Observation and dynamics of "mixed-valence isomers" and a thermodynamic estimate of electronic coupling parameters

Casey H. Londergan; J. Catherine Salsman; Benjamin J. Lear; Clifford P. Kubiak

doi:10.1016/j.chemphys.2005.10.021

Observation and dynamics of "mixed-valence isomers" and a thermodynamic estimate of electronic coupling parameters

Casey H. Londergan, J. Catherine Salsman, Benjamin J. Lear, Clifford P. Kubiak

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

35 Scopus citations

Abstract

The thermodynamics of mixed-valence isomers - the two limiting charge distributions in a mixed-valence complex - are reviewed and used as a basis for calculating the electronic coupling (H_AB). Infrared spectroscopy is used to determine equilibrium constants between the two mixed-valence isomers in the strongly coupled adiabatic limit. Equilibrium constants in the diabatic (H_AB = 0) limit are independently estimated from electrochemical data for corresponding symmetric complexes. Analysis of these data provide direct measurements of Δ Δ G⁰ = Δ G₀ ⁰ - Δ G₁ ⁰, the difference in thermodynamic driving force for electron transfer in the diabatic and strongly coupled adiabatic limits which it is shown can be interpreted within the framework of appropriate potential energy surfaces for ET to estimate H_AB.

Original language	English (US)
Pages (from-to)	57-62
Number of pages	6
Journal	Chemical Physics
Volume	324
Issue number	1 SPEC. ISS.
DOIs	https://doi.org/10.1016/j.chemphys.2005.10.021
State	Published - May 9 2006

All Science Journal Classification (ASJC) codes

General Physics and Astronomy
Physical and Theoretical Chemistry

Access to Document

10.1016/j.chemphys.2005.10.021

Cite this

@article{a11d5d0b08fb426bb88d6a8c42be606f,

title = "Observation and dynamics of {"}mixed-valence isomers{"} and a thermodynamic estimate of electronic coupling parameters",

abstract = "The thermodynamics of mixed-valence isomers - the two limiting charge distributions in a mixed-valence complex - are reviewed and used as a basis for calculating the electronic coupling (HAB). Infrared spectroscopy is used to determine equilibrium constants between the two mixed-valence isomers in the strongly coupled adiabatic limit. Equilibrium constants in the diabatic (HAB = 0) limit are independently estimated from electrochemical data for corresponding symmetric complexes. Analysis of these data provide direct measurements of Δ Δ G0 = Δ G0 0 - Δ G1 0, the difference in thermodynamic driving force for electron transfer in the diabatic and strongly coupled adiabatic limits which it is shown can be interpreted within the framework of appropriate potential energy surfaces for ET to estimate HAB.",

author = "Londergan, {Casey H.} and Salsman, {J. Catherine} and Lear, {Benjamin J.} and Kubiak, {Clifford P.}",

note = "Funding Information: We acknowledge helpful discussions with Dr. Marshall Newton about this work. This work was supported by NSF (CHE – 0315593).",

year = "2006",

month = may,

day = "9",

doi = "10.1016/j.chemphys.2005.10.021",

language = "English (US)",

volume = "324",

pages = "57--62",

journal = "Chemical Physics",

issn = "0301-0104",

publisher = "Elsevier",

number = "1 SPEC. ISS.",

}

TY - JOUR

T1 - Observation and dynamics of "mixed-valence isomers" and a thermodynamic estimate of electronic coupling parameters

AU - Londergan, Casey H.

AU - Salsman, J. Catherine

AU - Lear, Benjamin J.

AU - Kubiak, Clifford P.

N1 - Funding Information: We acknowledge helpful discussions with Dr. Marshall Newton about this work. This work was supported by NSF (CHE – 0315593).

PY - 2006/5/9

Y1 - 2006/5/9

N2 - The thermodynamics of mixed-valence isomers - the two limiting charge distributions in a mixed-valence complex - are reviewed and used as a basis for calculating the electronic coupling (HAB). Infrared spectroscopy is used to determine equilibrium constants between the two mixed-valence isomers in the strongly coupled adiabatic limit. Equilibrium constants in the diabatic (HAB = 0) limit are independently estimated from electrochemical data for corresponding symmetric complexes. Analysis of these data provide direct measurements of Δ Δ G0 = Δ G0 0 - Δ G1 0, the difference in thermodynamic driving force for electron transfer in the diabatic and strongly coupled adiabatic limits which it is shown can be interpreted within the framework of appropriate potential energy surfaces for ET to estimate HAB.

AB - The thermodynamics of mixed-valence isomers - the two limiting charge distributions in a mixed-valence complex - are reviewed and used as a basis for calculating the electronic coupling (HAB). Infrared spectroscopy is used to determine equilibrium constants between the two mixed-valence isomers in the strongly coupled adiabatic limit. Equilibrium constants in the diabatic (HAB = 0) limit are independently estimated from electrochemical data for corresponding symmetric complexes. Analysis of these data provide direct measurements of Δ Δ G0 = Δ G0 0 - Δ G1 0, the difference in thermodynamic driving force for electron transfer in the diabatic and strongly coupled adiabatic limits which it is shown can be interpreted within the framework of appropriate potential energy surfaces for ET to estimate HAB.

UR - http://www.scopus.com/inward/record.url?scp=33646257537&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33646257537&partnerID=8YFLogxK

U2 - 10.1016/j.chemphys.2005.10.021

DO - 10.1016/j.chemphys.2005.10.021

M3 - Article

AN - SCOPUS:33646257537

SN - 0301-0104

VL - 324

SP - 57

EP - 62

JO - Chemical Physics

JF - Chemical Physics

IS - 1 SPEC. ISS.

ER -

Observation and dynamics of "mixed-valence isomers" and a thermodynamic estimate of electronic coupling parameters

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this