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101.
1 INTRODUCTION The bimetallic nanoclusters are of standing inte- rest since they can exhibit catalytic, electronic and optical properties distinct from those of corre- sponding pure nanoclusters[1~4]. Palladium and pla- tinum, well known for their catalytic properties, are often used as the catalyst in different fuel cells[5~8]. Several experimental results illustrate that for the oxygen reduction reaction (ORR), which is one of the primary reactions taking place in many fuel cells and… 相似文献
102.
Efficient total syntheses of the herbertane sesquiterpene title compounds have been accomplished employing an Ireland ester Claisen rearrangement and ring-closing metathesis reaction sequence based strategy for the construction of two stereogenic vicinal quaternary carbon atoms on a cyclopentane. 相似文献
103.
The topology of the Ehrenfest force density revisited. A different perspective based on Slater‐type orbitals 下载免费PDF全文
Jan Dillen 《Journal of computational chemistry》2015,36(12):883-890
The topology of the Ehrenfest force density was studied with Slater‐type orbitals (STO). At larger distances from the nuclei, STOs generate similar artefacts as noticed before with Gaussian‐type orbitals. The topology of the Ehrenfest force density was found to be mainly homeomorphic with the topology of the electron density. For the first time, reliable integrations of several properties over force density atomic basins were performed successfully. Integration of the electron density of a number of hydrides, fluorides, and chlorides of first row elements over force density basins indicate substantial differences between the partial charges of the atoms as compared with those obtained from electron density basins. Calculations on saturated hydrocarbons confirm that the electronegativity of carbon atoms increases with increasing geometrical strain. Atomic interaction lines are observed to exist in the Ehrenfest force density between the hydrogen atoms of several so‐called “congested” molecules, and also in some inclusion complexes of alkanes with helium. However, interaction lines are lacking in several other controversial cases. © 2015 Wiley Periodicals, Inc. 相似文献
104.
Synthesis,Electrochemical and Luminescence Studies of Nickel and Vanadium Complexes Containing Tetradentate Schiff Base Ligand with N2O2 Donor Atoms 下载免费PDF全文
A symmetrical tetradentate Schiff base ligand was derived by the condensation of ortho‐vanillin and thiourea in 2:1 molar ratio and adjusted pH. Nickel and vanadyl complexes were obtained using the template method by the reaction of ortho‐vanillin and thiourea with Ni(OAc)2. 4H2O and VO(acac)2 (2:1:1 molar ratio) in absolute ethanol and adjusted pH. The Schiff base ligand and its complexes have been characterized by FT‐IR, 1H NMR, UV/Vis, elemental analysis and conductometry measurements. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metal to ligand stoichiometry and the molar conductance data revealed that the metal complexes were non‐electrolytes. The nickel and vanadyl complexes exhibited tetrahedral and square pyramidal coordination geometry, respectively. The emission spectra of the ligand and its complexes were studied in DMSO. Electrochemical properties of the ligand and its complexes were also investigated in the DMF solvent at the 150 mVs‐1 scan rate. The ligand and its complexes showed irreversible processes at this scan rate. 相似文献
105.
Yuko Ouchi Yasuhiro Morisaki Dr. Tomoki Ogoshi Dr. Yoshiki Chujo Prof. Dr. 《化学:亚洲杂志》2007,2(3):397-402
A reaction of the P‐chiral compound (S,S)‐1,2‐bis(boranato(tert‐butyl)methylphosphino)ethane with an azobenzene derivative gave stimuli‐responsive polymers with P‐chiral phosphines in the main chain. This is the first example of a stimuli‐responsive P‐chiral polymer. The polymer isomerized from the trans to the cis form upon UV irradiation and reverted to the trans form reversibly. The polymer was able to coordinate to platinum, and the resulting polymer complex exhibited the Cotton effect owing to the chirality of the phosphorus atoms. The structure of the P‐chiral polymer obtained could be changed reversibly by light and thermal stimuli, and the polymer chain was induced to rotate helically when complexed with transition metals through the chiral phosphorus atoms. 相似文献
106.
