Partition potential for hydrogen bonding in formic acid dimers

The ground-state energy and density of 4 low-energy conformations of the formic acid dimer were calculated via partition density functional theory (PDFT). The differences between isolated and PDFT monomer densities display similar deformation patterns for primary and secondary hydrogen bonds (HBs) among all 4 dimers. In contrast, the partition potential shows no transferable features in the bonding regions. These observations highlight the global character of the partition potential and the cooperative effect that occurs when a dimer is bound via more than 1 HB. We also provide numerical confirmation of the intuitive (but unproven) observation that fragment deformation energies are larger for systems with larger binding energies.     

Hydrogen bonding between formic acid and water: complete stabilization of the intrinsically unstable conformer

We studied hydrogen bonding between formic acid (FA) and water in solid argon and identified the first water complex with the higher-energy conformer cis-FA. In sharp contrast to cis-FA monomer, cis-FA interacting with water is very stable at low temperatures, which was explained by strong O-H...O hydrogen bonding. These benchmark results show that hydrogen bonding can terminate proton tunneling reactions and efficiently stabilize intrinsically unstable conformational structures in complex asymmetrical hydrogen-bonded networks. This general effect occurs when the energy difference between conformers is smaller than the hydrogen bond interaction energy, which opens perspectives in chemistry on intrinsically unstable conformers.     

Polar isomer of formic acid dimers formed in helium nanodroplets

The infrared spectrum of formic acid dimers in helium nanodroplets has been observed corresponding to excitation of the "free" OH and CH stretches. The experimental results are consistent with a polar acyclic structure for the dimer. The formation of this structure in helium, as opposed to the much more stable cyclic isomer with two O-H...O hydrogen bonds, is attributed to the unique growth conditions that exist in helium droplets, at a temperature of 0.37 K. Theoretical calculations are also reported to aid in the interpretation of the experimental results. At long range the intermolecular interaction between the two monomers is dominated by the dipole-dipole interaction, which favors the formation of a polar dimer. By following the minimum-energy path, the calculations predict the formation of an acyclic dimer having one O-H...O and one C-H...O contact. This structure corresponds to a local minimum on the potential energy surface and differs significantly from the structure observed in the gas phase.     

Hydrogen bonding in dimers of tritolyl and tritosylurea derivatives of triphenylmethanes

The crystal structure of the homodimer formed by the tritolylurea 3a proves the existence of a belt of six bifurcated hydrogen bonds between both NH and the O=C groups of the adjacent urea residues. For the tritosylurea 3b, four additional three-center hydrogen bonds, also involving the SO2 oxygen, are found in the crystalline state. Molecular dynamics simulations in a chloroform box confirm these patterns of the hydrogen bonds and the resulting elongation of the dimer 3b. 3b in comparison to 3a x 3a. The calculated complexation energies for the three dimeric combinations are nearly identical in agreement with the simultaneous formation of heterodimer 3a x 3b in a mixture of 3a and 3b.     

Quantum studies of hydrogen bonding in formic acid and water ice surface

The structure and spectroscopy (electronic and vibrational) of formic acid (HCOOH) dimers and trimers are investigated by means of the hybrid (B3LYP) density-functional theory. Adsorption of single and dimer HCOOH on amorphous water ice surface is modeled using two different water clusters. Particular attention has been given to spectroscopic consequences. Several hypotheses on formic acid film growing on ice and incorporation of a single water molecule in the formic acid film are proposed.     

Theoretical study of formic acid-sulfur dioxide dimers

We report the first theoretical study of noncovalent and covalent interactions in formic acid (FA)-SO(2) complexes. Using ab initio and DFT model chemistries, five stable noncovalent complexes were identified, as well as a covalent adduct, formic sulfurous anhydride HOSO(2)CHO. syn-FA is predicted to form two nonplanar bidentate complexes with SO(2): the more stable one contains a normal hydrogen bond donated by OH, and the less stable one contains a blue-shifted hydrogen bond donated by CH. Both are stabilized by charge transfer from FA to SO(2). anti-FA forms three planar complexes of nearly equal energy containing OH-to-SO(2) hydrogen bonds. Formic sulfurous anhydride forms via an endothermic concerted cycloaddition. Natural bond orbital analysis showed that the bidentate SO(2)-FA complexes are stabilized by n → π* donation from FA to SO(2), and back-donation from SO(2) n and π* orbitals into FA σ(OH)* or σ(CH)* orbitals. The bidentate formic acid-SO(2) complex that contains an O-H···O hydrogen bond is more stable than the similar nitric acid-SO(2) complex. The latter contains a stronger hydrogen bond but shows no O→S charge transfer interaction.     

