The Marcus dimension: identifying the nuclear coordinate for electron transfer from ab initio calculations† † Electronic supplementary information (ESI) available: Predicted spectra from the nuclear ensemble approach, correlation plots for m-DNB −, Marcus dimensions found for studied systems in vacuum, scans along the Marcus dimension in acetonitrile, wavefunction calculations, calculation of phonon masses and harmonic frequencies for the Marcus dimension, parameterization of the Marcus model, estimation of transmission coefficients, coordinates of the calculated adiabatic minima and of obtained ET dimensions. See DOI: https://doi.org/10.1039/d3sc01402a

ABSTRACT: The Marcus model forms the foundation for all modern discussion of electron transfer (ET). In this model, ET results in a change in diabatic potential energy surfaces, separated along an ET nuclear coordinate. This coordinate accounts for all nuclear motion that promotes electron transfer. It is usually assumed to be dominated by a collective asymmetric vibrational motion of the redox sites involved in the ET. However, this coordinate is rarely quantitatively specified. Instead, it remains a nebulous concept, rather than a tool for gaining true insight into the ET pathway. Herein, we describe an ab initio approach for quantifying the ET coordinate and demonstrate it for a series of dinitroradical anions. Using sampling methods at finite temperature combined with density functional theory c

SUBMITTER: Srut A 

PROVIDER: S-EPMC10466304 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature