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1.
2.
Virve A. Karttunen Mikko Linnolahti Tapani A. Pakkanen Janne Maaranen Päivi Pitkänen 《Theoretical chemistry accounts》2007,118(5-6):899-913
The performance of quantum chemical methods for geometry prediction of hafnocenes was evaluated. HF, B3LYP and MP2 in combination
with nonrelativistic (MHF) and relativistic (MWB and LANL2DZ) basis sets for hafnium together with standard basis sets 3-21G*,
6-31G* and 6-311G** for other elements were applied. Five basic structural parameters of the optimized structures of the hafnocenes
were compared with experimental crystal structures obtained from the Cambridge structural database. Altogether 80 hafnocenes
were included in the analysis. The results show that relativistic corrections are necessary for Hf atom. However, even the
Hartree–Fock (HF) method, when combined with relativistic pseudopotentials, reproduces the experimental crystal structures
with significant accuracy. The good performance of the HF method can be understood to originate from the absence of significant
near-degeneracy correlations for hafnium. On average, the B3LYP and MP2 methods provide structural parameters somewhat closer
to the experimental ones. 相似文献
3.
Summary Translational symmetry has been shown to be useful in the calculation of electronic structures of large lattice models. The number of unique integrals has been derived for cases of different dimensionality. For the unique integrals zero screening and approximation methods are described. The method has been applied to arrays of hydrogen atoms and to a zincblende surface model. When the size of the system is increased the translationally unique integrals are shown to become either zero or they can be calculated by simple coulombic approximations. 相似文献
4.
Tuula T. Pakkanen Tapani A. Pakkanen Kimmo Smolander 《Journal of Molecular Structure》1987,162(3-4):313-320
The structures of two glycinohydroxamoto (GHA) complexes of Ni(II) and Co(III) have been determined by single-crystal X-ray diffraction methods. The crystals of Ni(GHA)2 are monoclinic with a = 5.360(1), b = 7.315(4), c = 10.194(4) Å, β = 96.57(3), Z = 2, and space group P21/c. The crystals of Co(GHA)3•1/2 H2O are monoclinic with a = 22.467(19), b = 8.041(4), c = 13.700(11) Å, β = 116.01(7), Z = 8, and space group C2/c. The values of the final residuals R for Ni(GHA)2 and Co(GHA)3•1/2 H2O are 0.0275 and 0.032, respectvely. The molecular structures of Ni(GHA)2 and Co(GHA)3 consist of a square planar and an octahedral coordination, respectively, with the glycinohydroxamato (NH2CH2CONOH−) ligands coordinating to the metal ion via the N (amino) and the N (NOH−). These two complexes are the first well-established cases of coordination of the NHO− group of a hydroxamic acid to a transition metal via the nitrogen atom. 相似文献
5.
6.
Koshevoy IO Grachova EV Tunik SP Haukka M Pakkanen TA Heaton BT Iggo JA Podkorytov IS 《Dalton transactions (Cambridge, England : 2003)》2004,(22):3893-3899
Two novel heterometallic octahedral clusters [Rh(4)Pt(2)(CO)(11)(dppm)(2)](1) and [Ru(2)Rh(2)Pt(2)(CO)(12)(dppm)(2)](2) were synthesized by the reaction of [Rh(2)Pt(2)(CO)(6)(dppm)(2)] with [Rh(6)(CO)(14)(NCMe)(2)] and Ru(3)(CO)(12), respectively. Solid state structures of 1 and 2 have been established by a single crystal X-ray diffraction study. Two dppm ligands in 1 are bonded to one platinum and three rhodium atoms, which form an equatorial plane of the Rh(4)Pt(2) octahedron. Two rhodium and two platinum atoms bound to the diphosphine ligands in 2 are nonplanar to give an octahedral C2 symmetric Ru(2)Rh(2)Pt(2)(dppm)2 framework. The (31)P NMR investigation of and (1D, (31)P COSY, (31)P-[(103)Rh] HMQC) and simulation of 1D spectral patterns showed that in both clusters the structures of the M(6)(PP)(2) fragments found in the solid state are maintained in solution. 相似文献
7.