No-pair bonding in coinage metal dimers

High-level ab initio calculations at the coupled cluster with single and double substitutions and perturbative treatment of triple substitutions, CCSD(T), level of theory have been carried out for the dimers of coinage metal atoms Cu, Ag, and Au in the ground 1Sigma(g)+ state and in the excited 3Sigma(u)+ state. All of the calculations have been carried out with the inclusion of scalar-relativistic effects via the normalized elimination of the small component (NESC) method. For the dimers in the triplet state, nonzero bond dissociation energies are obtained which vary from 1.3 kcal/mol for 3Cu2 to 4.6 kcal/mol for 3Au2. Taking into account that, in bulky high-spin copper clusters, the bond dissociation energy per atom increases steeply to the value of ca. 19 kcal/mol, the results obtained in the present paper suggest that the bond dissociation energy per atom in high-spin gold clusters may reach extremely high values exceeding 20 kcal/mol thus becoming comparable to the usual bonding due to the spin-pairing mechanism.     

Raman jet spectroscopy of formic acid dimers: low frequency vibrational dynamics and beyond

The vibrational dynamics of formic acid dimer is quite regular at low fundamental excitation frequencies, whereas it evolves into a complex and irregular vibrational signature in the OH stretching region. This is evidenced by the first Raman investigation of the jet-cooled formic acid dimer and its three deuterated isotopomers. Subtle isotope effects in the inter-monomer stretching mode, which is directly observed for the first time at 194 cm(-1), find an interpretation based on hydrogen bond weakening due to quantum delocalization of the protons. The reported high-frequency jet spectra should provide essential experimental stepping stones towards a more complete understanding of this planar prototype for strong double hydrogen bonding.     

Hydrogen bonding between nucleic acid constituents and amino acid amide group

The formation of hydrogen-bonded complexes between 9-ethyladenine and acetamide in chloroform solution has been studied by infrared spectroscopy. Comparison of the mixed solution spectra with the sum of the spectra of the separate monomers in solution shows that cyclic heterodimers are formed when acetamide binds to adenine base. Information is also obtained about the atomic arrangement of these heterodimers, where acetamide is bound to adenine base predominantly through the pyrimidine ring. Hydrogen bonds of this nature have been also observed for concentrated aqueous solutions of adenosine 5′-monophosphate in the presence of acetamide using Raman spectroscopy.     

Hydrogen bond formations between pyrazine and formic acid and between pyrazine and trichloroacetic acid

The hydrogen bond formations between pyrazine and formic acids and between pyrazine and trichloroacetic acids were studied through observation of the Raman and infrared spectra for mixture of pyrazine and formic acid and also mixture of pyrazine and trichloroacetic acid at 77 K. It was observed that the mutual exclusion principle held for the Raman and infrared spectra of both mixtures, even for the spectra of the samples whose mixing mole ratio of acids was very low. This fact clearly indicates that the hydrogen bonded molecule does not exist in the form of formic acid-pyrazine or trichloroacetic acid-pyrazine whose geometry belongs to the Cs point group, but exists in the form of formic acid-pyrazine-formic acid or trichloroacetic acid-pyrazine-trichloroacetic acid belonging to the C(i) point group.     

Hydrogen bonding: A molecular orbital treatment by the EHT and the CNDO/2 methods of methanol and of formic acid

By both the EHT and the CNDO/2 calculations, the linear dimer of methanol is found to be more stable than the cyclic dimer. The hydrogen bonds in the trimer are stronger than those in linear dimers. The proton potential function, charge densities, and overlap populations in the linear dimer of methanol have been obtained. The CNDO/2 calculations show that the cis-form of formic acid is more stable than the trans-form, in agreement with experimental data. The cyclic dimer of formic acid is more stable than the open dimer. The -form of formic acid trimer is more stable than the -form. The proton potential function and the charge densities in the cyclic dimer of formic acid have been obtained. The CNDO/2 method gives more realistic proton potential functions for the dimers of methanol and formic acid. The O ... O stretching force constant in the dimers of methanol and formic acid have been estimated to be 0.13 × 10⁵ dynes/cm and 0.27 × 10⁵ dynes/cm, respectively, in agreement with experimental data.     

