Steve Scheiner

Definition of the hydrogen bond (IUPAC Recommendations 2011)

A novel definition for the hydrogen bond is recommended here. It takes into account the theoretical and experimental knowledge acquired over the past century. This definition insists on some evidence. Six criteria are listed that could be used as evidence for the presence of a hydrogen bond.

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

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–H···Y 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.

Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg

Electronic structure and bonding in metal phthalocyanines (Metal=Fe, Co, Ni, Cu, Zn, Mg) is investigated in detail using a density functional method. The metal atoms are strongly bound to the phthalocyanine ring in each case, by as much as 10 eV. The calculated orbital energy levels and relative total energies of these D4h structures indicate that Fe and Co phthalocyanines have 3A2g and 2Eg ground states, respectively, but that these states are changed upon interaction with strong-field axial ligands. The valence electronic structures of Fe and Co phthalocyanines differ significantly from those of the others. The HOMOs in Fe, Co, and Cu phthalocyanine are metal 3d-like, whereas in Ni and Zn phthalocyanines, the HOMO is localized on the phthalocyanine ring. The first ionization removes an electron from the phthalocyanine a1u orbital in all cases, with very little sensitivity of the ionization energy to the identity of the metal. Whereas the first reduction in Fe and Co phthalocyanine occurs at the metal, i...

The Pnicogen Bond: Its Relation to Hydrogen, Halogen, and Other Noncovalent Bonds

Among a wide range of noncovalent interactions, hydrogen (H) bonds are well known for their specific roles in various chemical and biological phenomena. When describing conventional hydrogen bonding, researchers use the notation AH···D (where A refers to the electron acceptor and D to the donor). However, the AH molecule engaged in a AH···D H-bond can also be pivoted around by roughly 180°, resulting in a HA···D arrangement. Even without the H atom in a bridging position, this arrangement can be attractive, as explained in this Account. The electron density donated by D transfers into a AH σ* antibonding orbital in either case: the lobe of the σ* orbital near the H atom in the H-bonding AH···D geometry, or the lobe proximate to the A atom in the HA···D case. A favorable electrostatic interaction energy between the two molecules supplements this charge transfer. When A belongs to the pnictide family of elements, which include phosphorus, arsenic, antimony, and bismuth, this type of interaction is called a pnicogen bond. This bonding interaction is somewhat analogous to the chalcogen and halogen bonds that arise when A is an element in group 16 or 17, respectively, of the periodic table. Electronegative substitutions, such as a F for a H atom opposite the electron donor atom, strengthen the pnicogen bond. For example, the binding energy in FH(2)P···NH(3) greatly exceeds that of the paradigmatic H-bonding water dimer. Surprisingly, di- or tri-halogenation does not produce any additional stabilization, in marked contrast to H-bonds. Chalcogen and halogen bonds show similar strength to the pnicogen bond for a given electron-withdrawing substituent. This insensitivity to the electron-acceptor atom distinguishes these interactions from H-bonds, in which energy depends strongly upon the identity of the proton-donor atom. As with H-bonds, pnicogen bonds can extract electron density from the lone pairs of atoms on the partner molecule, such as N, O, and S. The π systems of carbon chains can donate electron density in pnicogen bonds. Indeed, the strength of A···π pnicogen bonds exceeds that of H-bonds even when using strong proton donors such as water with the same π system. H-bonds typically have a high propensity for a linear AH···D arrangement, but pnicogen bonds show an even greater degree of anisotropy. Distortions of pnicogen bonds away from their preferred geometry cause a more rapid loss of stability than in H-bonds. Although often observed in dimers in the gas phase, pnicogen bonds also serve as the glue in larger aggregates, and researchers have found them in a number of diffraction studies of crystals.

Electronic structure and bonding in metal porphyrins, metal=Fe, Co, Ni, Cu, Zn

A systematic theoretical study of the electronic structure and bonding in metal meso-tetraphenyl porphines MTPP, M=Fe, Co, Ni, Cu, Zn has been carried out using a density functional theory method. The calculations provide a clear elucidation of the ground states for the MTPPs and for a series of [MTPP]x ions (x=2+, 1+, 1−, 2−, 3−, 4−), which aids in understanding a number of observed electronic properties. The calculation supports the experimental assignment of unligated FeTPP as 3A2g, which arises from the configuration (dxy)2(dz2)2(dxz)1(dyz)1. The calculated M–TPP binding energies, ionization potentials, and electron affinities are in good agreement with available experimental data. The influence of axial ligands and peripheral substitution by fluorine are in accord with the experimental observation that not only half-wave potentials (E1/2) of electrode reactions, but also the site of oxidation/reduction, may be dependent on the porphyrin basicity and the type of axial ligand coordination.

