Search results for "Hydrogen molecule"

CASSCF/CASPT2 analysis of the fragmentation of H2 on a Pd4 cluster

2009

Two reactive pathways are described for the dissociative adsorption of a hydrogen molecule on a Pd4 pyramidal cluster, by using DFT/B3LYP and CASSCF/CASPT2 computational methods. Because of the different spin multiplicities of the cluster in the initial and final states, the reaction proceeds through a spin multiplicity change, which occurs close to the transition states. The activation energy values are very similar when the DFT method is used, whereas the CASPT2 calculations predict that the concerted mechanism is disfavored. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

Communication: Rotational excitation of interstellar heavy water by hydrogen molecules

2010

Cross sections and rate coefficients for low lying rotational transitions in D(2)O induced by para-H(2) collisions are presented for the first time. Calculations have been performed at the close-coupling level with the deuterated variant of the H(2)O-H(2) interaction potential of Valiron et al. [J. Chem. Phys. 129, 134306 (2008)]. Rate coefficients are presented for temperatures between 1 and 30 K and are compared to the corresponding rate coefficients for H(2)O. Significant differences caused by the isotopic substitution are observed and are attributed to both kinematics and intramolecular geometry effects. Astrophysical implications are briefly discussed in view of the very recent detecti…

Diffusion and Reactions of Hydrogen inF2-Laser-IrradiatedSiO2Glass

2002

The diffusion and reactions of hydrogenous species generated by single-pulsed F2 laser photolysis of SiO-H bond in SiO2 glass were studied in situ between 10 and 330 K. Experimental evidence indicates that atomic hydrogen (H0) becomes mobile even at temperatures as low as approximately 30 K. A sizable number of H0 dimerize by a diffusion-limited reaction into molecular hydrogen (H2) that may migrate above approximately 200 K. Activation energies for the diffusion, inherently scattered due to the structural disorder in glass, are separated into three bands centered at approximately 0.1 eV for free H0, approximately 0.2 eV presumably for shallow-trapped H0, and approximately 0.4 eV for H2.

Character of the Reaction between Molecular Hydrogen and a Silicon Dangling Bond in Amorphous SiO2

2007

The passivation by diffusing H2 of silicon dangling bond defects (E′ centers, O3tSi•) induced by laser irradiation in amorphous SiO2 (silica) is investigated in situ at several temperatures. It is found that the reaction between the E′ center and H2 requires an activation energy of 0.39 eV and that its kinetics is not diffusionlimited. The results are compared with previous findings on the other fundamental paramagnetic point defect in silica, the oxygen dangling bond, which features completely different reaction properties with H2. Furthermore, a comparison is proposed with literature data on the reaction properties of surface E′ centers, of E′ centers embedded in silica films, and with th…

MP2 Study of Physisorption of Molecular Hydrogen onto Defective Nanotubes: Cooperative Effect in Stone–Wales Defects

2016

We use large-scale MP2 calculations to investigate the physisorption of molecular hydrogen on (9,0) defective carbon nanotubes (CNTs) of C72H18. These large (supra)molecular systems are typically studied using conventional DFT methods, which do not describe well the van der Waals interactions responsible for this process. Here we use CCSD(T)-calibrated MP2 calculations to estimate binding energies by considering four defective structures (hydrogenated divacancy, octagon-pentagon, and two Stone-Wales defects). The largest physisorption energies for the nondefective CNT are for configurations in which H2 points toward the center of one ring. The computed interaction energies for defect-free C…

Exercise-Driven Increase in Gut Microbial Hydrogen Production as a Possible Factor of Metabolic Health

2020

Synthesis, Structure, and Reactivity of (Dihydrogen)(hydrido)iron(II) Complexes Bearing Chiral Diphos­phanes

2015

The heterolytic cleavage of molecular hydrogen by [Fe(H2O)6][BF4]2 and the chiral phosphane (+)-1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene [(R,R)-Me-DuPhos] or its enantiomer [(S,S)-Me-DuPhos] yields the (dihydrogen)(hydrido)iron complexes [FeH(2-H2){(R,R)-Me-DuPhos}2]BF4 ([R,R-1]BF4) and [FeH(2-H2){(S,S)-Me-DuPhos}2]BF4 ([S,S-1]BF4), respectively. These complexes are fluxional in solution at room temperature, and the trans isomers are observed at 200 K. The ()-cis-[R,R-1]BF4 complex was identified crystallographically as the only stereoisomer at room temperature. The energetic and structural differences between the cis ( and ) and trans isomers were analyzed from a computational (DFT)…

Quantum mechanical study of the proton exchange in the ortho-para H2 conversion reaction at low temperature

2011

Ortho-para H2 conversion reactions mediated by the exchange of a H+ proton have been investigated at very low energy for the first time by means of a time independent quantum mechanical (TIQM) approach. State-to-state probabilities and cross sections for H+ + H 2 (v = 0, j = 0,1) processes have been calculated for a collision energy, Ec, ranging between 10-6 eV and 0.1 eV. Differential cross sections (DCSs) for H+ + H2 (v = 0, j = 1) → H+ + H2 (v′ = 0, j′ = 0) for very low energies only start to develop a proper global minimum around the sideways scattering direction ( ≈ 90°) at Ec = 10-3 eV. Rate coefficients, a crucial information required for astrophysical models, are provided between 10…

Rotational excitation of mono- and doubly-deuterated water by hydrogen molecules

2011

Rate coefficients for rotational transitions in HDO and D2O induced by H2 collisions below 300 K are presented. Calculations have been performed at the close-coupling and coupledstates levels with the deuterated variants of the H2O–H2 interaction potential of Valiron et al. The HDO–H2 and D2O–H2 rate coefficients are compared to the corresponding rate coefficients for HDO–He and H2O–H2, respectively. Significant differences are observed. In particular the new HDO rate coefficients are found to be significantly larger (by up to three orders of magnitude) than the corresponding HDO–He rate coefficients. The impact of the new HDO rate coefficients is examined with the help of non-LTE radiative…

Spectroscopie Raman Anti-Stokes Cohérente femtoseconde (DRASC – fs) : expériences et modélisation dans le cas du mélange H2 – N2 à basse pression

2006

Dans l'objectif du diagnostic de la temperature dans les milieux en combustion, la Diffusion Raman Anti-Stokes Coherente resolue en temps (DRASC - fs) est utilisee pour sonder H 2 dans les melanges H 2 -N 2 a basse pression. Le dispositif DRASC mis en place est decrit en detail. Un nouveau modele de la reponse DRASC temporelle, prenant en compte tous les effets collisionnels specifiques a l'hydrogene (effets dits « de vitesse ») est presentee, ainsi que la comparaison avec l'experience, l'accord se revelant tres satisfaisant.