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

11 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.

Funders	Funder number
Office of Basic Energy Sciences
U. S. Department of Energy
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

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

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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.",

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AU - Galib, Mirza

AU - Schenter, Gregory K.

AU - Mundy, Christopher J.

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Y1 - 2018/1/16

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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.

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KW - AIMD

KW - Classical MD

KW - Landau-Zener transmission coefficient

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JO - Chemical Physics Letters

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

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Keywords

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