A New Noncovalent Force: Comparison of P∙∙∙N Interaction with Hydrogen and Halogen Bonds

When PH(3) is paired with NH(3), the two molecules are oriented such that the P and N atoms face one another directly, without the intermediacy of a H atom. Quantum calculations indicate that this attraction is due in part to the transfer of electron density from the lone pair of the N atom to the σ(∗) antibond of a P-H covalent bond. Unlike a H-bond, the pertinent hydrogen is oriented about 180° away from, instead of toward, the N, and the N lone pair overlaps with the lobe of the P-H σ(∗) orbital that is closest to the P. In contrast to halogen bonds, there is no requirement of a σ-hole of positive electrostatic potential on the P atom, nor is it necessary for the two interacting atoms to be of differing potential. In fact, the two atoms can be identical, as the global minimum of the PH(3) homodimer has the same structure, characterized by a P···P attraction. Natural bond orbital analysis, energy decomposition, and visualization of total electron density shifts reveal other similarities and differences between the three sorts of molecular interaction.

Effects of substituents upon the P···N noncovalent interaction: the limits of its strength.

Previous work has documented the ability of the P atom to form a direct attractive noncovalent interaction with a N atom, based in large measure on the charge transfer from the N lone pair into the σ* antibonding orbital of the P-H that is turned away from the N atom. As the systems studied to date include only hydrides, the present work considers how substituents affect the interaction and examines whether P···N might compete with other attractive forces such as H-bonds. It is found that the addition of electron-withdrawing substituents greatly strengthens the P···N interaction to the point where it exceeds that of the majority of H-bonds. The highest interaction energy occurs in the FH(2)P···N(CH(3))(3) complex, amounting to 11 kcal/mol. A breakdown of the individual forces involved attributes the stability of the interaction to approximately equal parts electrostatic and induction energy, with a smaller contribution from dispersion.

Ab initio study of intermolecular potential of H2O trimer

Nonadditive contribution to the interaction energy in water trimer is analyzed in terms of Heitler–London exchange, SCF deformation, induction and dispersion nonadditivities. Nonadditivity originates mainly from the SCF deformation effect which is due to electric polarization. However, polarization does not serve as a universal mechanism for nonadditivity in water. In the double‐donor configuration, for example, the Heitler–London exchange contribution is the most important and polarization yields the wrong sign. Correlation effects do not contribute significantly to the nonadditivity. A detailed analysis of the pair potential is also provided. The present two‐body potential and its components are compared to the existing ab initio potentials (MCY) as well as to empirical ones (RWK2,TIP,SPC). The ways to improve these potentials are suggested.

Correction of the basis set superposition error in SCF and MP2 interaction energies. The water dimer

There has been some discussion concerning whether basis set superposition error is more correctly evaluated using the full set of ghost orbitals of the partner molecule or some subset thereof. A formal treatment is presented, arguing that the full set is required at the Mo/ller–Plesset level. Numerical support for this position is provided by calculation of the interaction energy between a pair of water molecules, using a series of moderate sized basis sets ranging from 6‐31G** to the [432/21] contraction suggested by Clementi and Habitz. These energies, at both the SCF and MP2 levels, behave erratically with respect to changes in details of the basis set, e.g., H p‐function exponent. On the other hand, after counterpoise correction using the full set of partner ghost orbitals, the interaction energies are rather insensitive to basis set and behave in a manner consistent with calculated monomer properties. For long intersystem separations, the contribution of correlation to the interaction is repulsive de...

Nonadditive effects in HF and HCl trimers

Nonadditive effects are calculated for (HF)3 and (HCl)3 complexes and analyzed via the combination of perturbation theory of intermolecular forces with Mo/ller–Plesset perturbation theory (MPPT). In both systems the nonadditivity is dominated by the self‐consistent field (SCF) deformation effect, i.e., mutual polarization of the monomer wavefunctions. Heitler–London exchange and correlation effects are of secondary importance. Three‐body terms exhibit much lesser basis set dependence than the two‐body effects and even quite moderate basis sets which are not accurate enough for treatment of two‐body forces can yield three‐body effects of quantitative quality. This is due in large measure to the additivity of strongly basis set dependent components such as uncorrelated and correlated electrostatics and dispersion. Various approximate models for the three‐body potentials and total interaction in the (HF)3 cluster are analyzed from the point of view of their ability to predict the orientation dependence of in...