DFT studies on hydrogen-bonding, Stacking, and XH···π<i>-</i>Bonded systems in presence of external electric field

Dutta, Biswa Jyoti; Bhattacharyya, Pradip

doi:10.1002/qua.24950

Cited by 20 publications

(12 citation statements)

References 53 publications

(41 reference statements)

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“…Figure shows the gap between the energies of the HOMO and LUMO calculated at CAM‐B3LYP/aug‐cc‐pV Q Z level of theory for all molecules studied here. As expected, for all systems, the HOMO–LUMO gap (or the hardness) decreases as the applied electric field strength increases. One should highlight that the curves of Figure present significant changes in their slopes after the critical field values, which are also observed in Figure , and where smaller bond distances in the polar molecules are obtained (Fig.…”

Section: Resultssupporting

confidence: 82%

Molecules under external electric field: On the changes in the electronic structure and validity limits of the theoretical predictions

2018

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A detailed analysis of the electronic structure of the ground and first excited spin state of three diatomic molecules ( N2, BH and CO) under static applied electric field is performed at CCSD(T), DFT, MRCI and MRCI(Q) levels of theory. Our findings have revealed that by boosting the applied field one induces changes in the occupation numbers of molecular orbitals, giving rise to changes in the equilibrium geometry and in the HOMO-LUMO energy gap. Specifically, singlet to triplet spin transition can be induced by increasing the applied electric field beyond a critical value. Accordingly, affecting the accuracy of the widely used expression of energy expanded in Taylor series with respect to the applied electric field. © 2018 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 82%

Molecules under external electric field: On the changes in the electronic structure and validity limits of the theoretical predictions

2018

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“…An external electric field (EEF) can modulate the nature and strength of intermolecular interactions, [1][2][3][4] affect the products of known chemical processes, [5][6][7][8][9] energies of the electronic states 10,11 and consequently response properties of molecules. [12][13][14][15] The EEF has been employed for molecular sensing 16,17 and recently for catalysis.…”

Section: Introductionmentioning

confidence: 99%

Solvent effects on ion–receptor interactions in the presence of an external electric field

Novák

Foroutan‐Nejad

Marek

2016

Phys. Chem. Chem. Phys.

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In this work we investigated the influence of an external electric field on the arrangement of the solvent shells around ions interacting with a carbon-based receptor. Our survey reveals that the mechanism of interaction between a monoatomic ion and a π-type ion receptor varies by the variation in the solvent polarity, the nature of the ion, and the strength of the external field. The characteristics of the ion-surface interaction in nonpolar solvents are similar to those observed in a vacuum. However, in water, we identified two mechanisms. Soft and polarizable ions preferentially interact with the π-receptor. In contrast, two bonded states were found for hard ions. A fully solvated ion, weakly interacting with the receptor at weak field, and a strong π-complex at the strong-field regime were identified. An abrupt variation in the potential energy surface (PES) associated with the rearrangement of the solvation shell on the surface of the receptor induced by an external field was observed both in implicit and explicit solvent environments. The electric field at which the solvation shell breaks is proportional to the hardness of the ion as has been suggested recently based on experimental observations.

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“…In the last two decades, the benzene-methane complex has been used as a model system to study the CH-π interaction, which is considered to be a weak hydrogen bond 11 12 and has been found to play important roles in the physical, chemical, and biological properties of a variety of substances 13 14 15 16 17 18 19 20 . Hydrogen bonds are formed between two molecules with strongly contrasting electronegativities, one of which is terminated by a hydrogen atom 21 .…”

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confidence: 99%

Strong orbital interaction in a weak CH-π hydrogen bonding system

2016

Sci Rep

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For the first time, the intermolecular orbital interaction between benzene and methane in the benzene-methane complex, a representative of weak interaction system, has been studied by us using ab initio calculations based on different methods and basis sets. Our results demonstrate obvious intermolecular orbital interaction between benzene and methane involving orbital overlaps including both occupied and unoccupied orbitals. Similar to interatomic orbital interaction, the intermolecular interaction of orbitals forms “bonding” and “antibonding” orbitals. In the interaction between occupied orbitals, the total energy of the complex increases because of the occupation of the antibonding orbital. The existence of the CH-π hydrogen bond between benzene and methane causes a decrease in rest energy level, leading to at least −1.51 kcal/mol intermolecular interaction energy. Our finding extends the concept of orbital interaction from the intramolecular to the intermolecular regime and gives a reliable explanation of the deep orbital reformation in the benzene-methane complex.

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DFT studies on hydrogen-bonding, Stacking, and XH···π-Bonded systems in presence of external electric field

Cited by 20 publications

References 53 publications

Molecules under external electric field: On the changes in the electronic structure and validity limits of the theoretical predictions

Molecules under external electric field: On the changes in the electronic structure and validity limits of the theoretical predictions

Solvent effects on ion–receptor interactions in the presence of an external electric field

Strong orbital interaction in a weak CH-π hydrogen bonding system

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