On Dipole Moments and Hydrogen Bond Identification in Water Clusters

Bakó, Imre; Mayer, I.

doi:10.1021/acs.jpca.6b03187

Cited by 25 publications

(27 citation statements)

References 58 publications

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“…Mayer have shown that in water molecules the dipole moment enhances with the cluster size [44]. In the present cause, we observed almost odd-even oscillation for larger size DMSO clusters, when the dipole moment is plotted as a function of cluster size (See Fig.…”

Section: Energetics' and Choice Of Functionalssupporting

confidence: 67%

“…Furthermore, the use of BSSE correction increases the BE values. Prior studies on the molecular aggregates have shown that the counterpoise correction provides error as the fragments within the complex is improved by the basic functions, while such extension is not possible in the calculation of the isolated fragments Venkataramanan Page 15 [44]. Recently, Grimme et al showed that incorporation of dispersion for geometrical optimization provides better results than performing BSSE correction [45].…”

Section: Energetics' and Choice Of Functionalsmentioning

confidence: 99%

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Density functional theory study on the dihydrogen bond cooperativity in the growth behavior of dimethyl sulfoxide clusters

Venkataramanan

Suvitha

Kawazoe

2018

Journal of Molecular Liquids

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Highlights The ground state geometry of DMSO clusters prefer an ouroboros shape. σ-hole on the odd numbered clusters helps for the highly directional growth. AIM analysis shows the existence of intermolecular dihydrogen bonds. Cooperative effects help to increase the stability of the DMSO cluster. Venkataramanan Page 3 AbstractWe have carried out a density functional theory study on the structures of DMSO clusters and analysed the structure and their stability using molecular electrostatic potential and quantum theory of atoms-in-molecules (QTAIM). The ground state geometry of the DMSO clusters, prefer to exist in ouroboros shape. Pair wise interaction energy calculation show the interaction between methyl groups of adjacent DMSO molecules and a destabilization is is created by the methyl groups which are away from each other. Molecular electrostatic potential analysis shows the existence of σ-hole on the odd numbered clusters, which helps in their highly directional growth. QTAIM analysis show the existence of two intermolecular hydrogen bonds, of type SO···HC hydrogen bonds and methyl CH···HC dihydrogen bonds. The computed and Laplacian values were all positive for the intermolecular bonds, supporting the existence of noncovalent interactions. The computed ellipticity for the dihydrogen bonds have values > 2, which confirms the delocalization of electron, are mainly due to the hydrogen-hydrogen interactions of methyl groups. A plot of total hydrogen bonding energy vs the observed total local electron density shows linearity with correlation coefficient of near unity, which indicates the cooperative effects of intermolecular dihydrogen H···H bonds. Venkataramanan Page 4 Graphical Abstract 2 3 4 5

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Section: Energetics' and Choice Of Functionalssupporting

confidence: 67%

Section: Energetics' and Choice Of Functionalsmentioning

confidence: 99%

Density functional theory study on the dihydrogen bond cooperativity in the growth behavior of dimethyl sulfoxide clusters

Venkataramanan

Suvitha

Kawazoe

2018

Journal of Molecular Liquids

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“…It has been shown through detailed quantum calculations that the dipole moment and polarization of water increases with the degree of hydrogen bonding. 26,28,29,34,35 For instance, the dipole moment of a water monomer in the gas phase is 1.855 D, while calculations shows that the average dipole of individual water molecules is ~ 2.1 D in hydrogen bonded dimers and ~2.3 D in cyclic trimer clusters. 26 In this work we wish to employ insight gained from these detailed first principles calculations to estimate the coefficients in Eq.…”

Section: D: Application To Watermentioning

confidence: 99%

On the cooperativity of association and reference energy scales in thermodynamic perturbation theory

Marshall

2016

The Journal of Chemical Physics

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Equations of state for hydrogen bonding fluids are typically described by two energy scales. A short range highly directional hydrogen bonding energy scale as well as a reference energy scale which accounts for dispersion and orientationally averaged multi-pole attractions. These energy scales are always treated independently. In recent years, extensive first principles quantum mechanics calculations on small water clusters have shown that both hydrogen bond and reference energy scales depend on the number of incident hydrogen bonds of the water molecule. In this work, we propose a new methodology to couple the reference energy scale to the degree of hydrogen bonding in the fluid. We demonstrate the utility of the new approach by showing that it gives improved predictions of water-hydrocarbon mutual solubilities.

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“…The results obtained using the proposed methodology agrees qualitatively better with the experimental IR, NMR, and CD spectra, compared with other methodologies. Despite of some interactions between solvent and solute were neglected due to the formulation of the method, is considered that the dipole moment of the solvents should have influence on the specific electric interactions between the solvents and the DHPT molecules (water = 1.84 Debye for an isolated water monomer and ~2.5 to 2.8 Debye in condensed phase, DMSO = 3.96 Debye).…”

Section: Resultsmentioning

confidence: 99%

Theoretical and experimental evidence of conformational transformation in stereoisomers of nucleoside analogues

Hernández-Hernández

Cleaves

et al. 2018

Int J of Quantum Chemistry

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A theoretical and experimental characterization of N(1)-(2 0 ,3 0 -dihydroxypropil)thymine (DHPT), a potential prebiotic nucleoside analogue of 5-methyluridine, is performed. A proposed methodology based on a solvation method was used to study conformational transformations of the different low-energy conformers of DHPT according to time-dependent IR spectroscopy. NMR and CD spectroscopy provides additional evidence of these transformations. The conformational transformations appear to be due to solvent and DHPT interactions. This highlights the importance of experimental conditions on conformer ratio equilibrium, in particular, the interpretation of experimental conditions used for determining the stereoisomers' absolute configuration. K E Y W O R D S conformational transformations, nucleoside analogues, stereoisomers

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On Dipole Moments and Hydrogen Bond Identification in Water Clusters

Cited by 25 publications

References 58 publications

Density functional theory study on the dihydrogen bond cooperativity in the growth behavior of dimethyl sulfoxide clusters

Density functional theory study on the dihydrogen bond cooperativity in the growth behavior of dimethyl sulfoxide clusters

On the cooperativity of association and reference energy scales in thermodynamic perturbation theory

Theoretical and experimental evidence of conformational transformation in stereoisomers of nucleoside analogues

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