Hydrogen bonding between phosphate and amino acid side chains

Hydrogen bonds between polar groups of amino acid side chains (histidine, lysine, glutamic acid) and phosphate ions have been studied by infrared spectroscopy. Proton transfer from amino acid groups to phosphate occur mainly in case that tribasic and dibasic phosphate ions take part in hydrogen bonds. Conformational changes and continuum are strongly related to the degree of proton transfer and hydration. It is pointed out that the aforementioned properties should be of great significance for nucleation and growth of prostatic and renal stones.     

Hydrogen bonding in the hydroxysulfinyl radical‐formic acid‐water system: A theoretical study

Quantum chemical methods have been employed to evaluate the possible configurations of the 1:1 and 1:2 HOSO‐formic acid complexes and 1:1:1 HOSO‐formic acid‐water complexes. The first type of complex involves two H bonds, while the other two types comprise three H bonds in a ring. The complexes are relatively stable, with CBS‐QB3 computed binding energies of 14.3 kcal mol^?1, 23.4 kcal mol^?1, and 21.1 kcal mol^?1 for the lowest‐energy structures of the 1:1, 1:2, and 1:1:1 complexes, respectively. Complex formations induce a large spectral red‐shift and an enhancement of the IR intensity for the H‐bonded OH stretching modes relative to those in the parent monomers. TDDFT calculations of the low‐lying electronic excited states demonstrate that the complexes are photochemically quite stable in the troposphere. Small spectral shifts in comparison to the free HOSO radical suggest that the radical and the complexes would not be easily distinguishable using standard UV/vis absorption spectroscopy. © 2016 Wiley Periodicals, Inc.     

Theoretical study of the bonding in Fe---M dimers

The electronic structures of Fe₂, FeMn, FeCo, FeCu and FeNi have been calculated using Gaussian-76 SCF techniques. Gaussian basis sets contracted to [4s, 2p, 1d] functions are used on each atom resulting in sets of near double zeta accuracy in the valence region. The calculated UHF electronic ground state configurations for these Fe---M dimers are comparable with those experimentally determined. By examining the Mulliken atomic overlap population analysis, a correlation is found between the Mössbauer spectrum and calculated binding strengths in these dimers. Our calculations, fixed at r_e of 2.3 Å, show that the binding strengths decrease from FeCu, FeMn, Fe₂, FeCo, FeNi.     

Geometry and bonding in substituted silacyclopropanes

Minimum energy geometries for silirane, 1; 1,1-difluoro-, 1; 1;1-difluorotetramethyl-, 3; 1,1-dimethyl-, 4; hexamethylsilirane, 5; 7-siladispiro[2.0.2.1]heptane, 6; and its 7,7-dimethyl derivative, 7, have been calculated using the CNDO/2 approximation. Good agreement has been obtained between the predicted structure for 7 and an experimental structure for a related compound. The calculations indicate that the enhanced stability observed for the spirocyclopropyl compounds such as 6 or 7 is due for the most part to increased overlap in the σ framework of the silirane ring resulting from increased contributions of the $\text{s}$ orbitals of the spiro carbon atoms to the bonding. Hyperconjugation between filled Walsh orbitals of the spirocyclopropyl rings and acceptor orbitals on silicon does not contribute as much to the stabilization of 6 and 7 as does the increased σ overlap. The calculations predict that the 1,1-difluorosiliranes, 2 and 3, should have thermodynamic stability comparable to or greater than the other siliranes, but much higher reactivity due to charge separation.     

Hydrogen bonding in polymer mixtures

The enthalpy–infrared frequency shift correlation for simple acids and bases is extended to study hydrogen bonding in polymer systems. The acidity of a polymer is calibrated by comparing the shifts in hydroxyl absorption frequency of the acidic polymer when mixed with a series of bases with the corresponding spectral shifts of known acids with the same bases. The basicity of a polymer is calibrated by measuring the hydroxyl frequency shifts of known acids when mixed with the basic polymer. For polymers containing carbonyl groups, the shift in carbonyl absorption is also a measure of basicity. The acidity and basicity constants obtained for polymers are in good agreement with the values for small-molecule analogs. The enthalpies of hydrogen bond formation in polymer mixtures are calculated from the acidity or basicity constants.