Electronic Density Approaches to the Energetics of Noncovalent Interactions

Ma, Yan; Politzer, Peter

doi:10.3390/i5040130

Cited by 3 publications

(2 citation statements)

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“…Many‐body induction as well as charge transfer have been proposed to be the main reasons for such effects 9. 16 Most of the explanations offered so far rely on more or less arbitrary procedures to extract these energetic components from electronic structure calculations 29–32. It is our opinion that real‐space procedures might shed new light on these matters to narrow down the origin of cooperativity by providing orbital‐invariant results that are independent from external references.…”

Section: Introductionmentioning

confidence: 99%

“…[9,16] Most of the explanations offered so far rely on more or less arbitrary procedures to extract these energetic components from electronic structure calculations. [29][30][31][32] It is our opinion that real-space procedures might shed new light on these matters to narrow down the origin of cooperativity by providing orbital-invariant results that are independent from external references. This paper aims to give a detailed real-space account of the contributions to the interaction energy among water molecules in the formation of the water dimer and small cyclic water clusters (H 2 O) n with n = 3-6 (see Figure 1) to provide insight into the cooperative effects of hydrogen bonding.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen‐Bond Cooperative Effects in Small Cyclic Water Clusters as Revealed by the Interacting Quantum Atoms Approach

Guevara‐Vela

Chávez-Calvillo

García‐Revilla

et al. 2013

Chemistry A European J

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The cooperative effects of hydrogen bonding in small water clusters (H2 O)n (n=3-6) have been studied by using the partition of the electronic energy in accordance with the interacting quantum atoms (IQA) approach. The IQA energy splitting is complemented by a topological analysis of the electron density (ρ(r)) compliant with the quantum theory of atoms-in-molecules (QTAIM) and the calculation of electrostatic interactions by using one- and two-electron integrals, thereby avoiding convergence issues inherent to a multipolar expansion. The results show that the cooperative effects of hydrogen bonding in small water clusters arise from a compromise between: 1) the deformation energy (i.e., the energy necessary to modify the electron density and the configuration of the nuclei of the isolated water molecules to those within the water clusters), and 2) the interaction energy (Eint ) of these contorted molecules in (H2 O)n . Whereas the magnitude of both deformation and interaction energies is enhanced as water molecules are added to the system, the augmentation of the latter becomes dominant when the size of the cluster is increased. In addition, the electrostatic, classic, and exchange components of Eint for a pair of water molecules in the cluster (H2 O)n-1 become more attractive when a new H2 O unit is incorporated to generate the system (H2 O)n with the last-mentioned contribution being consistently the most important part of Eint throughout the hydrogen bonds under consideration. This is opposed to the traditional view, which regards hydrogen bonding in water as an electrostatically driven interaction. Overall, the trends of the delocalization indices, δ(Ω,Ω'), the QTAIM atomic charges, the topology of ρ(r), and the IQA results altogether show how polarization, charge transfer, electrostatics, and covalency contribute to the cooperative effects of hydrogen bonding in small water clusters. It is our hope that the analysis presented in this paper could offer insight into the different intra- and intermolecular interactions present in hydrogen-bonded systems.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hydrogen‐Bond Cooperative Effects in Small Cyclic Water Clusters as Revealed by the Interacting Quantum Atoms Approach

Guevara‐Vela

Chávez-Calvillo

García‐Revilla

et al. 2013

Chemistry A European J

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Intermolecular Interaction Energies from Experimental Charge Density Studies

Dominiak¹,

Espinosa²,

Ángyán³

2011

Modern Charge-Density Analysis

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The packing interactions have been evaluated in the context of the self-assembly mechanism of crystal growth and also for its impacts on the aromaticity of the trimesate anion. The structure of ethylammonium trimesate hydrate (1) measured at 100 K and a charge density model, derived in part from theoretical structures, is reported. Theoretical structure factors were obtained from the geometry-optimized periodic wave function. The trimesic acid portion of 1 is fully deprotonated and participates in a variety hydrogen bonding motifs. Topological analysis of the charge density model reveals the most significant packing interactions and is then compared to a complementary analysis performed by the Hirshfeld surface method. The results presented herein demonstrate that in organic salt crystals the small structural motifs are most stable and once formed as stand-alone structures, may direct the self-assembly process. Moreover, when intermolecular interactions supported by the electrostatic forces are analyzed, the care must be taken with interpretation of the results of Hirshfeld surface analysis for organic salts crystals.

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