Theoretical study of cooperative effects in the homo‐ and heteromeric hydrogen bond chains (HCN)nHF withn= 1, 2, and 3

Araújo, Regiane C. M. U.; Soares, Verneck M.; Oliveira, Boaz G.; Lopes, Kelson C.; Ventura, Elizete; Monte, Silmar A. do; Santana, Otávio Luís de; Carvalho, Antônio B.; Ramos, Mozart N.

doi:10.1002/qua.21132

Cited by 29 publications

(12 citation statements)

References 17 publications

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“…It is especially important to point out that these ΔE C values are not the essence of the hydrogen bond strengths because the energies of the IV and V complexes are uncooperative. In other words, the total energy values of −247.14216984 H and −247.14384609 H cannot be divided equally among the unsymmetrical hydrogen bonds-N···H d and N···H c of IV, as well as N···H d , N···H g , and N···H a' of V-as already reported in several studies on the formation of cluster systems [86][87][88]. The ternary complexes, IV and V, are formed by two and three hydrogen bonds, respectively, where, in addition to the predominance of the electrostatic potential [89] already quoted here, it is well-known that charge transfer is one of the most important effects in intermolecular interactions [90].…”

Section: Structurementioning

confidence: 55%

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

Oliveira

Araújo

2011

J Mol Model

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B3LYP calculations, ChelpG atomic charges, and quantum theory of atoms in molecules (QTAIM) integrations were used to investigate the binary (1:1) and ternary (1:2) hydrogen-bonded complexes formed by aziridine (1) and ammonia (2). In a series of analysis, geometry data, electronic parameters, vibrational oscillators, and topological descriptors were used to evaluate hydrogen bond strength, and additionally to determine the more prominent molecular deformations upon the formation of C(2)H(5)N···NH(3) (1:1) and C(2)H(5)N···2NH(3) (1:2) systems. Taking a spectroscopic viewpoint, results obtained from analysis of the harmonic infrared spectrum were examined. From these, new vibrational modes and red- and blue-shifts related to the stretch frequencies of either donors or acceptors of protons were identified. Furthermore, the molecular topology of the electronic density modeled in accord with QTAIM was absolutely critical in defining bond critical points (BCP) and ring critical points (RCP) on the heterocyclic structures. Taking all the results together allowed us to identify and characterize all the N···H hydrogen bonds, as well as the strain ring of the aziridine and its stability.

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Section: Structurementioning

confidence: 55%

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

Oliveira

Araújo

2011

J Mol Model

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“…Arauju et al showed that the cooperative effect in hetero hydrogen-bonded chains was greater than that for homo chains for a series of (HCN) n -HF and (HCN) n (n = 1, 2, 3) clusters [71]. Additionally, as the chains become longer there was a corresponding increase in the cooperative effects observed [71].…”

Section: Interplay Between Non-covalent Interactionsmentioning

confidence: 86%

“…Interestingly, the hydrogen bond strength in the decamer was about 160 % higher than in the dimer, despite the hydrogen bonds being 3-center hydrogen bonds as opposed to being typical 2-center hydrogen bonds [70]. Arauju et al showed that the cooperative effect in hetero hydrogen-bonded chains was greater than that for homo chains for a series of (HCN) n -HF and (HCN) n (n = 1, 2, 3) clusters [71]. Additionally, as the chains become longer there was a corresponding increase in the cooperative effects observed [71].…”

Section: Interplay Between Non-covalent Interactionsmentioning

confidence: 94%

Interplay of Hydrogen, Halogen, Lithium and Beryllium Bonds in Complexes of Thiirane

McDowell

Joseph

2015

Challenges and Advances in Computational Chemistry and Physics

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Hydrogen, halogen, lithium and beryllium bonding are briefly surveyed as a prelude to a report of a computational study of the interplay between these various non-covalent interactions. Our study used model dimers and trimers involving the thiirane molecule, (CH 2 ) 2 S, complexed with small molecules like HF, ClF, BrF, LiF and BeH 2 to assess and investigate the interplay between the different noncovalent interactions. The model trimer systems show positive cooperative effects when thiirane is one of the terminal molecules, whereas a negative cooperative effect is evident when it is at the center of the trimer. The changes in selected molecular properties, including the redistribution of charge densities obtained by the natural population analysis (NPA), implemented in the natural bond orbital (NBO) procedure, and an Atoms in Molecules (AIM) topological analysis, were useful in understanding these cooperative effects. Introduction Overview of Non-Covalent InteractionsNon-covalent interactions in molecular systems is a topic of much scientific interest as it spans a number of scientific subdisciplines. They are responsible for the existence of condensed phases, for which the forces operative between interacting neutral molecules are strong enough to limit the volume of samples of a particular material but weak enough to ensure the fluidity of such materials in bulk.Such interactions are usually dominated by classical electrostatic forces, through the interaction between the permanent multipole moments of the interacting molecular species. These electrostatic forces are usually augmented by classical polarization and quantum-mechanical dispersion forces, and their long-range behavior dependent on some inverse power of their molecular separation (usually measured by the distance between the center of masses of the interacting molecules). At equilibrium

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“…in (a) indicates a loss of charge in the C-C bond. Although is not cooperative 67 , the value of -0.016 e.u. shows a receiving of charge in H. For (b) and (c) complexes, the diminutions of charge of +0.052 e.u.…”

Section: Intermolecular Energiesmentioning

confidence: 93%

Blue-Shifting Hydrogen Bonds and Secondary Interactions in the C3h6…hcf3, C2h4o…hcf3 and C2h4s…hcf3 Cyclic Complexes

Oliveira

2011

J. Chil. Chem. Soc.

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In this article, a theoretical study of molecular properties of small cyclic systems is presented. Through the calculations performed at the B3LYP/6-311++G(d,p) level of theory, the optimized geometries of the C 3 H 6 ···HCF 3 , C 2 H 4 O···HCF 3 and C 2 H 4 S···HCF 3 hydrogen-bonded complexes were determined. By analyzing the structural parameters, it was observed a contraction of the C-H bond length of the fluoroform (HCF 3 ). As such, the examination of the harmonic infrared spectrum accused the existence of a blue-shift effect in this bond, once its stretch frequency is displaced to upward values accompanied by a significant diminishing on the absorption intensity. In the purpose to comprehend this vibrational phenomenon, topological parameters computed at the light of the Quantum Theory of Atoms in Molecules (QTAIM) were also used. An interesting aspect is the non-linearity deviation on the hydrogen bonds (O···H) and (S···H) due to the formation of a secondary interaction (H

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Theoretical study of cooperative effects in the homo‐ and heteromeric hydrogen bond chains (HCN)_nHF withn= 1, 2, and 3

Cited by 29 publications

References 17 publications

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

Interplay of Hydrogen, Halogen, Lithium and Beryllium Bonds in Complexes of Thiirane

Blue-Shifting Hydrogen Bonds and Secondary Interactions in the C3h6…hcf3, C2h4o…hcf3 and C2h4s…hcf3 Cyclic Complexes

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