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Parameters of the EPR signals of monomeric dinitrosyl-iron complexes with 1H-1,2,4-triazole-3-thiol (DNIC-MT), obtained by treating MT+ferrous iron in DMSO solution with gaseous NO, have been compared with those of the crystalline monomeric DNIC-MT with tetrahedral structure. Dissolved DNIC-MT were characterized by the isotropic EPR signal centered at g=2.03 with half-width of 0.7 mT and quintet hyperfine structure when recorded at ambient temperature or the anisotropic EPR signal with g( perpendicular)=2.045, g( parallel)=2.014 from frozen solution at 77 kappa, Cyrillic. DNIC-MT in crystalline state showed the structure-less symmetrical singlet EPR signal centered at g=2.03 and half-width of 1.7 mT at both room and liquid nitrogen temperature. The Lorentz shape of this signal indicates the strong exchange interaction between these complexes in the DNIC-MT crystal. Being dissolved in DMSO the crystalline sample of DNIC-MT demonstrated the EPR signal typical for DNIC-MT, obtained by treating MT+ferrous iron in DMSO solution with gaseous NO. Low spin (S=1/2) d(9) electron configuration of DNIC-MT with tetrahedral structure (formula [(MT-S(.))(2)Fe(-1)(NO(+))(2)](+)) was suggested to be responsible for the signal of DNIC-MT in crystalline state. Dissolving of the crystals of DNIC-MT may result in the change of their spatial and electronic structure, namely, tetrahedral structure of the complexes characterized by low spin d(9) electronic configuration transforms into a plane-square structure with d(7) electronic configuration and low spin S=1/2 state (formula [(MT- S(-))(2)Fe(+)(NO(+))(2)](+)). The latter was suggested to be characteristic of other DNICs with various thiol-containing ligands in the solutions. The proposed mechanism of these DNICs formation from ferrous iron, thiol and NO shows that the process could be accompanied by the ionization of NO molecules to NO(+) and NO(-) ions in the complexes. Detailed analysis of the shape of the EPR signals of these complexes provided additional information about the exchange interaction typical for DNIC-MT in crystals.
The construction and basic performances of wavelength-dispersive soft-X-ray emission spectroscopy (SXES) devices attached to a transmission electron microscope were presented. An energy resolution of 0.23 eV was obtained at the aluminum L-emission energy. A Cu L-emission spectrum obtained showed four L-emission lines of Lalpha, Lbeta, Ll and Leta. Angle-resolved measurements of boron K-emission spectra of hexagonal-BN (h-BN) were presented. It clearly showed anisotropic emission intensity of the transition from pi-bonding state to 1s core hole. B K-emission spectra of h- and cubic-BNs showed a difference in energy positions of sigma-bonding peaks. An electron energy-loss spectrum of B K-edge and a B K-emission spectrum of cubic-BN were compared with a result of a LDA band calculation. It showed that high symmetry points in the band diagram appeared as peak and/or shoulder structures in those spectra. Interband transitions appeared in the imaginary part of the dielectric function of cubic-BN experimentally obtained were assigned in the band diagram. These results demonstrated a method to analyze the entire electronic structure of materials in the nanoscale using high energy-resolution spectroscopy methods based on transmission electron microscopy.
The cluster compounds KNa3In9 [K2Na6(In12)(In)6] and Na2In [(Na)8(In4)], which contain In12 icosahedra interbridged by 4-bonded In atoms and isolated In4 tetrahedra, respectively, both have classical closed-shell electronic configurations but show metallic transport properties. These contrasts have been studied by means of first-principles density functional methods (LMTO-ASA). Several bands cross the Fermi level in both compounds, consistent with their metallic properties. In KNa3In9, the metal atom framework alone is sufficient to generate a metallic characteristic. The alkali-metal s and indium p orbitals mix considerably in both phases, providing for substantial covalent contributions to their stabilities as well as bands crossing Ef. The participation of Na atoms in the 3D bonding networks is more striking in cation-richer Na2In than in KNa3In9.
State of the art CASSCF and CASPT2 calculations have been performed to elucidate the nature of the electronic transitions observed in the experimental spectrum of the octacyanomolybdate(V) cation. Assuming a triangular dodecahedral structure for this complex gives a convincing agreement between theory and experiment. All absorption bands are assigned to low-lying charge-transfer transitions involving excitations from ligand orbitals to 4dx2-y2. The calculated molecular orbitals reveal weak pi interactions between the metal and ligand orbitals, compared to much stronger sigma interactions. This calculated electronic structure substantiates the previous hypothesis concerning the giant spin ground states of magnetic clusters and networks containing Mo(CN)8(3-) as a constituent part.
