Hydrogen Bonding without Borders:  An Atoms-in-Molecules Perspective

Parthasarathi, Ramakrishnan; Subramanian, V.; Sathyamurthy, N.

doi:10.1021/jp060571z

Cited by 385 publications

(301 citation statements)

References 17 publications

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“…Further, the electron density at the bcp is used as a measure of the strength of the bonding interaction. [63][64][65][66][67][68] In the present study, the bcp analysis was done at MPWB1K and M06-2X levels. For some selected systems, the effect of solvation was considered by optimizing the structures using the polarizable continuum model (PCM) 69 at MPWB1K/6-311G(d,p) level of theory.…”

Section: Methodsmentioning

confidence: 99%

Typical aromatic noncovalent interactions in proteins: A theoretical study using phenylalanine

et al. 2008

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A systematic study of CH...pi, OH...pi, NH...pi, and cation...pi interactions has been done using complexes of phenylalanine in its cationic, anionic, neutral, and zwitterionic forms with CH(4), H(2)O, NH(3), and NH(4) (+) at B3LYP, MP2, MPWB1K, and M06-2X levels of theory. All noncovalent interactions are identified by the presence of bond critical points (bcps) of electron density (rho(r)) and the values of rho(r) showed linear relationship to the binding energies (E(total)). The estimated E(total) from supermolecule, fragmentation, and rho(r) approaches suggest that cation...pi interactions are in the range of 36 to 46 kcal/mol, whereas OH...pi, and NH...pi interactions have comparable strengths of 6 to 27 kcal/mol and CH...pi interactions are the weakest (0.62-2.55 kcal/mol). Among different forms of phenylalanine, cationic form generally showed the highest noncovalent interactions at all levels of theory. Cooperativity of multiple interactions is analyzed on the basis of rho(r) at bcps which suggests that OH...pi and NH...pi interactions show positive, whereas CH...pi and cation...pi interactions exhibit negative cooperativity with respect to the side chain hydrogen bond interactions. In general, side chain interactions are strengthened as a result of aromatic interaction. Solvation has no significant effect on the overall geometry of the complex though slight weakening of noncovalent interactions by 1-2 kcal/mol is observed. An assessment of the four levels of theory studied herein suggests that both MPWB1K and M06-2X give better performance for noncovalent interactions. The results also support the fact that B3LYP is inadequate for the study of weak interactions.

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Section: Methodsmentioning

confidence: 99%

Typical aromatic noncovalent interactions in proteins: A theoretical study using phenylalanine

et al. 2008

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“…It is clear then that the barriers for large amplitude motions that break the H bond in X-HؒؒؒY are more important in determining the presence of an observable hydrogen bond than the X-HؒؒؒY binding energy [117]. If this criterion is applied, one could indeed see the "border" between hydrogen-bonding and van der Waals interaction [118]. Hence, in the list of criteria no specific energy cutoff is given, and it is suggested that the X-HؒؒؒY bond must have sufficient strength to be observed under the given experimental conditions.…”

Section: Distance and Energy Criteria: Crystallographic Evidencementioning

confidence: 99%

Defining the hydrogen bond: An account (IUPAC Technical Report)

Arunan

Desiraju

Klein³

et al. 2011

Pure and Applied Chemistry

879

605

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Abstract:The term "hydrogen bond" has been used in the literature for nearly a century now. While its importance has been realized by physicists, chemists, biologists, and material scientists, there has been a continual debate about what this term means. This debate has intensified following some important experimental results, especially in the last decade, which questioned the basis of the traditional view on hydrogen bonding. Most important among them are the direct experimental evidence for a partial covalent nature and the observation of a blue-shift in stretching frequency following X-HؒؒؒY hydrogen bond formation (XH being the hydrogen bond donor and Y being the hydrogen bond acceptor). Considering the recent experimental and theoretical advances, we have proposed a new definition of the hydrogen bond, which emphasizes the need for evidence. A list of criteria has been provided, and these can be used as evidence for the hydrogen bond formation. This list is followed by some characteristics that are observed in typical hydrogen-bonding environments.

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“…3, we provide the ranges for weak, moderate and strong hydrogen bonds, according to the classification made by Parthasarathi et al 31 The majority of the bond energy values fall in the moderate bond region. At the same time, several type 1 bonds fall in the strong bond region.…”

mentioning

confidence: 99%

New insights into the solubility of graphene oxide in water and alcohols

Neklyudov

Khafizov

Sedov

et al. 2017

Phys. Chem. Chem. Phys.

116

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aOne of the main advantages of graphene oxide (GO) over its non-oxidized counterpart is its ability to form stable solutions in water and some organic solvents. At the same time, the nature of GO solutions is not completely understood; the existing data are scarce and controversial. Here, we demonstrate that the solubility of GO, and the stability of the as-formed solutions depend not just on the solute and solvent cohesion parameters, as commonly believed, but mostly on the chemical interactions at the GO/solvent interface. By the DFT and QTAIM calculations, we demonstrate that the solubility of GO is afforded by strong hydrogen bonding established between GO functional groups and solvent molecules.The main functional groups taking part in hydrogen bonding are tertiary alcohols; epoxides play only a minor role. The magnitude of the bond energy values is significantly higher than that for typical hydrogen bonding. The hydrogen bond energy between GO functional groups and solvent molecules decreases in the sequence: water 4 methanol 4 ethanol. We support our theoretical results by several experimental observations including solution calorimetry. The enthalpy of GO dissolution in water, methanol and ethanol is À0.1815 AE 0.0010, À0.1550 AE 0.0012 and À0.1040 AE 0.0010 kJ g À1 , respectively, in full accordance with the calculated trend. Our findings provide an explanation for the well-known, but poorly understood solvent exchange phenomenon.

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Hydrogen Bonding without Borders: An Atoms-in-Molecules Perspective

Cited by 385 publications

References 17 publications

Typical aromatic noncovalent interactions in proteins: A theoretical study using phenylalanine

Typical aromatic noncovalent interactions in proteins: A theoretical study using phenylalanine

Defining the hydrogen bond: An account (IUPAC Technical Report)

New insights into the solubility of graphene oxide in water and alcohols

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