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1.
Aarnts MP Wilms MP Peelen K Fraanje J Goubitz K Hartl F Stufkens DJ Baerends EJ Vlcek A 《Inorganic chemistry》1996,35(19):5468-5477
Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) ?, b = 13.902(3) ?, c = 19.643(2) ?, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) ?(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion. 相似文献
2.
Tatiana Murakhtina Jasper Heuft Evert Jan Meijer Daniel Sebastiani 《Chemphyschem》2006,7(12):2578-2584
A combined experimental and ab initio study is presented of the 1H NMR chemical shift distribution of aqueous hydrogen chloride solution as a function of acid concentration, based on Car-Parrinello molecular dynamics simulations and fully periodic NMR chemical-shift calculations. The agreement of computed and experimental spectra is very good. From first-principles calculations, we can show that the individual contributions of Eigen and Zundel ions, regular water molecules, and the chlorine solvation shell to the NMR line are very distinct and almost independent of the acid concentration. From the computed instantaneous NMR distributions, it is further possible to characterize the average variation in hydrogen-bond strength of the different complexes. 相似文献
3.
Klaseboer E Chevaillier JP Gourdon C Masbernat O 《Journal of colloid and interface science》2000,229(1):274-285
Experiments and modeling of the drainage of the thin liquid film between two deformable spherical drops approaching each other at constant velocity in another liquid are being presented. Two numerical models based on the lubrication theory have been developed considering the cases of immobile or mobile drop interfaces. The absolute film thickness and the thinning rate have been measured using laser interferometry for a wide range of capillary numbers. In all studied cases, the model with immobile interfaces was found to give the best predictions of the experimental time evolution of the film thickness and radial expansion. These results made it possible to derive a typical time scale of the drainage process. Copyright 2000 Academic Press. 相似文献
4.
Even systems in which strong electron correlation effects are present, such as the large near-degeneracy correlation in a
dissociating electron pair bond exemplified by stretched H2, are represented in the Kohn–Sham (KS) model of non-interacting electrons by a determinantal wavefunction built from the
KS molecular orbitals. As a contribution to the discussion on the status and meaning of the KS orbitals we investigate, for
the prototype system of H2 at large bond distance, and also for a one-dimensional molecular model, how the electron correlation effects show up in the
shape of the KS σ
g
orbital. KS orbitals φHL and φFCI obtained from the correlated Heitler-London and full configuration interaction wavefunctions are compared to the orbital
φLCAO, the traditional linear combination of atomic orbitals (LCAO) form of the (approximate) Hartree-Fock orbital. Electron correlation
manifests itself in an essentially non-LCAO structure of the KS orbitals φHL and φFCI around the bond midpoint, which shows up particularly clearly in the Laplacian of the KS orbital. There are corresponding
features in the kinetic energy density t
s
of the KS system (a well around the bond midpoint) and in the one-electron KS potential v
s
(a peak). The KS features are lacking in the Hartree-Fock orbital, in a minimal LCAO approximation as well as in the exact
one.
Received: 11 December 1996 / Accepted: 10 January 1997 相似文献
5.
Evert J. Ditzel Xavier L. R. Fontaine Norman N. Greenwood John D. Kennedy Mark Thornton-Pett 《无机化学与普通化学杂志》1992,616(10):79-85
The action of SMe2 on the ten-vertex nido-ruthenaborane [6-(η6-C6Me6)RuB9Hl3] ( 1 ) provides a high-yield route to the unsubstituted isocloso-ruthenaborane [1-(η6-C6Me6)RuB9H9] (2). The benzene analogue [1-(η6-C6Me6)RuB9H9] is prepared similarly. By contrast, reaction of (1) with PhNH2 gives a variety of B-phenylamino isocloso derivatives, including orange crystals of [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB 9 H8] ( 3 ), red-orange [1-(η6-C6Me6)-2,3-(PhNH)2-isocloso-1-RuB9H7] ( 4 ) and dark-red [1-(η6-C6Me6)-5,6,7-(PhNH)3-isocloso-1-RuB9H6] ( 5 ). Detailed 1H and 11B nmr properties of these various compounds are described. The structure of ( 3 ) has been established by a single-crystal X-ray diffraction study of the solvate [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB9H8] · 1/2 CH2Cl2; the crystals were monoclinic, space group C2/c, with a = 1895.1(3), b = 1556.6(3), c = 1716.4(3) pm, β = 104.37(1)° and z = 8. 相似文献
6.
Neugebauer J Louwerse MJ Belanzoni P Wesolowski TA Baerends EJ 《The Journal of chemical physics》2005,123(11):114101
In this study, we investigate the performance of the frozen-density embedding scheme within density-functional theory [J. Phys. Chem. 97, 8050 (1993)] to model the solvent effects on the electron-spin-resonance hyperfine coupling constants (hfcc's) of the H2NO molecule. The hfcc's for this molecule depend critically on the out-of-plane bending angle of the NO bond from the molecular plane. Therefore, solvent effects can have an influence on both the electronic structure for a given configuration of solute and solvent molecules and on the probability for different solute (plus solvent) structures compared to the gas phase. For an accurate modeling of dynamic effects in solution, we employ the Car-Parrinello molecular-dynamics (CPMD) approach. A first-principles-based Monte Carlo scheme is used for the gas-phase simulation, in order to avoid problems in the thermal equilibration for this small molecule. Calculations of small H2NO-water clusters show that microsolvation effects of water molecules due to hydrogen bonding can be reproduced by frozen-density embedding calculations. Even simple sum-of-molecular-densities approaches for the frozen density lead to good results. This allows us to include also bulk solvent effects by performing frozen-density calculations with many explicit water molecules for snapshots from the CPMD simulation. The electronic effect of the solvent at a given structure is reproduced by the frozen-density embedding. Dynamic structural effects in solution are found to be similar to the gas phase. But the small differences in the average structures still induce significant changes in the computed shifts due to the strong dependence of the hyperfine coupling constants on the out-of-plane bending angle. 相似文献
7.