The electronic and chemical structure of the interface between the amino acid L-cysteine and Au was determined by photoemission spectroscopy (PES). L-cysteine was deposited by repeatedly dipping Au substrates into solutions of L-cysteine in methanol with various concentrations. To enable repeat deposition without significant contamination, the dipping procedure was performed in a glovebox directly connected to the ultrahigh vacuum (UHV) chamber in a N2 atmosphere. X-ray photoemission spectroscopy (XPS) measurements between deposition steps allowed to characterize the chemical interaction at the interface to be characterized. Ultraviolet photoemission spectroscopy (UPS) measurements yielded the orbital line-up at the interface as well as the highest occupied molecular orbital (HOMO) structure of L-cysteine. The charge injection barrier between the L-cysteine HOMO and the Au Fermi level was found to be 3.0 eV. The interface dipole between the Au substrate and the L-cysteine overlayer was determined to be 1.03 eV. The results also indicate the formation of an interface state approximately 1.5 eV above the HOMO of the L-cysteine.
Paramagnetic NMR spectroscopy has been underutilized in the study of metalloproteins. One difficulty of the technique is that paramagnetic relaxation broadens signals from nuclei near paramagnetic centers. In systems with low electronic relaxation rates, this makes such signals difficult to observe or impossible to assign by traditional methods. We show how the challenges of detecting and assigning signals from nuclei near the metal center can be overcome through the combination of uniform and selective 2H, 13C, and 15N isotopic labeling with NMR experiments that utilize direct one-dimensional (2H, 13C, and 15N) and two-dimensional (13C-X) detection. We have developed methods for calculating NMR chemical shifts and relaxation rates by density functional theory (DFT) approaches. We use the correspondence between experimental NMR parameters and those calculated from structural models of iron-sulfur clusters derived from X-ray crystallography to validate the computational approach and to investigate how structural differences are manifested in these values. We have applied this strategy to three iron-sulfur proteins: Clostridium pasteurianum rubredoxin, Anabaena [2Fe-2S] ferredoxin, and human [2Fe-2S] ferredoxin. Provided that an accurate structural model of the iron-sulfur cluster and surrounding residues is available from diffraction data, our results show that DFT calculations can return NMR observables with excellent accuracy. This suggests that it might be possible to use calculations to refine structures or to generate structural models of active sites when crystal structures are unavailable. The approach has yielded insights into the electronic structures of these iron-sulfur proteins. In rubredoxin, the results show that substantial unpaired electron spin is delocalized across NH...S hydrogen bonds and that the reduction potential can be changed by 77 mV simply by altering the strength of one of these hydrogen bonds. In reduced [2Fe-2S] ferredoxins, hyperfine shift data have provided quantitative information on the degree of valence trapping. The approach described here for iron-sulfur proteins offers new avenues for detailed studies of these and other metalloprotein systems.
Two oxo-bis(benzene-1,2-dithiolato)chromate(V) complexes, namely, [CrO(L(Bu))2]1- and [CrO(L(Me))2]1-, have been synthesized and studied by UV-vis, EPR, magnetic circular dichroism (MCD), and X-ray absorption spectroscopy and by X-ray crystallography; their electro- and magnetochemistries are reported. H2L(Bu) represents the pro-ligand 3,5-di-tert-butylbenzene-1,2-dithiol, and H2L(Me) is the corresponding 4-methyl-benzene-1,2-dithiol. A structural feature of interest for both the complexes is the folding of the dithiolate ligands about the S-S vector providing Cs symmetry to the complexes. Geometry optimizations using all-electron density functional theory with scalar relativistic corrections at the second-order Douglas-Kroll-Hess (DKH2) and zeroth-order regular approximation (ZORA) levels result in excellent agreement with the experimentally determined structures and electronic and S K-edge X-ray absorption spectra. From DFT calculations, the Cs instead of C2v symmetry for the complexes is attributed to the strong S(3p) --> Cr(3d(x2-y2)) pi-donation in Cs geometry providing additional stability to the complexes.
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A joint experimental and theoretical work to explain the electronic and geometrical structure of an in situ prepared film of iron phthalocyanine (FePc) on silicon (100) is presented. FePc molecular films have been characterized by core and valence photoemission spectroscopy (PES) and x-ray absorption spectroscopy (XAS), and the results have been interpreted and simulated by density functional theory (DFT) calculations. C1s and N1s PE spectra have been analyzed by taking into account all chemically nonequivalent C and N atoms in the molecule. In the Fe2p(32) spectra it has been possible to resolve two components that can be related to the open shell structure of the molecule. By valence PES and N1s XAS data, the geometrical orientation of the FePc molecules in the film could be determined. Our results indicate that for the FePc on Si(100), the molecules within the film are mainly standing on the surface. The experimental N1s XAS spectra are very well reproduced by the theoretical calculations, which are both angle and atomic resolved, giving a detailed description of the electronic and geometric structure of the FePc film. Furthermore, the asymmetry and the intensity angle variation of the first N1s XAS threshold feature could be explained by the presented DFT calculations as due to the chemical nonequivalence of the N atoms and the symmetry character of the lowest unoccupied molecular orbital.
