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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 BF 4 --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:
Journal Article: 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.
@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}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on December 24, 2018
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