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

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

Journal Article · 24 December 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.

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

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

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1416960

Report Number(s):: PNNL-SA-130814; PII: S0009261417311260; TRN: US1800977

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

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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Cited By (1)

The activation energy for water reorientation differs between IR pump-probe and NMR measurements Piskulich, Zeke A.; Thompson, Ward H. The Journal of Chemical Physics, Vol. 149, Issue 16 https://doi.org/10.1063/1.5050203	journal	October 2018

Figures / Tables (7)

Figure 1(p. 2)

Δ W ), solvent reorganization energy (

λ

), and the location (

n^{†}

) of the transition barrier

Δ W^{†}

in Marcus’ parabolic model of equal curvatures (a). Two crossing points arise due to the difference in the curvature; the one with the lower barrier (

n_{-}^{†}

) is located at the “normal region” and the one with the higher barrier (

n_{+}^{†}

) is located at the “abnormal region”. (b) For

Δ W

is largely negative and

| Δ W | ≫ λ

, a single crossing occurs at the “abnormal region” in the original Marcus model (

K_{R} = K_{P}

) (c), whereas in the extended model (

K_{R} \neq K_{P}

) crossing occurs at two “abnormal regions” (d)." data-ostiid="1416960">

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
marcus theory
Landau-Zener transmission coefficient
AIMD
Classical MD
solvent exchange
2DIR