Characterization of C-H-O Hydrogen Bonds on the Basis of the Charge Density

Koch, Uwe; Popelier, Paul L. A.

doi:10.1021/j100024a016

Cited by 2,982 publications

(2,375 citation statements)

References 17 publications

Supporting

221

Mentioning

2,094

Contrasting

Unclassified

Order By: Relevance

“…By any measure used, the intramolecular N-H…O hydrogen bond is the most significant of these; the density at the associated bcp is very large for a neutral H-bond, 26 as is the potential energy density.…”

Section: Hydrogen Atom Treatmentmentioning

confidence: 99%

Experimental and theoretical charge density distribution in Pigment Yellow 101

Váradi

Tan

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The charge density distribution in 2,2'-Dihydroxy-1,1'-naphthalazine (Pigment Yellow 101; P.Y.101) has been determined using high-resolution X-ray diffraction and multipole refinement, along with density functional theory calculations. Topological analysis of the resulting densities highlights the localisation of single/double bonds in the central C=N-N=C moiety of the molecule in its ground state. The density in the N-N is examined in detail, where we show that very small differences between experiment and theory are amplified by use of the Laplacian of the density. Quantification of hydrogen bonds highlights the importance of the intramolecular N-H…O interaction, known to be vital for retention of fluorescence in the solid state, relative to the many but weak intermolecular contacts located.However, a popular method for deriving H-bond strengths from density data appears to struggle with the intramolecular N-H…O interaction. We also show that theoretical estimation of anisotropic displacements for hydrogen atoms brings little benefit overall, and degrades agreement with experiment for one intra-molecular contact.2

show abstract

Section: Hydrogen Atom Treatmentmentioning

confidence: 99%

Experimental and theoretical charge density distribution in Pigment Yellow 101

Váradi

Tan

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…Figure 4 displays the Mulliken net populations on the "own" molecule for each of the five localized orbitals corresponding to the individual water monomers in the (H 2 O) 28 cluster. (The case of using the NLO localized orbitals is shown, the other three are quite analogous.)…”

Section: Resultsmentioning

confidence: 99%

On Dipole Moments and Hydrogen Bond Identification in Water Clusters

Bakó

Mayer

2016

J. Phys. Chem. A

View full text Add to dashboard Cite

It is demonstrated that the localized orbitals calculated for a water cluster have small delocalization tails along the hydrogen bonds, that are crucial in determining the resulting dipole moments of the system. (By cutting them, one gets much smaller dipole moments for the individual monomers-close to the values one obtains by using a Badertype analysis.) This means that the individual water monomers can be delimited only in a quite fuzzy manner, and the electronic charge density in a given point cannot be assigned completely to that or another molecule. Thus one arrives to the brink of breaking the concept of a water cluster consisting of individual molecules. The analysis of the tails of the localized orbitals can also be used to identify the pairs of water molecules actually forming hydrogen bonds. *

show abstract

“…The atomic energy of Hatoms involved in the H···H interaction is usually lower when compared with the energy of a geminal H-atom, ∆E(H) < 0 in Table 3. However, the local stabilizing energy contribution A similar analysis was performed on the CH···O close contacts present in all conformers of the NiNTPA complex - [63][64][65] Each conformer of the NiNTPA complex has two close contacts, either CH···HC or CH···O, which were not seen by the QTAIM analysis as additional bonds even though the necessary condition, the distance criterion, is satisfied. For instance, the distance between two H-atoms, CH24···H29C, in S-c conformer is 2.108 Å and this is significantly shorter than similar contact in, e.g.…”

Section: Resultsmentioning

confidence: 99%

A Density Functional Theory- and Atoms in Molecules-based Study of NiNTA and NiNTPA Complexes toward Physical Properties Controlling their Stability. A New Method of Computing a Formation Constant

Cukrowski

Govender

2010

Inorg. Chem.

View full text Add to dashboard Cite

The log K 1 value of analytical quality was obtained for the NiNTPA complex using the DFTcomputed (at the B3LYP/6-311++G(d,p) level of theory in solvent, CPCM/UAKS) G (aq) values of the lowest energy conformers of the ligands, NTA (nitrilotriacetic acid) and NTPA (nitrilotri-3-propanoic acid), and Ni(II) complexes (NiNTA and NiNTPA). The described mathematical protocol is of general nature. The topological analysis, based on the Quantum Theory of Atoms in Molecules (QTAIM) of Bader, was used to characterize coordination bonds, chelating rings and additional intramolecular interactions in the complexes. The topological data, but not the structural analysis, explained the observed difference in stability of the NiNTA and NiNTPA complexes. It was found that the structural H···H contacts (classically regarded H-clashes, a steric hindrance destabilizing the complex) are in fact the H-H bonds contributing to the overall stability of NiNTPA. Also a CH-O bond was found in NiNTPA. The absence of intramolecular bonds between the atoms that fulfill a distance criterion in NiNTPA is explained by the formation of adjacent intramolecular rings that have larger electron density at the ring critical points when compared with the rings containing these atoms. It is postulated that the strength of a chelating ring (a chelating effect) can be measured by the electron density at the ring critical point. It was found that the strain energy, E s , in the as-in-complex NTPA ligand (E s is significantly lowered by the presence of the intramolecular bonded interactions found by QTAIM) is responsible for the decrease in strength of NiNTPA; the E s ratio (NTPA/NTA) of 1.9 correlates well with the experimental log K 1 ratio (NTA/NTPA) of 1.98.2

show abstract

Characterization of C-H-O Hydrogen Bonds on the Basis of the Charge Density

Cited by 2,982 publications

References 17 publications

Experimental and theoretical charge density distribution in Pigment Yellow 101

Experimental and theoretical charge density distribution in Pigment Yellow 101

On Dipole Moments and Hydrogen Bond Identification in Water Clusters

A Density Functional Theory- and Atoms in Molecules-based Study of NiNTA and NiNTPA Complexes toward Physical Properties Controlling their Stability. A New Method of Computing a Formation Constant

Contact Info

Product

Resources

About