Computational study of the process of hydrogen bond breaking: The case of the formamide–formic acid complex

Pacios, Luis F.

doi:10.1002/jcc.20475

Cited by 12 publications

(7 citation statements)

References 77 publications

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“…AIM charges were computed with AIMAll41 using the PROAIM integration scheme of AIMPAC while NPA charges were obtained with GAUSSIAN 03. Isocontour maps of ρ( r ) and η( r ) as well as three‐dimensional (3D) pictures of ELF domains were plotted from numerical grids computed with CheckDen (Pacios, unpublished observation) 42. 3D images in Figure 4 were rendered with VMD 1.8.4 43.…”

Section: Methodsmentioning

confidence: 99%

Characterization of two types of intermolecular interactions on halogen monoxide monohydrates

2009

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Monohydrates of halogen monoxides ClO.H2O and BrO.H2O have been studied by means of DFT (B3LYP) and ab initio (MP2) correlated calculations with aug-cc-pVnZ basis sets ranging from triple- up to quintuple-zeta. These complexes might be formed in the troposphere and stratosphere and participate in chemical reactions involved in ozone depletion. Two stable structures are found that differ in the intermolecular interaction which takes place, namely: conventional XO...HOH hydrogen bond and OX...OH2 halogen bond. We demonstrate that both types of interactions participate in the formation of these complexes yet all the computational methods tested predict a slightly greater stability for the latter OX...O link. Both intermolecular interactions are characterized upon analyzing electron density distribution, charge transfer effects, and electron localization domains. These analyses reveal the central role played by electron redistribution. Because of this, the greater spatial extent of the electron density in Cl or Br as compared to H could be the main cause to yield a slightly greater stability for the O-X...O halogen bond with respect to the O...H-O hydrogen bond.

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Section: Methodsmentioning

confidence: 99%

Characterization of two types of intermolecular interactions on halogen monoxide monohydrates

2009

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“…A step interval of 0.07 bohr was chosen in each direction to set the spatial grids of ELF basins which required about 10 7 points per geometry. Contour maps of ρ(r) and η(r) were calculated with CHECKDEN, a program to compute ED, ELF and many other related functions at spatial grids of different number of dimensions [41].…”

Section: Methodsmentioning

confidence: 99%

Change with the Intermolecular Distance of Electron Properties of Hydrogen Bond Dimers at Equilibrium and Non-equilibrium Geometries

Pacios

2005

Struct Chem

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The change with the intermolecular distance R of a number of electron properties obtained from the electron density ρ(r) and the electron localization function η(r) along with some selected structural features is investigated for seven dimers linked by conventional hydrogen bonds (HBs). Five nonequilibrium geometries apart from the equilibrium one are optimized in MP2/6-311++G(d,p) ab initio calculations for every dimer. The variation with R of topological descriptors and integrated properties computed from ρ(r) and η(r) reveals that not only features characteristics of hydrogen bonding are still noticed inside the equilibrium distance R eq but the sign and magnitude of HB trends are kept at R < R eq . Only at the shortest intermolecular distances where dramatic structural changes occur, these trends revert their direction although in most cases HB characteristics are still noticed.

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“…Such behavior of the electron density is typical for the process of bond breaking (e.g. hydrogen-bond breaking in the formamide-formic acid complex) [57] or for weak multicentered intermolecular interactions. [58,59] However, bifurcated hydrogen bonds described in the literature, in which the proton interacts with two acceptor atoms, feature two bond critical points with similar or different electron densities depending on the geometry.…”

Section: [Cp*mh(dppe)]·tfementioning

confidence: 99%

Directionality of Dihydrogen Bonds: The Role of Transition Metal Atoms

Filippov¹,

Belkova²,

Epstein³

et al. 2012

ChemPhysChem

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A theoretical study on two series of electron-rich group 8 hydrides is carried out to evaluate involvement of the transition metal in dihydrogen bonding. To this end, the structural and electronic parameters are computed at the DFT/B3PW91 level for hydrogen-bonded adducts of [(PP(3))MH(2)] and [Cp*MH(dppe)] (M = Fe, Ru, Os; PP(3) = κ(4)-P(CH(2)CH(2)PPh(2))(3), dppe = κ(2)-Ph(2)PCH(2)CH(2)PPh(2)) with CF(3)CH(2)OH (TFE) as proton donor. The results are compared with those of adduct [Cp(2)NbH(3)]⋅TFE featuring a "pure" dihydrogen bond, and classical hydrogen bonds in pyridine⋅TFE and Me(3)N⋅TFE. Deviation of the H⋅⋅⋅H-A fragment from linearity is shown to originate from the metal participation in dihydrogen bonding. The latter is confirmed by the electronic parameters obtained by NBO and AIM analysis. Considered together, orbital interaction energies and hydrogen bond ellipticity are salient indicators of this effect and allow the MH⋅⋅⋅HA interaction to be described as a bifurcate hydrogen bond. The impact of the M⋅⋅⋅HA interaction is shown to increase on descending the group, and this explains the experimental trends in mechanisms of proton-transfer reactions via MH⋅⋅⋅HA intermediates. Strengthening of the M⋅⋅⋅H interaction in the case of electron-rich 5d metal hydrides leads to direct proton transfer to the metal atom.

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Computational study of the process of hydrogen bond breaking: The case of the formamide–formic acid complex

Cited by 12 publications

References 77 publications

Characterization of two types of intermolecular interactions on halogen monoxide monohydrates

Characterization of two types of intermolecular interactions on halogen monoxide monohydrates

Change with the Intermolecular Distance of Electron Properties of Hydrogen Bond Dimers at Equilibrium and Non-equilibrium Geometries

Directionality of Dihydrogen Bonds: The Role of Transition Metal Atoms

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