Deuterium enrichment of interstellar methanol explained by atom tunneling

We calculate, down to low temperature and for different isotopes, the reaction rate constants for the hydrogen abstraction reaction H + H(3)COH → H(2) + CH(2)OH/CH(3)O. These explain the known abundances of deuterated forms of methanol in interstellar clouds, where CH(2)DOH can be almost as abundant as CH(3)OH. For abstraction from both the C- and the O-end of methanol, the barrier-crossing motion involves the movement of light hydrogen atoms. Consequently, tunneling plays a dominant role already at relatively high temperature. Our implementation of harmonic quantum transition state theory with on the fly calculation of forces and energies accounts for these tunneling effects. The results are in good agreement with previous semiclassical and quantum dynamics calculations (down to 200 K) and experimental studies (down to 295 K). Here we extend the rate calculations down to lower temperature: 30 K for abstraction from the C-end of methanol and 80 K for abstraction from the OH-group. At all temperatures, abstraction from the C-end is preferred over abstraction from the O-end, more strongly so at lower temperature. Furthermore, the tunneling behavior strongly affects the kinetic isotope effects (KIEs). D + H(3)COH → HD + CH(2)OH has a lower vibrationally adiabatic barrier than H + H(3)COH → H(2) + CH(2)OH, giving rise to an inverse KIE (k(H)/k(D) < 1) at high temperature, in accordance with previous experiments and calculations. However, since tunneling is more facile for the light H atom, abstraction by H is favored over abstraction by D below ~135 K, with a KIE k(H)/k(D) of 11.2 at 30 K. The H + D(3)COD → HD + CD(2)OD reaction is calculated to be much slower than the D + H(3)COH → HD + CH(2)OH, in agreement with low-temperature solid-state experiments, which suggests the preference for H (as opposed to D) abstraction from the C-end of methanol to be the mechanism by which interstellar methanol is deuterium-enriched.     

Hydrogenation of CO on a silica surface: an embedded cluster approach

The sequential addition of H atoms to CO adsorbed on a siliceous edingtonite surface is studied with an embedded cluster approach, using density functional theory for the quantum mechanical (QM) cluster and a molecular force field for the molecular mechanical (MM) cluster. With this setup, calculated QM/MM adsorption energies are in agreement with previous calculations employing periodic boundary conditions. The catalytic effect of the siliceous edingtonite (100) surface on CO hydrogenation is assessed because of its relevance to astrochemistry. While adsorption of CO on a silanol group on the hydroxylated surface did not reduce the activation energy for the reaction with a H atom, a negatively charged defect on the surface is found to reduce the gas phase barriers for the hydrogenation of both CO and H2C=O. The embedded cluster approach is shown to be a useful and flexible tool for studying reactions on (semi-)ionic surfaces and specific defects thereon. The methodology presented here could easily be applied to study reactions on silica surfaces that are of relevance to other scientific areas, such as biotoxicity of silica dust and geochemistry.     

Structure and stability of the (001) alpha-quartz surface

The structure and surface energies of the cleaved, reconstructed, and fully hydroxylated (001) alpha-quartz surface of various thicknesses are investigated with periodic density functional theory (DFT). The properties of the cleaved and hydroxylated surface are reproduced with a slab thickness of 18 atomic layers, while a thicker 27-layer slab is necessary for the reconstructed surface. The performance of the hybrid DFT functional B3LYP, using an atomic basis set, is compared with the generalised gradient approximation, PBE, employing plane waves. Both methodologies give similar structures and surface energies for the cleaved and reconstructed surfaces, which validates studying these surfaces with hybrid DFT. However, there is a slight difference between the PBE and B3LYP approach for the geometry of the hydrogen bonded network on the hydroxylated surface. The PBE adsorption energy of CO on a surface silanol site is in good agreement with experimental values, suggesting that this method is more accurate for hydrogen bonded structures than B3LYP. New hybrid functionals, however, yield improved weak interactions. Since these functionals also give superior activation energies, we recommend applying the new functionals to contemporary issues involving the silica surface and adsorbates on this surface.     

Photodissociation of the phosphine-substituted transition metal carbonyl complexes Cr(CO)(5)L and Fe(CO)(4)L: a theoretical study

The photochemistry of the phosphine-substituted transition metal carbonyl complexes Cr(CO)(5)PH(3) and ax-Fe(CO)(4)PH(3) is studied with time-dependent DFT theory to explore the propensity of the excited molecules to expel their ligands. The influence of the PH(3) ligand on the properties of these complexes is compared with the photodissociation behavior of the binary carbonyl complexes Cr(CO)(6) and Fe(CO)(5). The lowest excited states of Cr(CO)(5)PH(3) are metal-to-ligand charge transfer (MLCT) states, of which the first three are repulsive for PH(3) but modestly bonding for the axial and equatorial CO ligands. The repulsive nature is due to mixing of the initial MLCT state with a ligand field (LF) state. A barrier is encountered along the dissociation coordinate if the avoided crossing between these states occurs beyond the equilibrium distance. This is the case for expulsion of CO but not for the PH(3) group as the avoided state crossing occurs within the equilibrium Cr-P distance. The lowest excited state of ax-Fe(CO)(4)PH(3) is a LF state that is repulsive for both PH(3) and the axial CO. Excited-state quantum dynamics calculations for this state show a branching ratio of 99 to 1 for expulsion of the axial phosphine ligand over an axial CO ligand. The nature of the phosphorus ligand in these Cr and Fe complexes is only of modest importance. Complexes containing the three-membered phosphirane or unsaturated phosphirene rings have dissociation curves for their lowest excited states that are similar to those having a PH(3) ligand. Analysis of their ground-state Cr-P bond properties in conjunction with frontier orbital arguments indicate these small heterocyclic groups to differ from the PH(3) group mainly by their enhanced sigma-donating ability. All calculations indicate that the excited Cr(CO)(5)L and Fe(CO)(4)L molecules (L = PH(3), PC(2)H(5), and PC(2)H(3)) prefer dissociation of their phosphorus substituent over that of an CO ligand. This suggests that the photochemical approach may be a viable complement to the ligand exchange and redox methods that are currently employed to demetalate transition metal complexed organophosphorus compounds.     

Consistent theoretical description of 1,3-dipolar cycloaddition reactions

The cycloaddition reactions of 18 1,3-dipolar molecules to ethylene and acetylene have been reinvestigated by quantum chemical methods that are based on a second-order perturbation treatment of electron correlation. It is found that SCS-MP2 and the new perturbative B2-PLYP density functional provide accurate reaction barriers and outperform MP2 as well as standard density functionals such as B3-LYP. The new second-order based methods have the additional advantage that they perform better with increasing quality of the one-particle space, as is desired for a good quantum chemical method. The errors for the reaction enthalpies are in general larger than for the barriers when compared to CBS-QB3 literature values, which is related to strong changes in the electronic structures, but the deviations are again smaller than with MP2 or B3-LYP and are also more systematic. The results of a detailed basis set study suggest that properly polarized triple-zeta AO basis sets represent a good compromise between accuracy and computational speed. The combination of very inaccurate density functionals with small (double-zeta) basis sets, which yields good results for the initial part of the reactions due to error compensation, is not recommended.