solvent Structure, Dynamics, and Ion Mobility in Aqueous Solutions at 25 °C
journal, May 1998

  • Koneshan, S.; Rasaiah, Jayendran C.; Lynden-Bell, R. M.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 21
  • DOI: 10.1021/jp980642x

Proton transfer through the water gossamer
journal, July 2013

  • Hassanali, Ali; Giberti, Federico; Cuny, Jérôme
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 34
  • DOI: 10.1073/pnas.1306642110

Computer Simulation of Proton Solvation and Transport in Aqueous and Biomolecular Systems
journal, February 2006

  • Voth, Gregory A.
  • Accounts of Chemical Research, Vol. 39, Issue 2
  • DOI: 10.1021/ar0402098

Water Dynamics and Proton Transfer in Nafion Fuel Cell Membranes
journal, April 2008

  • Moilanen, David E.; Spry, D. B.; Fayer, M. D.
  • Langmuir, Vol. 24, Issue 8
  • DOI: 10.1021/la703358a

Reaction rate theory: What it was, where is it today, and where is it going?
journal, June 2005

  • Pollak, Eli; Talkner, Peter
  • Chaos: An Interdisciplinary Journal of Nonlinear Science, Vol. 15, Issue 2
  • DOI: 10.1063/1.1858782

The theory of absolute reaction rates
journal, January 1938

The transition state method
journal, January 1938

Generalized transition state theory in terms of the potential of mean force
journal, September 2003

  • Schenter, Gregory K.; Garrett, Bruce C.; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 119, Issue 12
  • DOI: 10.1063/1.1597477

Variational Transition State Theory
journal, October 1984

Theory of activated rate processes: A new derivation of Kramers’ expression
journal, July 1986

  • Pollak, Eli
  • The Journal of Chemical Physics, Vol. 85, Issue 2
  • DOI: 10.1063/1.451294

The stable states picture of chemical reactions. II. Rate constants for condensed and gas phase reaction models
journal, September 1980

  • Grote, Richard F.; Hynes, James T.
  • The Journal of Chemical Physics, Vol. 73, Issue 6
  • DOI: 10.1063/1.440485

Statistical mechanics of isomerization dynamics in liquids and the transition state approximation
journal, January 1978

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 68, Issue 6
  • DOI: 10.1063/1.436049

Current Status of Transition-State Theory
journal, January 1996

  • Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953748q

Potential of mean force by constrained molecular dynamics: A sodium chloride ion-pair in water
journal, August 1991

Transmission Coefficients, Committors, and Solvent Coordinates in Ion-Pair Dissociation
journal, January 2014

  • Mullen, Ryan Gotchy; Shea, Joan-Emma; Peters, Baron
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 2
  • DOI: 10.1021/ct4009798

Reaction Rate Theory in Coordination Number Space: An Application to Ion Solvation
journal, March 2016

  • Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 14
  • DOI: 10.1021/acs.jpcc.6b00443

Understanding the Rates and Molecular Mechanism of Water-Exchange around Aqueous Ions Using Molecular Simulations
journal, June 2014

  • Annapureddy, Harsha V. R.; Dang, Liem X.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 30
  • DOI: 10.1021/jp502922c

Water Exchange Rates and Molecular Mechanism around Aqueous Halide Ions
journal, March 2014

  • Annapureddy, Harsha V. R.; Dang, Liem X.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 28
  • DOI: 10.1021/jp500402j

Computational studies of water exchange around aqueous Li + with polarizable potential models
journal, August 2013

  • Dang, Liem X.; Annapureddy, Harsha V. R.
  • The Journal of Chemical Physics, Vol. 139, Issue 8
  • DOI: 10.1063/1.4819135

Water Exchange around Li + and Na + in LiCl(aq) and NaCl(aq) from MD Simulations
journal, July 1998

  • Hermansson, Kersti; Wojcik, Mark
  • The Journal of Physical Chemistry B, Vol. 102, Issue 31
  • DOI: 10.1021/jp973465t

Nuclear quantum effects in water exchange around lithium and fluoride ions
journal, February 2015

  • Wilkins, David M.; Manolopoulos, David E.; Dang, Liem X.
  • The Journal of Chemical Physics, Vol. 142, Issue 6
  • DOI: 10.1063/1.4907554

Water exchange dynamics around H3O+ and OH− ions
journal, May 2015

Computer Simulation of Methanol Exchange Dynamics around Cations and Anions
journal, June 2015

Pressure dependence and activation volume for the water exchange mechanism in NaCl(aq) from MD simulations
journal, September 1997

Computational Studies of Water-Exchange Rates around Aqueous Mg 2+ and Be 2+
journal, July 2014

  • Dang, Liem X.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 50
  • DOI: 10.1021/jp503243x

Rate theory on water exchange in aqueous uranyl ion
journal, March 2017

Water exchange on magnesium(II) in aqueous solution: a variable temperature and pressure17O NMR study
journal, November 1997

Experimental determination of the nature of diffusive motions of water molecules at low temperatures
journal, March 1985

Chemical and Electrochemical Electron-Transfer Theory
journal, October 1964

Electron transfers in chemistry and biology
journal, August 1985

  • Marcus, R. A.; Sutin, Norman
  • Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3
  • DOI: 10.1016/0304-4173(85)90014-X

Rate theories, dephasing processes, and nonlinear optical lineshapes
journal, September 1989

  • Yan, Yi Jing; Mukamel, Shaul
  • The Journal of Physical Chemistry, Vol. 93, Issue 19
  • DOI: 10.1021/j100356a022

Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants
journal, February 2016

  • Roy, Santanu; Skoff, David; Perroni, Dominic V.
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b12370

Vibrational spectroscopy of water in hydrated lipid multi-bilayers. II. Two-dimensional infrared and peak shift observables within different theoretical approximations
journal, October 2011

  • Gruenbaum, Scott M.; Pieniazek, Piotr A.; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 135, Issue 16
  • DOI: 10.1063/1.3655671

Dynamics of Water Confined in Reversed Micelles: Multidimensional Vibrational Spectroscopy Study
journal, September 2013

  • Bakulin, Artem A.; Cringus, Dan; Pieniazek, Piotr A.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 49
  • DOI: 10.1021/jp405853j

Ion-water hydrogen-bond switching observed with 2D IR vibrational echo chemical exchange spectroscopy
journal, December 2008

  • Moilanen, D. E.; Wong, D.; Rosenfeld, D. E.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 2
  • DOI: 10.1073/pnas.0811489106

Water exchange on metal ions: experiments and simulations
journal, June 1999

Effects of Alkali Metal Halide Salts on the Hydrogen Bond Network of Liquid Water
journal, April 2005

  • Cappa, Christopher D.; Smith, Jared D.; Wilson, Kevin R.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 15
  • DOI: 10.1021/jp0445324

Hydrogen Bonding in Liquid Water and in the Hydration Shell of Salts
journal, February 2016

Marcus Theory of Ion-Pairing
journal, July 2017

  • Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 8
  • DOI: 10.1021/acs.jctc.7b00332

Dynamical aspects of the sodium(1+)-chloride ion pair association in water
journal, May 1992

  • Rey, R.; Guardia, E.
  • The Journal of Physical Chemistry, Vol. 96, Issue 11
  • DOI: 10.1021/j100190a104

The Role of Collective Solvent Coordinates and Nonequilibrium Solvation in Charge-Transfer Reactions
journal, October 2001

  • Schenter, Gregory K.; Garrett, Bruce C.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 40
  • DOI: 10.1021/jp011981k

Calculating free energies using average force
journal, November 2001

  • Darve, Eric; Pohorille, Andrew
  • The Journal of Chemical Physics, Vol. 115, Issue 20
  • DOI: 10.1063/1.1410978

Nonphysical sampling distributions in Monte Carlo free-energy estimation: Umbrella sampling
journal, February 1977

THE weighted histogram analysis method for free-energy calculations on biomolecules. I. The method
journal, October 1992

  • Kumar, Shankar; Rosenberg, John M.; Bouzida, Djamal
  • Journal of Computational Chemistry, Vol. 13, Issue 8
  • DOI: 10.1002/jcc.540130812

Marcus rate theory and the relationship between Brønsted exponents and energy of reaction
journal, January 1973

Electron Transfer Reactions in Condensed Phases
journal, October 1984

GROMACS 4:  Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation
journal, February 2008

  • Hess, Berk; Kutzner, Carsten; van der Spoel, David
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 3
  • DOI: 10.1021/ct700301q

Energy component analysis for dilute aqueous solutions of lithium(1+), sodium(1+), fluoride(1-), and chloride(1-) ions
journal, February 1984

  • Chandrasekhar, Jayaraman; Spellmeyer, David C.; Jorgensen, William L.
  • Journal of the American Chemical Society, Vol. 106, Issue 4
  • DOI: 10.1021/ja00316a012

Ion-water interaction potentials derived from free energy perturbation simulations
journal, October 1990

The missing term in effective pair potentials
journal, November 1987

  • Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P.
  • The Journal of Physical Chemistry, Vol. 91, Issue 24
  • DOI: 10.1021/j100308a038

Computational Study of Room Temperature Molten Salts Composed by 1-Alkyl-3-methylimidazolium CationsForce-Field Proposal and Validation
journal, November 2002

  • de Andrade, Jones; Böes, Elvis S.; Stassen, Hubert
  • The Journal of Physical Chemistry B, Vol. 106, Issue 51
  • DOI: 10.1021/jp0216629

Molecular dynamics with coupling to an external bath
journal, October 1984

  • Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
  • The Journal of Chemical Physics, Vol. 81, Issue 8
  • DOI: 10.1063/1.448118

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985

PLUMED: A portable plugin for free-energy calculations with molecular dynamics
journal, October 2009

  • Bonomi, Massimiliano; Branduardi, Davide; Bussi, Giovanni
  • Computer Physics Communications, Vol. 180, Issue 10
  • DOI: 10.1016/j.cpc.2009.05.011

The influence of temperature and density functional models in ab initio molecular dynamics simulation of liquid water
journal, January 2005

  • VandeVondele, Joost; Mohamed, Fawzi; Krack, Matthias
  • The Journal of Chemical Physics, Vol. 122, Issue 1
  • DOI: 10.1063/1.1828433

Nosé–Hoover chains: The canonical ensemble via continuous dynamics
journal, August 1992

  • Martyna, Glenn J.; Klein, Michael L.; Tuckerman, Mark
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463940

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

Effect of cut-off distance used in molecular dynamics simulations on fluid properties
journal, September 2010

Separable dual-space Gaussian pseudopotentials
journal, July 1996

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Hydration and mobility of ions in solution
journal, December 1983

  • Impey, R. W.; Madden, P. A.; McDonald, I. R.
  • The Journal of Physical Chemistry, Vol. 87, Issue 25
  • DOI: 10.1021/j150643a008

Mass density fluctuations in quantum and classical descriptions of liquid water
journal, June 2017

  • Galib, Mirza; Duignan, Timothy T.; Misteli, Yannick
  • The Journal of Chemical Physics, Vol. 146, Issue 24
  • DOI: 10.1063/1.4986284
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