# 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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Item Type: Journal Article, refereed, original work 07 Faculty of Science > Department of Chemistry 540 Chemistry English 22 February 2017 05 Apr 2017 08:32 06 Apr 2017 14:29 American Chemical Society (ACS) 1549-9618 NCCR-MARVEL, LightChEC https://doi.org/10.1021/acs.jctc.6b01077 28225613

Content: Accepted Version
Filetype: PDF - Registered users only until 22 February 2018
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Embargo till: 2018-02-22
Content: Other
Filetype: PDF (Supporting Information) - Registered users only
Size: 10MB

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