B3LYP/6-311CCG (3df,3pd) and CCSD (T)/6-311CCG (2d,2p) calculations show that the reaction of Li2O with CH4 can proceed by two distinct reaction channels, that is, channel A: Li2OCCH4/CH3LiCLiOH, and channel B: Li2OCCH4/CH3OHCLi2 (1SC). The former is predicted to be endothermic by about 111.1 kJ/mol with an energy barrier of 157.4 kJ/mol, and the latter endothermic by about 219.1kJ/mol with an energy barrier of 322.3kJ/mol. With the relatively lower energy required, the formation of CH3Li would be more feasible comparing to the formation of methanol with a rather higher energy barrier.

The reaction singlet potential energy curves of reactions Ni (d9s13D)+CH2 (3B1)→H2+ NiC and Ni (d9s13D) + CH2 (3B1)→trans-HNiCH, and the electronic and geometric structures and vibrational frequencies of all intermediates and transition states in the reactions above have been studied at B3LYP/6-311+ G (2d,2p) and B3LYP/6-311þþG (3df,2p) levels. The former reaction is predicted to be endothermic by about 32.9kJmol21, and the latter exothermic by about 65.9kJ mol21. At low energy levels, the formation of trans-HNiCH would be the dominant process, while at high energy levels, the formation of H2+ NiC would be the dominant process.

The singlet state potential energy curve of the reaction NI (d101S) +CH4→NICH2+H2, the electronic and geometric structures and vibrational frequencies of all intermediates and transition states in the reaction path were studied by B3LYP method. In the reaction, an atom-molecule complex NiCCH4acting as precursorin the breaking of C-H bond was predicted. For NiCH4, a frequency of 2988cm-1 is typical of methane molecularly adsorbed on Ni.Frequencies of 2531 and 2438cm-1are indicative of the formation ofa C-H...metal bond and a frequency of 355-1is typicalof Ni-CH4 stretching mode.A nickel hydrdo-methyl complex HniCH3is frmed upon the very low bamier in sertion of Ni0into a C-H bond of CH4. For HNiCH3,frequencies of 2980 and 2853cm-1 are representative of CH3 coadsorbed with H on Ni, and a frequency of 565cm-1 is indicative of the HNi-CH3 stretching mode. Adihydrogen complex of atom ni ckel carbene (H2) NiCH2 proceeds from the migration of a-hydrogen from carbon to metal with considerably large barrier,indicating that this is the rate-determining step in the whole spectively.Sybsequently, the whole reaction .For (H2) NiCH2, frequencies of 3344 and 694cm-1 are characteristic of H-H and (H2) NI-CH2 stretching modes respectively.Subsequently,the final products NiCH2 and H2 evolve after the elimination of H2 fron the transition-metal center.For NiCH2, a frequency of 754cm-1 is assigned to the Ni-Ch2 stretching mode. For all intermediates and transition states in the reaction path,the electron transfer is exclusively from nickel to carbon. Ingeneral, the overall reaction is mildly exothermic by1.6KJmol-1relative to Ni(d101S)+CH4reactants.

The interaction of CO and CO2 with nickel has been studied comparatively using the ab initio method. The results show that the carbon-oxygen bond is weakened when CO interacts with nickel, and the weakening is more obvious in the bridged adsorbed model than that in the linear one. The calculated vibrational frequencies are close to those found experimentally. Three interaction modes of CO2 with a Ni2 small cluster are found to be possible in which the most stable one has a bidentate structure, i.e. two oxygen atoms bonded to two adjacent nickel atoms, respectively. The weakening of the carbon-oxygen bond is more remarkable in the CO2 adsorbed model than in the CO adsorbed one. The Ni2 cluster structure suitable for CO2 is different from that for CO except that the Ni-Ni interatom distance in the CO bridged adsorbed species is significantly close to that in CO2 bidentate species.

The hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by Zn (II), Cu (II) and Co(II) complexes of imidazole groups have been investigated kinetically in the pH range 6.0-8.0 at the presence of three kinds of surfactants and 25.0±0.01℃, respectively. The results indicated that Zn (II) complex exhibit a great catalytic function in micellar solution with higher pH value, but when reactions were performed in weak acid solutions, Cu (II) complex catalyzed the hydrolysis of PNPP more efficiently than Zn (II) and Co (II) complexes did, which may be attributable to the different ionization states of the corresponding complexes in micellar media with different pH values and the different nucleophilic ability of active species in different complexes. In addition, these complexes showed more reactivity in zwitterionic (LSS) and nonionic (Brij35) micelles than that in cationic (CTAB) micelle, which may be explained by the electrostatic interaction between metal ions of these complexes and the head groups of surfactants or the substrate. The relative kinetic and thermodynamic parameters were obtained by kinetic analysis employing ternary complex model for metallomicellar catalysis.