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

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

doi:10.1016/j.cplett.2017.12.041

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

Journal Article · Sat Dec 23 23:00:00 EST 2017 · Chemical Physics Letters

DOI:https://doi.org/10.1016/j.cplett.2017.12.041· OSTI ID:1416960

Roy, Santanu ^[1]; Galib, Mirza ^[1]; Schenter, Gregory K. ^[1]; Mundy, Christopher J. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1416960

Report Number(s):: PNNL-SA--130814; PII: S0009261417311260

Journal Information:: Chemical Physics Letters, Journal Name: Chemical Physics Letters Vol. 692; ISSN 0009-2614

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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