Reactions of hydrogen atom with hydrogen peroxide

Rate coefficients are calculated using canonical variational transition state theory with multidimensional tunneling (CVT/SCT) for the reactions H + H2O2 --> H2O + OH (1a) and H + H2O2 --> HO2 + H2 (1b). Reaction barrier heights are determined using two theoretical approaches: (i) comparison of parametrized rate coefficient calculations employing CVT/SCT to experiment and (ii) high-level ab initio methods. The evaluated experimental data reveal considerable variations of the barrier height for the first reaction: although the zero-point-exclusive barrier for (1a) derived from the data by Klemm et al. (First Int. Chem. Kinet. Symposium 1975, 61) is 4.6 kcal/mol, other available measurements result in a higher barrier of 6.2 kcal/mol. The empirically derived zero-point-exclusive barrier for (1b) is 10.4 kcal/mol. The electronic structure of the system at transition state geometries in both reactions was found to have "multireference" character; therefore special care was taken when analyzing electronic structure calculations. Transition state geometries are optimized by multireference perturbation theory (MRMP2) with a variety of one-electron basis sets, and by a multireference coupled cluster (MR-AQCCSD) method. A variety of single-reference benchmark-level calculations have also been carried out; included among them are BMC-CCSD, G3SX(MP3), G3SX, G3, G2, MCG3, CBS-APNO, CBS-Q, CBS-QB3, and CCSD(T). Our data obtained at the MRMP2 level are the most complete; the barrier height for (1a) using MRMP2 at the infinite basis set limit is 4.8 kcal/mol. Results are also obtained with midlevel single-reference multicoefficient correlation methods, such as MC3BB, MC3MPW, MC-QCISD/3, and MC-QCISD-MPWB, and with a variety of hybrid density functional methods, which are compared with high-level theory. On the basis of the evaluated experimental values and the benchmark calculations, two possible recommended values are given for the rate coefficients.     

Influence of gaseous hydrogen on the hydrogen transfer reaction between phenanthrene and hydrogen donors

Transfer hydrogenation of phenanthrene was performed in the presence of superbases or strong acids and gaseous hydrogen. The influence of hydrogen on the yield of these reactions was discussed with respect to the mechanism of hydrogen transfer.     

Unique hydrogen bonds between 9-anthracenyl hydrogen and anions

Unique hydrogen bonds of the 9-H of anthracene moieties in hosts 1 and 2 with fluoride and pyrophosphate ions were observed on the basis of the (1)H NMR experiments. Furthermore, hosts 1 and 2 act as a colorimetric sensor and a fluorescent chemosensor for the recognition of fluoride ion, respectively.     

Unusual hydrogen bonding in L‐cysteine hydrogen fluoride

L‐Cysteine hydrogen fluoride, or bis(L‐cysteinium) difluoride–L‐cysteine–hydrogen fluoride (1/1/1), 2C₃H₈NO₂S⁺·2F⁻·C₃H₇NO₂S·HF or L‐Cys⁺(L‐Cys...L‐Cys⁺)F⁻(F⁻...H—F), provides the first example of a structure with cations of the `triglycine sulfate' type, i.e.A⁺(A...A⁺) (where A and A⁺ are the zwitterionic and cationic states of an amino acid, respectively), without a doubly charged counter‐ion. The salt crystallizes in the monoclinic system with the space group P2₁. The dimeric (L‐Cys...L‐Cys⁺) cation and the dimeric (F⁻...H—F) anion are formed via strong O—H...O or F—H...F hydrogen bonds, respectively, with very short O...O [2.4438 (19) Å] and F...F distances [2.2676 (17) Å]. The F...F distance is significantly shorter than in solid hydrogen fluoride. Additionally, there is another very short hydrogen bond, of O—H...F type, formed by a L‐cysteinium cation and a fluoride ion. The corresponding O...F distance of 2.3412 (19) Å seems to be the shortest among O—H...F and F—H...O hydrogen bonds known to date. The single‐crystal X‐ray diffraction study was complemented by IR spectroscopy. Of special interest was the spectral region of vibrations related to the above‐mentioned hydrogen bonds.     

