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Directionality and the Role of Polarization in Electric Field Effects on Radical Stability

Abstract (Expand)

ccurate quantum-chemical calculations are used to analyze the effects of charges on the kinetics and thermodynamics of radical reactions, with specific attention given to the origin and directionality … of the effects. Conventionally, large effects of the charges are expected to occur in systems with pronounced charge-separated resonance contributors. The nature (stabilization or destabilization) and magnitude of these effects thus depend on the orientation of the interacting multipoles. However, we show that a significant component of the stabilizing effects of the external electric field is largely independent of the orientation of external electric field (e.g. a charged functional group, a point charge, or an electrode) and occurs even in the absence of any pre-existing charge separation. This effect arises from polarization of the electron density of the molecule induced by the electric field. This polarization effect is greater for highly delocalized species such as resonance-stabilized radicals and transition states of radical reactions. We show that this effect on the stability of such species is preserved in chemical reaction energies, leading to lower bond-dissociation energies and barrier heights. Finally, our simplified modelling of the diol dehydratase-catalyzed 1,2-hydroxyl shift indicates that such stabilizing polarization is likely to contribute to the catalytic activity of enzymes.

Authors: Ganna Gryn'ova, Michelle L. Coote

Date Published: 2017

Publication Type: Journal

Charge Transport in Highly Ordered Organic Nanofibrils: Lessons from Modelling

Abstract (Expand)

H-Aggregates featuring tight π-stacks of the conjugated heterocyclic cores represent ideal morphologies for 1D organic semiconductors. Such nanofibrils have larger electronic couplings between the … adjacent cores compared to the herringbone crystal or amorphous assemblies. In this work, we show that for a set of seven structurally and electronically distinct cores, including quaterthiophene and oligothienoacenes, the co-planar dimer model captures the impact of the monomer's electronic structure on charge transport, but more advanced multiscale modelling, featuring molecular dynamics and kinetic Monte-Carlo simulations, is needed to account for the packing and disorder effects. The differences in the results between these two computational approaches arise from the sensitivity of the electronic coupling strength to the relative alignment of adjacent cores, in particular the long-axis shift between them, imposed by the oligopeptide side chains. Our results demonstrate the dependence of the performance of H-aggregates on the chemical nature of the cores and the presence of the side chains, as well as the limitations in using the simple dimer model for a rapid computational pre-screening of the conjugated cores.

Authors: Ganna Gryn’ova, Adrien Nicolaï, Antonio Prlj, Pauline Ollitrault, Denis Andrienko, Clemence Corminboeuf

Date Published: 2017

Publication Type: Journal

Development of Hydrodynamic Coarse-Grain Models for Brownian Dynamics Simulations of Crowded Protein Systems

Abstract

Not specified

Author: Martin Reinhardt

Date Published: 2017

Publication Type: Master's Thesis

Modeling and Simulation of Membrane Proteins to Understand their Structure, Dynamics and Function

Abstract

Not specified

Author: Ghulam Mustafa

Date Published: 2017

Publication Type: Doctoral Thesis

Computational Studies on the Relation Between Macromolecular Dynamics and Protein Binding and Function.

Abstract

Not specified

Author: Antonia Stank

Date Published: 2017

Publication Type: Doctoral Thesis

Horofunction Compactifications of Symmetric Spaces

Abstract (Expand)

We consider horofunction compactifications of symmetric spaces with respect to invariant Finsler metrics. We show that any (generalized) Satake compactification can be realized as a horofunction … compactification with respect to a polyhedral Finsler metric.

Authors: Thomas Haettel, Anna-Sofie Schilling, Cormac Walsh, Anna Wienhard

Date Published: 2017

Publication Type: Misc

Anosov representations and proper actions

Abstract (Expand)

We establish several characterizations of Anosov representations of word hyperbolic groups into real reductive Lie groups, in terms of a Cartan projection or Lyapunov projection of the Lie group. Using … a properness criterion of Benoist and Kobayashi, we derive applications to proper actions on homogeneous spaces of reductive groups.

Authors: François Guéritaud, Olivier Guichard, Fanny Kassel, Anna Wienhard

Date Published: 2017

Publication Type: Journal

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