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

Santanu Roy; Mirza Galib; Gregory K. Schenter; Christopher J. Mundy

doi:10.1016/j.cplett.2017.12.041

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

Santanu Roy
, Mirza Galib
, Gregory K. Schenter
, Christopher J. Mundy

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

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, 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 computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Original language	English
Pages (from-to)	407-415
Number of pages	9
Journal	Chemical Physics Letters
Volume	692
DOIs	https://doi.org/10.1016/j.cplett.2017.12.041
State	Published - Jan 16 2018
Externally published	Yes

Funding

This work was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The research was performed using PNNL Institutional Computing. PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. This work was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The research was performed using PNNL Institutional Computing. PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.

Keywords

2DIR
AIMD
Classical MD
Landau-Zener transmission coefficient
Marcus theory
Solvent exchange

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10.1016/j.cplett.2017.12.041

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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{\textquoteright} philosophy of electron transfer, 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 computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.",

keywords = "2DIR, AIMD, Classical MD, Landau-Zener transmission coefficient, Marcus theory, Solvent exchange",

author = "Santanu Roy and Mirza Galib and Schenter, \{Gregory K.\} and Mundy, \{Christopher J.\}",

note = "Publisher Copyright: {\textcopyright} 2017",

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doi = "10.1016/j.cplett.2017.12.041",

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AU - Roy, Santanu

AU - Galib, Mirza

AU - Schenter, Gregory K.

AU - Mundy, Christopher J.

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Y1 - 2018/1/16

N2 - 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, 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 computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

AB - 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, 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 computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

KW - 2DIR

KW - AIMD

KW - Classical MD

KW - Landau-Zener transmission coefficient

KW - Marcus theory

KW - Solvent exchange

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M3 - Article

AN - SCOPUS:85039559302

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VL - 692

SP - 407

EP - 415

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

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

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