Oxidation of hydrogen chloride with hydrogen peroxide in aqueous solution

Evolution of chlorine into the gas phase upon mixing of aqueous solutions of hydrogen chloride and hydrogen peroxide was studied. The threshold hydrogen chloride concentration corresponding to the onset of the chlorine evolution was determined.     

Electron and hydrogen transfer in small hydrogen fluoride anion clusters

A new stable structure has been found for the anion clusters of hydrogen fluoride. The ab initio method was used to optimize the structures of the (HF)(3)(-), (HF)(4)(-), (HF)(5)(-), and (HF)(6)(-) anion clusters with an excess "solvated" electron. Instead of the well-known "zig-zag" (HF)(n)(-) structure, a new form, (HF)(n-1)F(-)···H, was found with lower energy. In this new form, the terminal hydrogen atom in the (HF)(n)(-) chain is separated from the other part of the cluster and the inner hydrogens transfer along the hydrogen bonds toward the outside fluoride. The negative charge also transfers from the terminal HF molecule of the chain to the center fluoride atoms. The (HF)(n)(-) clusters for n = 4, 5, and 6 have not yet been observed experimentally. These results should assist in the search for these systems and also provide a possible way to study the proton and electron transfer in some large hydrogen bonding systems.     

On the difference between hydrogen fluoride and hydrogen chloride crystals

The geometrical and energetical parameters of hydrogen fluoride and hydrogen chloride crystals are calculated using the periodic Hartree–Fock method with 6-31G and 6-31G(d,p) basis sets. The comparison of the stabilisation energies reveals that HCl crystals are about 75% less stable than HF crystals. The activation energy for collective proton movements are computed and discussed in view of data of isolated infinite chains. The barriers of 13.1 and 40.0 kcal mol⁻¹ at 6-31G(d,p) level are found for HF and HCl crystals.     

Gas chromatographic analysis of traces of hydrogen sulfide in hydrogen

Summary A simple gas chromatographic method has been developed for analysis of hydrogen sulfide in hydrogen at the 0.5 to 100 ppm level. After enriching the traces of hydrogen sulfide by absorption in a gas loop packed with the chosen column support at 77 K it was determined by using a Chromosorb G column with silicone 550 and phthalic anhydride as liquid phases, hydrogen as carrier gas and a thermal conductivity detector. The detection limit was found to be about 0.5 ppm of hydrogen sulfide.     

Nonconventional hydrogen bonding between clusters of gold and hydrogen fluoride

The bonding patterns between small neutral gold Au(3 < or = n < or = 7) and hydrogen fluoride (HF)(1 < or = m < or = 4) clusters are discussed using a high-level density functional approach. Two types of interactions, anchoring Au-F and F-H...Au, govern the complexation of these clusters. The F-H...Au interaction exhibits all the characteristics of nonconventional hydrogen bonding and plays a leading role in stabilizing the lowest-energy complexes. The anchor bonding mainly activates the conventional F-H...F hydrogen bonds within HF clusters and reinforces the nonconventional F-H...Au one. The strength of the F-H...Au bonding, formed between the terminal conventional proton donor group FH and an unanchored gold atom, depends on the coordination of the involved gold atom: the less it is coordinated, the stronger its nonconventional proton acceptor ability. The strongest F-H...Au bond is formed between a HF dimer and the singly coordinated gold atom of a T-shape Au4 cluster and is accompanied by a very large red shift (1023 cm(-1)) of the nu(F-H) stretch. Estimations of the energies of formation of the F-H...Au bonds for the entire series of the studied complexes are provided.     