Nakanishi W Nakamoto T Hayashi S Sasamori T Tokitoh N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(1):255-268
To clarify the nature of five-center, six-electron (5c-6e) C(2)Z(2)O interactions, atoms-in-molecules (AIM) analysis has been applied to an anthraquinone, 1,8-(MeZ)(2)ATQ (1 (Z=Se), 2 (Z=S), and 3 (Z=O)), and a 9-methoxyanthracene system, 9-MeO-1,8-(MeZ)(2)ATC (4 (Z=Se), 5 (Z=S), and 6 (Z=O)), as well as 1-(MeZ)ATQ (7 (Z=Se), 8 (Z=S), and 9 (Z=O)) and 9-MeO-1-(MeZ)ATC (10 (Z=Se), 11 (Z=S), and 12 (Z=O)). The total electronic energy density (H(b)(r(c))) at the bond critical points (BCPs), an appropriate index for weak interactions, has been examined for 5c-6e C(2)Z(2)O and 3c-4e CZO interactions of the n(p)(O)sigma*(Z--C) type in 1-12. Some hydrogen-bonded adducts were also re-examined for convenience of comparison. The total electronic energy densities varied in the following order: OO (3: H(b)(r(c))=0.0028 au)=OO (6: 0.0028 au)>OO (9: 0.0025 au)> or =NNHF (0.0024 au)> or =OO (12: 0.0023 au)>H(2)OHOH (0.0015 au)>SO (8: 0.0013 au)=SO (2: 0.0013 au)> or =SO (11: 0.0012 au)=SO (5: 0.0012 au)>HFHF (0.0008 au)=SeO (10: 0.0008 au)=SeO (4: 0.0008 au)> or =SeO (1: 0.0007 au)> or =SeO (7: 0.0006 au)>HCNHF (-0.0013 au). H(b)(r(c)) values for SO were predicted to be smaller than the hydrogen bond of H(2)OHOH and H(b)(r(c)) values for SeO are very close to or slightly smaller than that for HFHF in both the ATQ and 9-MeOATC systems. In the case of Z=Se and S, H(b)(r(c)) values for 5c-6e C(2)Z(2)O interactions are essentially equal to those for 3c-4e CZO if Z is the same. The results demonstrate that two n(p)(O)sigma*(Z--C) 3c-4e interactions effectively connect through the central n(p)(O) orbital to form the extended hypervalent 5c-6e system of the sigma*(C--Z)n(p)(O)sigma*(Z--C) type for Z=Se and S in both systems. Natural bond orbital (NBO) analysis revealed that n(s)(O) also contributes to some extent. The electron charge densities at the BCPs, NBO analysis, and the total energies calculated for 1-12, together with the structural changes in the PhSe derivatives, support the above discussion. 相似文献
107.
Pina Romaniello 《Journal of fluorine chemistry》2004,125(2):145-149
The effect of fluorine atoms on the second-order optical nonlinear response of 4-nitro-4′-methoxy-trans-stilbene and polyene derivatives containing up to three double bonds (n=1, 2, 3) has been investigated within a semiempirical context (PM3 Hamiltonian). Experimental data reported in literature indicate a βvec(SHG) value of 34, 47 and 76 (×10−30 esu) for n=1, 2, 3, respectively, at 0.65 eV in CHCl3 solutions. Our calculations show that fluorinating the nitrophenyl group the βvec(SHG) is doubled. Further increase in the second-order nonlinear response can be obtained fluorinating the CC bond linkers between the aromatic moieties.Besides, the effect of different donor-acceptor pairs has been studied and the results interpreted in the two-state model context.Some results concerning the third-harmonic generation (THG), γ (THG), are presented, and a possible interpretation proposed. 相似文献
108.
Masaoki Oku Toetsu Shishido Takeshi Shinohara Qiang Sun Yoshiyuki Kawazoe Kazuo Nakajima Kazuaki Wagatsuma 《Journal of solid state chemistry》2004,177(2):457-460
The solid solutions of ScBRh3-ScRh3 and CeBRh3-CeRh3 are synthesized by the arc melting method, where RBRh3 and RRh3 (R=rare earth element) have perovskite and AuCu3 type structures, respectively. The binding energy of Sc 2p3/2 for ScBxRh3 increases with the boron concentration. The Knight shift of 45Sc observed by nuclear magnetic resonance spectroscopy decreases with increase of boron concentration. The decrement of the Knight shift corresponds the Sc 4s electron density at the Fermi level. The intensity ratio of f2: f1: f0 of Ce 3d XPS spectrum changes with boron concentration of CeBxRh3. It is concluded that in both cases of ScBxRh3 and CeBxRh3 the charge on the atoms on A-site changes with the concentration of the atoms on B-site, where the atoms are not directly bound. 相似文献
109.
Vanfleteren D Ghillemijn D Van Neck D Bultinck P Waroquier M Ayers PW 《Journal of computational chemistry》2011,32(16):3485-3496
For the Hirshfeld-I atom in the molecule (AIM) model, associated single-atom energies and interaction energies at the Hartree-Fock level are efficiently determined in one-electron Hilbert space. In contrast to most other approaches, the energy terms are fully consistent with the partitioning of the underlying one-electron density matrix (1DM). Starting from the Hirshfeld-I AIM model for the electron density, the molecular 1DM is partitioned with a previously introduced double-atom scheme (Vanfleteren et al., J Chem Phys 2010, 132, 164111). Single-atom density matrices are constructed from the atomic and bond contributions of the double-atom scheme. As the Hartree-Fock energy can be expressed solely in terms of the 1DM, the partitioning of the latter over the AIM naturally leads to a corresponding partitioning of the Hartree-Fock energy. When the size of the molecule or the molecular basis set does not grow too large, the method shows considerable computational advantages compared with other approaches that require cumbersome numerical integration of the molecular energy integrals weighted by atomic weight functions. 相似文献
110.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(9):667-673
After reporting the structure of a new polymorph of 1,3,5‐trifluoro‐2,4,6‐triiodobenzene (denoted BzF3I3 ), C6F3I3, (I), which crystallized in the space group P 21/c , we perform a comparative analysis with the already reported P 21/n polymorph, (II) [Reddy et al. (2006). Chem. Eur. J. 12 , 2222–2234]. In polymorph (II), type‐II I…I halogen bonds and I…π interactions connect molecules in such a way that a three‐dimensional structure is formed; however, the way in which molecules are connected in polymorph (I), through type‐II I…I halogen bonds and π–π interactions, gives rise to an exfoldable lamellar structure, which looks less tightly bound than that of (II). In agreement with this structural observation, both the melting point and the melting enthalpy of (I) are lower than those of (II). 相似文献