Efficient Constrained Density Functional Theory Implementation for Simulation of Condensed Phase Electron Transfer Reactions

Holmberg, Nico; Laasonen, Kari

doi:10.1021/acs.jctc.6b01085

Cited by 48 publications

(69 citation statements)

References 110 publications

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“…44 The Hirshfeld or "stockholder" approach to population analysis 66 is often used to define an atom in a molecule, [67][68][69] but is applied here to monomers A and B of the noncovalent A• • • B complex, as in other recent applications of cDFT. 44, 70 The number of electrons on monomer A,…”

Section: Theory and Methodsmentioning

confidence: 99%

Electrostatics, Charge Transfer, and the Nature of the Halide–Water Hydrogen Bond

Herbert

Carter-Fenk

2021

J. Phys. Chem. A

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Binary halide-water complexes X − (H2O) are examined by means of symmetry-adapted perturbation theory, using charge-constrained promolecular reference densities to extract a meaningful chargetransfer component from the induction energy. As is known, the X − (H2O) potential energy surface (for X = F, Cl, Br, or I) is characterized by symmetric left and right hydrogen bonds separated by a C2v-symmetric saddle point, with a tunneling barrier height that is < 2 kcal/mol except in the case of F − (H2O). Our analysis demonstrates that the charge-transfer energy is correspondingly small (< 2 kcal/mol except for X = F), and thus considerably smaller than the electrostatic interaction energy. Nevertheless, charge transfer plays a crucial role determining the conformational preferences of X − (H2O) and provides a driving force for the formation of quasi-linear X• • • H-O hydrogen bonds. Charge-transfer energies correlate well with measured O-H vibrational redshifts for both halidewater complexes as well as OH − (H2O) and NO − 2 (H2O), providing some indication of a general mechanism.

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Section: Theory and Methodsmentioning

confidence: 99%

Electrostatics, Charge Transfer, and the Nature of the Halide–Water Hydrogen Bond

Herbert

Carter-Fenk

2021

J. Phys. Chem. A

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“…The theoretical foundations of CDFT [20][21][22] and CDFT-CI 26,27 have been discussed extensively in the literature. Here, we will present only the main attributes of the algorithm that we have implemented to perform CDFT-CI simulations of HER in solvated environments, as an extension of our earlier implementation 39 which was limited to systems with a single constraint and two diabatic states.…”

Section: B Configuration Interaction Based On Constrained Dftmentioning

confidence: 99%

“…A detailed description of the properties and efficient construction of the Becke weight function is given in our earlier publication. 39 The constraint target value, N c , is a measure of the desired number of electrons per molecular group in each of the diabatic electronic states. Because the formal number of electrons per molecule is poorly defined when molecules interact strongly, 27,41 we employ so called fragment based constraints to define the constraint target values.…”

Section: B Configuration Interaction Based On Constrained Dftmentioning

confidence: 99%

Diabatic model for electrochemical hydrogen evolution based on constrained DFT configuration interaction

Holmberg

Laasonen

2018

The Journal of Chemical Physics

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The accuracy of density functional theory (DFT) based kinetic models for electrocatalysis is diminished by spurious electron delocalization effects, which manifest as uncertainties in the predicted values of reaction and activation energies. In this work, we present a constrained DFT approach to alleviate overdelocalization effects in the Volmer-Heyrovsky mechanism of the hydrogen evolution reaction (HER). This method is applied a posteriori to configurations sampled along a reaction path to correct their relative stabilities. Concretely, the first step of this approach involves describing the reaction in terms of a set of diabatic states that are constructed by imposing suitable density constraints on the system. Refined reaction energy profiles are then recovered by performing a configuration interaction (CDFT-CI) calculation within the basis spanned by the diabatic states. After a careful validation of the proposed method, we examined HER catalysis on open-ended carbon nanotubes and discovered that CDFT-CI increased activation energies and decreased reaction energies relative to DFT predictions. We believe that a similar approach could also be adopted to treat overdelocalization effects in other electrocatalytic proton-coupled electron transfer reactions, e.g., in the oxygen reduction reaction.

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“…S1 confirms that the density of the amorphous aggregates has reached equilibrium within the above MD simulation time. In more precise, site energy and electronic coupling fluctuate due to the molecular vibrations 34 – 37 . The calculation of site energy and electronic coupling over a long time interval provides reasonable statistical time averages, but is time-consuming.…”

Section: Methodsmentioning

confidence: 99%

Parameter-Free Multiscale Simulation Realising Quantitative Prediction of Hole and Electron Mobilities in Organic Amorphous System with Multiple Frontier Orbitals

Kubo

Kaji

2018

Sci Rep

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In amorphous organic semiconducting systems, hole and electron transfer has been considered to occur based on the overlap of highest occupied molecular orbitals (HOMOs) and that of lowest unoccupied molecular orbitals (LUMOs) between two adjacent molecules, respectively. Other molecular orbitals (MOs), HOMO−1, HOMO−2, … and LUMO+1, LUMO+2, …, have been neglected in charge transport calculations. However, these MOs could potentially contribute to charge transport. In this study, our multiscale simulations show that carriers are effectively transported not only via HOMOs or LUMOs but also via other MOs when the MOs are close in energy. Because these multiple MOs are active in charge transports, here we call them multiple frontier orbitals. Molecules with multiple frontier orbitals are found to possess high carrier mobility. The findings in this study provide guidelines to aid design of materials with excellent charge transport properties.

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Efficient Constrained Density Functional Theory Implementation for Simulation of Condensed Phase Electron Transfer Reactions

Cited by 48 publications

References 110 publications

Electrostatics, Charge Transfer, and the Nature of the Halide–Water Hydrogen Bond

Electrostatics, Charge Transfer, and the Nature of the Halide–Water Hydrogen Bond

Diabatic model for electrochemical hydrogen evolution based on constrained DFT configuration interaction

Parameter-Free Multiscale Simulation Realising Quantitative Prediction of Hole and Electron Mobilities in Organic Amorphous System with Multiple Frontier Orbitals

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