Ligand substitution of the mixed-metal clusters FeRu2(CO)12 and Fe2Ru(CO)12 with triphenylphosphine and trimethylphosphite has been studied. Mono- and di-substituted derivatives have been synthesized and characterized structurally. The following crystal and molecular structures are reported: Fe2Ru(CO)11PPh3: triclinic, space group P, a 9.203(2), b 11.903(3), c 15.117(4) Å, α 81.54(2), β 87.28(2), γ 66.72(2)°, Z = 2; Fe2Ru(CO)11P(OMe)3: orthorhombic, space group Pna21, a 17.220(5), b 14.572(4), c 8.708(6) Å, Z = 4, FeRu2(CO)11PPh3: monoclinic, space group P21/n, a 11.435(3), b 16.034(5), c 16.642(4) Å, β 93.35(2)°, Z = 4; FeRu2(CO)10(PPh3)2: orthorhombic, space group Pccm, a 14.854(4), b 17.180(7), c 16.786(12) Å, Z = 4.Ligand substitution is found to occur preferentially at the ruthenium centers of the FeRu2 and Fe2Ru clusters. Monosubstitution causes expansion of both of the clusters while the overall geometry is practically unchanged. Disubstitution of FeRu2(CO)12 causes contraction of the cluster and leads to a formation of carbonyl bridges. The structural trends have been interpreted in terms of electronic and packing effects of ligand substitution. The X-ray structures of Fe2Ru(CO)12 and FeRu2(CO)12 are not known; the ligand substitution studies indicate that Fe2Ru(CO)12 has the same structure as Fe3(CO)12, and that FeRu3(CO)12 does not have a Ru3(CO)12 structure as postulated previously from the IR studies. 相似文献
8.
Hukkamäki J Suvanto S Suvanto M Pakkanen TT 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):10288-10295
Mesoporous high surface area MCM-41 and SBA-15 type silica materials with fibrous morphology were synthesized and used as support materials for the ALCVD (atomic layer chemical vapor deposition) preparation of Co/MCM-41 and Co/SBA-15 catalysts. Co/MCM-41 and Co/SBA-15 catalysts were prepared by deposition of Co2(CO)8 from the gas phase onto the surfaces of preheated support materials in a fluidized bed reactor. For both silica materials, two different kinds of preparation methods, direct deposition and a pulse deposition method, were used. Pure silica supports as well as supported cobalt catalysts were characterized by various spectroscopic (IR) and analytical (X-ray diffraction, Brunauer-Emmett-Teller, elemental analysis) methods. MCM-41 and SBA-15 fibers showed considerable ability to adsorb Co2(CO)8 from the gas phase. For MCM-41 and SBA-15 silicas, cobalt loadings of 13.7 and 12.1 wt % were obtained using the direct deposition method. The cobalt loadings increased to 23.0 and 20.7 wt % for MCM-41 and SBA-15 silicas, respectively, when the pulse deposition method was used. The reduction behavior of silica-supported cobalt catalysts was found to depend on the catalyst preparation method and on the mesoporous structure of the support material. Almost identical reduction properties of SBA-15-supported catalysts prepared by different deposition methods are explained by the structural properties of the mesoporous support and, in particular, by the chemical structure of the inner surfaces and walls of the mesopores. Pulse O2/H2 chemisorption experiments showed catalytically promising redox properties and surface stability of the prepared MCM-41- and SBA-15-supported cobalt catalysts. 相似文献
9.
We formulate a sufficient condition for the existence of a consistent price system (CPS), which is weaker than the conditional full support condition (CFS). We use the new condition to show the existence of CPSs for certain processes that fail to have the CFS property. In particular this condition gives sufficient conditions, under which a continuous function of a process with CFS admits a CPS, while the CFS property might be lost. 相似文献