Ensing B Buda F Gribnau MC Baerends EJ 《Journal of the American Chemical Society》2004,126(13):4355-4365
Previously, we have shown that the ferryl ion ([FeIVO]2+) is easily produced from Fenton's reagent (i.e., a mixture of Fe2+ ions and H2O2 in aqueous solution), using DFT and Car-Parrinello MD calculations. To verify that the ferryl ion can indeed act as the active species in oxidation reactions with Fenton's reagent, we study in the present paper the reactivity of the ferryl ion toward an organic substrate, in particular the oxidation of methane to methanol. In the first part of this paper, we perform static DFT calculations on the reaction of CH4 with the [(H2O)5FeIVO]2+ complex in vacuo that show a strong prevalence of the oxygen-rebound mechanism over the methane coordination mechanism. This is in agreement with the static DFT results for methane oxidation by biocatalysts MMO and P450, but not with those for methane oxidation by bare metal-oxo ions, where the methane coordination mechanism prevails. The highest energy barrier in the oxygen-rebound mechanism is only 3 kcal/mol in vacuo, whereas in the methane coordination mechanism the highest barrier is 23 kcal/mol. Overall the oxidation reaction energy is downhill by 47 kcal/mol. We conclude that the ferryl ion can indeed act as the oxidative intermediate in the Fenton oxidation of organic species. In the second part of this paper, we perform a preliminary assessment of solvent effects on the oxidation by the ferryl ion in aqueous solution using the method of constrained (first principles) molecular dynamics. The free energy barrier of the H-abstraction reaction from methane by the ferryl ion (i.e., the first step in the rebound mechanism) in aqueous solution is, with 22 kcal/mol in solution, significantly higher than in vacuo. Given the fact that methane has a relatively strong C-H bond (ca. 10 kcal/mol stronger than the C-H bonds in the more typical Fenton's reagent substrates), we infer that for many organic substrates oxidation with the ferryl ion as an active intermediate may be a perfectly viable route. 相似文献
8.
Bickelhaupt FM DeKock RL Baerends EJ 《Journal of the American Chemical Society》2002,124(7):1500-1505
Exceptionally short N [bond] F bond distances of only 1.217 A (crystal) and 1.246 A (gas phase) have been reported for N(2)F(+), making it the shortest N [bond] F bond ever observed. To trace the origin of this structural phenomenon, we have analyzed the model systems N(2)X(+), NF(3)X(+), and NH(3)X(+) (X [double bond] F, H) using generalized gradient approximation density functional theory at BP86/TZ2P. In good agreement with experiment, the computations yield an extremely short N [bond] F bond for N(2)F(+): we find N [bond] F bond distances in N(2)F(+), NF(4)(+), and NH(3)F(+) of 1.245, 1.339, and 1.375 A, respectively. The N [bond] X bonding mechanisms are quantitatively analyzed in the framework of Kohn-Sham MO theory. At variance with the current hypothesis, reduced steric and other Pauli repulsion (of substituents or lone pairs at N with F) rather than the extent of s [bond] p hybridization of N (i.e., sp versus sp(3)) are responsible for the much shorter N [bond] F distance in N(2)F(+) compared to NF(4)(+). The results for our nitrogen compounds are furthermore discussed in the more general context of how bond lengths are determined by both bonding and repulsive orbital interactions. 相似文献
9.
Robert van Leeuwen Oleg Gritsenko Evert Jan Baerends 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1995,33(4):229-238
In this work we analyze the exchange-correlation potentialv xc within the Kohn-Sham approach to density functional theory for the case of atomic systems. The exchange-correlation potential is written as the sum of two potentials. One of these potentialsv xc,scr is the long-range. Coulombic potential of the coupling constant integrated exchange-correlation hole which represents the screening of the two-particle interactions due to exchange-correlation effects. The other potentialv xc,scr resp contains the functional derivative with respect to the electron density of the coupling constant integrated pair-correlation function representing the sensitivity of this exchange-correlation screening to density variations. As explicit expression of the exchange-part of this functional derivative is derived using an approximation for the Greens function of the Kohn-Sham system and is shown to display a distinct atomic shell structure. The corresponding potentialv xc,scr resp has a clear step structure and is constant within the atomic shells and changes rapidly at the atomic shell boundaries. Numerical examples are presented for the Be and Kr atoms using the Optimized Potential Model (OPM). 相似文献
10.
Abstract Novel moni-β-lactams derived from esters of amino acids have been prepared in one step by the high pressure promoted [2 + 2] cycloaddition of enol ethers with isocyanates derived from esters of amino acids. The effect of substituents in the enol ether and in the isocyanate on the scope of the synthesis has been demonstrated. 相似文献