scholarly journals Characterizing the interplay of Pauli repulsion, electrostatics, dispersion and charge transfer in halogen bonding with energy decomposition analysis

2018 ◽  
Vol 20 (2) ◽  
pp. 905-915 ◽  
Author(s):  
Jonathan Thirman ◽  
Elric Engelage ◽  
Stefan M. Huber ◽  
Martin Head-Gordon
Keyword(s):  
Charge Transfer ◽  
Bond Strength ◽  
Halogen Bond ◽  
Decomposition Analysis ◽  
Halogen Bonding ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Pauli Repulsion

Variational energy decomposition analysis establishes charge-transfer as the origin of halogen bond strength differences that go against electrostatics.

scholarly journals Energy decomposition analysis approaches and their evaluation on prototypical protein–drug interaction patterns

2015 ◽  
Vol 44 (10) ◽  
pp. 3177-3211 ◽  
Author(s):  
Maximillian J. S. Phipps ◽  
Thomas Fox ◽  
Christofer S. Tautermann ◽  
Chris-Kriton Skylaris
Keyword(s):  
Drug Interaction ◽  
Charge Transfer ◽  
Interaction Energy ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Chemical Components ◽  
Protein Drug ◽  
Interaction Patterns ◽  
Energy Decomposition

The partitioning of the interaction energy into chemical components such as electrostatics, polarization, and charge transfer is possible with energy decomposition analysis approaches. We review and evaluate these for biomolecular applications.

scholarly journals From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis

2021 ◽  
Vol 72 (1) ◽  
pp. 641-666
Author(s):  
Yuezhi Mao ◽  
Matthias Loipersberger ◽  
Paul R. Horn ◽  
Akshaya Das ◽  
Omar Demerdash ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Intermolecular Interaction ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Radical Cations ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Energy Decomposition ◽  
Functional Theory ◽  
Pauli Repulsion

Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. These energetic contributions are identified by performing DFT calculations with constraints that disable components of the interaction. This review describes the second-generation version of the absolutely localized molecular orbital EDA (ALMO-EDA-II). The effects of different physical contributions on changes in observables such as structure and vibrational frequencies upon complex formation are characterized via the adiabatic EDA. Example applications include red- versus blue-shifting hydrogen bonds; the bonding and frequency shifts of CO, N2, and BF bound to a [Ru(II)(NH3)5]2 + moiety; and the nature of the strongly bound complexes between pyridine and the benzene and naphthalene radical cations. Additionally, the use of ALMO-EDA-II to benchmark and guide the development of advanced force fields for molecular simulation is illustrated with the recent, very promising, MB-UCB potential.

scholarly journals Through-Bond and Through-Space Interactions in [2,2]Cyclophanes

2021 ◽  
Author(s):  
Sérgio Galembeck ◽  
Renato Orenha ◽  
Rafael Madeira ◽  
Letícia Peixoto ◽  
Renato Parreira
Keyword(s):  
Electron Density ◽  
Noncovalent Interactions ◽  
Topological Analysis ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Relative Importance ◽  
Energy Decomposition ◽  
Covalent Contribution ◽  
Pauli Repulsion ◽  
Open Question

The interpretation of the distortions of the electron distribution in [2,2]cyclophanes (22-CPs) is controversial. Some studies indicate that there is an accumulation of electron density (ρ) outside the cavity of 22-CPs. The nature of through-space (ts) interaction is still under debate. The relative importance of ts and through-bond (tb) is an open question. In an attempt to clarify these points, we have investigated five 22-CPs and their corresponding toluene dimers by molecular orbitals analysis, electron density difference analysis, some topological analysis of ρ (quantum theory of atoms in molecules (QTAIM), electron localization function (ELF) and noncovalent interactions (NCI)), and energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV). ρ is concentrated inside the inter-ring region. All the analyses indicated that ts is predominant. The ts is composed by attractive dispersion and Pauli repulsion, with a small covalent contribution. Except for 1 and 6, all the compounds present inter-ring bond paths.

scholarly journals Water Adlayers on Noble Metal Surfaces: Insights from Energy Decomposition Analysis

2020 ◽  
Author(s):  
Paul Clabaut ◽  
Ruben Staub ◽  
Joachim Galiana ◽  
Elise Antonetti ◽  
Stephan Steinmann
Keyword(s):  
Charge Transfer ◽  
Noble Metal ◽  
Metal Surfaces ◽  
Decomposition Analysis ◽  
Function Technique ◽  
Energy Decomposition Analysis ◽  
Water Molecules ◽  
Energy Decomposition ◽  
Small Surface ◽  
Many Body Interactions

Water molecules adsorbed on noble metal surfaces are of fundamental interest in surface science, heterogeneous catalysis and as a model for the metal/water interface. Herein, we analyse 27 water structures adsorbed on five noble metal surfaces (Cu, Ag, Au, Pd, Pt) via density functional theory and energy decomposition analysis based on the block localized wave function technique. The structures, ranging from the monomers to ice adlayers, reveal that the charge-transfer from water to the surface is nearly independent from the charge-transfer between the water molecules, while the polarization energies are cooperative. Dense water-water networks with small surface dipoles, such as the sqrt(39) x sqrt(39) unit cell (experimentally observed on Pt(111) ) are favored compared to the highly ordered and popular H<sup>up</sup> and H<sup>down</sup> phases. The second main result of our study is that the many-body interactions, which stabilize the water assemblies on the metal surfaces, are dominated by the polarization energies, with the charge-transfer scaling with the polarization energies. Hence, if an empirical model could be found that reproduces the polarization energies, the charge-transfer could be predicted as well, opening exciting perspectives for force field development.

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