Vertical vs. Adiabatic Ionization Energies in Solution and Gas-Phase: Probing Ionization-Induced Reorganization in Conformationally-Mobile Bichromophoric Actuators Using Photoelectron Spectroscopy, Electrochemistry and Theory

Authors

Maxim Vadimovich Ivanov, Marquette University
Denan Wang, Marquette UniversityFollow
Depeng Zhang, Marquette University
Rajendra Rathore, Marquette UniversityFollow
Scott A. Reid, Marquette UniversityFollow

Document Type

Article

Language

eng

Publication Date

9-2018

Publisher

Royal Society of Chemistry

Source Publication

Physical Chemistry Chemical Physics

Source ISSN

1463-9076

Abstract

Ionization-induced structural and conformational reorganization in various π-stacked dimers and covalently linked bichromophores is relevant to many processes in biological systems and functional materials. In this work, we examine the role of structural, conformational, and solvent reorganization in a set of conformationally mobile bichromophoric donors, using a combination of gas-phase photoelectron spectroscopy, solution-phase electrochemistry, and density functional theory (DFT) calculations. Photoelectron spectral analysis yields both adiabatic and vertical ionization energies (AIE/VIE), which are compared with measured (adiabatic) solution-phase oxidation potentials (E_ox). Importantly, we find a strong correlation of E_ox with AIE, but not VIE, reflecting variations in the attendant structural/conformational reorganization upon ionization. A careful comparison of the experimental data with the DFT calculations allowed us to probe the extent of charge stabilization in the gas phase and solution and to parse the reorganizational energy into its various components. This study highlights the importance of a synergistic approach of experiment and theory to study ionization-induced structural and conformational reorganization.

Comments

Accepted version. Physical Chemistry Chemical Physics, Vol. 20, No. 40 (September 2018): 25615-25622. DOI. © 2018 Royal Society of Chemistry. Used with permission.

Recommended Citation

Ivanov, Maxim Vadimovich; Wang, Denan; Zhang, Depeng; Rathore, Rajendra; and Reid, Scott A., "Vertical vs. Adiabatic Ionization Energies in Solution and Gas-Phase: Probing Ionization-Induced Reorganization in Conformationally-Mobile Bichromophoric Actuators Using Photoelectron Spectroscopy, Electrochemistry and Theory" (2018). Chemistry Faculty Research and Publications. 984.
https://epublications.marquette.edu/chem_fac/984