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Dehydrogenation free energy of Co$^{2+}$(aq) from density functional theory-based molecular dynamics


Hodel, Florian; Luber, Sandra (2017). Dehydrogenation free energy of Co$^{2+}$(aq) from density functional theory-based molecular dynamics. Journal of Chemical Theory and Computation, 13(3):974-981.

Abstract

Electron and proton transfers are important steps occurring in chemical reactions. The often used approach of calculating the energy differences of those steps using methods based on geometry optimizations neglects the influence of dynamic effects. To further investigate this issue and inspired by research in water oxidation, we calculate in the present study the dehydrogenation free energy of aqueous Co2+, which is the free energy change associated with the first step of the water oxidation reaction mechanism of recently investigated model Co(II)-aqua catalysts. We employ a method based on a thermodynamic integration scheme with strong ties to Marcus theory to obtain free energy differences, solvent reorganization free energies, and dynamic structural information on the systems from density functional theory-based molecular dynamics. While this method is computationally orders of magnitude more expensive than a static approach, it potentially allows for predicting the validity of the approximation of neglecting dynamic effects.

Abstract

Electron and proton transfers are important steps occurring in chemical reactions. The often used approach of calculating the energy differences of those steps using methods based on geometry optimizations neglects the influence of dynamic effects. To further investigate this issue and inspired by research in water oxidation, we calculate in the present study the dehydrogenation free energy of aqueous Co2+, which is the free energy change associated with the first step of the water oxidation reaction mechanism of recently investigated model Co(II)-aqua catalysts. We employ a method based on a thermodynamic integration scheme with strong ties to Marcus theory to obtain free energy differences, solvent reorganization free energies, and dynamic structural information on the systems from density functional theory-based molecular dynamics. While this method is computationally orders of magnitude more expensive than a static approach, it potentially allows for predicting the validity of the approximation of neglecting dynamic effects.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:22 February 2017
Deposited On:05 Apr 2017 08:32
Last Modified:06 Apr 2017 14:29
Publisher:American Chemical Society (ACS)
ISSN:1549-9618
Funders:NCCR-MARVEL, LightChEC
Publisher DOI:https://doi.org/10.1021/acs.jctc.6b01077
PubMed ID:28225613

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