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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]
  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) (SC-22)
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.
Roy, Santanu, Galib, Mirza, Schenter, Gregory K., & Mundy, Christopher J. On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics. United States. doi:10.1016/j.cplett.2017.12.041.
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. doi:10.1016/j.cplett.2017.12.041. https://www.osti.gov/servlets/purl/1416960.
@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 = {2017},
month = {12}
}

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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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