Photosynthetic hydrogen production

Among various technologies for hydrogen production, the use of oxygenic natural photosynthesis has a great potential as can use clean and cheap sources—water and solar energy. In oxygenic photosynthetic microorganisms electrons and protons produced from water and redirected by the photosynthetic electron-transport chain via ferredoxin to the hydrogen-producing enzymes hydrogenase or nitrogenase. By these enzymes, e^? and H⁺ recombine and form molecular hydrogen. Hydrogenase activity can be very high but is extremely sensitive to the photosynthetically evolved O₂ that leads to reduced and unstable H₂ production. However, presently, several approaches are developed to improve the energetic efficiency to generate H₂. This review examines the main available pathways to improve the photosynthetic H₂ production.     

Fluorine hydrogen short contacts and hydrogen bonds in substituted benzamides

A series of fluorine substituted benzamides 1-10 was synthesised and investigated by spectroscopic methods (NMR, IR, MS) and X-ray structure analysis. The configuration of these compounds strongly depends on solvent, temperature and substitution pattern. Unexpectedly, some of these compounds form weak intramolecular hydrogen bonds/short NH?FC contacts in CDCl₃ solution and in the solid state.     

Reversibly adsorbed hydrogen on a molybdena-alumina catalyst reduced with hydrogen

The elution of hydrogen and water desorbed from a MoO₃Al₂O₃ catalyst reduced with hydrogen at 550°C was investigated at 550°C and at O°C. Only hydrogen may be eluted at 550°C, and neither hydrogen may be eluted at 550°C, and neither hydrogen, nor water desorbs at O°C. The reversibly adsorbed hydrogen is responsible for the deactivation of the catalyst used in disproportion ation of propylene at 0–80°C without evacuation at elevated temperatures after reduction.

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, MoO₃/Al₂O₃, 550°C, 550 0°C. 550°C , 0°C , . , 0–80°C , .

     

Adsorption of molecular hydrogen and hydrogen sulfide on Au clusters

The authors present theoretical results describing the adsorption of H2 and H2S molecules on small neutral and cationic gold clusters (Au(n)((0/+1)), n=1-8) using density functional theory with the generalized gradient approximation. Lowest energy structures of the gold clusters along with their isomers are considered in the optimization process for molecular adsorption. The adsorption energies of H2S molecule on the cationic clusters are generally greater than those on the corresponding neutral clusters. These are also greater than the H2 adsorption energies on the corresponding cationic and neutral clusters. The adsorption energies for cationic clusters decrease with increasing cluster size. This fact is reflected in the elongations of the Au-S and Au-H bonds indicating weak adsorption as the cluster grows. In most cases, the geometry of the lowest energy gold cluster remains planar even after the adsorption. In addition, the adsorbed molecule gets adjusted such that its center of mass lies on the plane of the gold cluster. Study of the orbital charge density of the gold adsorbed H2S molecule reveals that conduction is possible through molecular orbitals other than the lowest unoccupied molecular orbital level. The dissociation of the cationic Au(n)SH2+ cluster into Au(n)S+ and H2 is preferred over the dissociation into Au(m)SH2+ and Au(n-m), where n=2-8 and m=1-(n-1). H2S adsorbed clusters with odd number of gold atoms are more stable than neighboring even n clusters.     

The hydrogen bond

The concept of the hydrogen bond is a century old but remains youthful because of its vital role in so many branches of science and because of continued advances in experiment, theory and simulation. We discuss the structural and energetic characteristics of normal hydrogen bonds X–H···Y as well as some exceptions to the normal, including proton-shared and ion-pair bonds. We consider the harmonic and anharmonic vibration of X–H in a variety of complexes, and demonstrate that there is no fundamental difference between blue-shifting and red-shifting bonds. We discuss water clusters and liquid water and indicate possible directions of future progress.     

Shell-confined hydrogen atom

Calculations of electronic energy and static dipole polarizability are reported for the hydrogen atom in the ns states (n = 1-6) confined between two impenetrable concentric spheres of inner and outer radii placed at the locations of the radial nodes corresponding to the free hydrogen ns (n = 2-7) orbitals. Interesting new conditions of degeneracy arising due to the shell confinement are discussed. Shell-confined states of unusually high polarizability are predicted for hydrogen atom as the inner sphere radius is shifted towards the outer nodal points of the free atom corresponding to the higher principal quantum numbers.