The geometry, electronic configurations, harmonic vibrational frequencies and stability of the structural isomers of Al(n)As(n) clusters (n=1-4) have been investigated using density functional theory. For dimers and trimers, the lowest energy structures are planar cumulenic rings (IIs, VIs) with D(nh) symmetry. The caged structure with T(d) symmetry (IXs) lie lowest in energy among the tetramers. The AlAs bond dominates the structures for many isomers so that one preferred dissociation channel is loss of the AlAs monomer. The atomic charges, hybridization and chemical bonding in the different structures are also discussed. Comparisons with valence-isoelectronic Si(2n), Al(n)P(n) and Ga(n)As(n) clusters of same size, the properties of the aluminum arsenide clusters are analogous to those of their corresponding Al(n)P(n), Si(2n) counterparts. The results can explain the modification and refinement of Si phase in AlSi alloy in the molecular level.
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The geometry, electronic configurations, harmonic vibrational frequencies, and stability of the structural isomers of aluminum phosphide clusters have been investigated using the density functional theory. For dimers and trimers, the lowest energy structures are cyclic (IIs, IIIs) with D(nh) symmetry. The caged structure with Td symmetry (Xs) lie lowest in energy among the tetramers. The Al--P bond dominates the structures for many isomers so that one preferred dissociation channel is loss of the AlP monomer. The hybridization and chemical bonding in the different structures are also discussed. Comparisons with silicon and boron nitride clusters, the ground state structures of Al(n)P(n) clusters are analogous to those of their corresponding Si(2n) counterparts. This similarity follows the isoelectronic principle.
New data are reported for the mass-spectrometry fragmentation patterns of helium clusters, either pure or containing a Ne or an Ar atom. The patterns for He(n)+ and Ar+He(n) show clear evidence of structure, while those of Ne+He(n) do not. To better understand the surprising result for the Ne+He(n) fragments, diffusion quantum Monte Carlo (DMC) calculations of the energies and structural properties of these ions were performed using a diatomics-in-molecule (DIM) parametrization of the potential energy. Using DIM for electronic energy evaluation allows us to sample 10(9) configurations even for a cluster as large as Ne+He14. The results of the DMC calculation are very surprising. For n > 7, the DMC random walkers rarely venture within 100 cm(-1) of the minimum potential energy. Analysis of the resulting particle density distributions shows that the zero-point energy does more than spread the wave function around the potential-energy minima, resulting in very diffuse wave functions. For some of the clusters the quantum effects nearly exclude the region of the potential minimum from the overall wave function. An important result of this effect is that the incremental bonding energy of the nth helium atom varies quite smoothly with n, for n > 5. This eliminates the expected shell structure and explains the lack of magic-number-type features in the data.
An atomic force microscope was used to locally perturb and detect the charge density in carbon nanotubes. Changing the tip voltage varied the Fermi level in the nanotube. The local charge density increased abruptly whenever the Fermi level was swept through a van Hove singularity in the density of states, thereby coupling the cantilever's mechanical oscillations to the nanotube's local electronic properties. By using our technique to measure the local band gap of an intratube quantum-well structure, created by a nonuniform uniaxial strain, we have estimated the nanotube chiral angle. Our technique does not require attached electrodes or a specialized substrate, yielding a unique high-resolution spectroscopic tool that facilitates the comparison between local electronic structure of nanomaterials and further transport, optical, or sensing experiments.
The three diamagnetic square planar complexes of nickel(II), palladium(II), and platinum(II) containing two S,S-coordinated 3,5-di-tert-butylbenzene-1,2-dithiolate ligands, (L(Bu))(2-), namely [M(II)(L(Bu))(2)](2-), have been synthesized. The corresponding paramagnetic monoanions [M(II)(L(Bu))(L(Bu)(*))](-) (S = (1)/(2)) and the neutral diamagnetic species [M(II)(L(Bu)(*))(2)] (M = Ni, Pd, Pt) have also been generated in solution or in the solid state as [N(n-Bu)(4)][M(II)(L(Bu))(L(Bu)(*))] salts. The corresponding complex [Cu(III)(L(Bu))(2)](-) has also been investigated. The complexes have been studied by UV-vis, IR, and EPR spectroscopy and by X-ray crystallography; their electro- and magnetochemistry is reported. The electron-transfer series [M(L(Bu))(2)](2-,-,0) is shown to be ligand based involving formally one (L(Bu)(*))(-) pi radical in the monoanion or two in the neutral species [M(II)(L(Bu)(*))(2)] (M = Ni, Pd, Pt). Geometry optimizations using all-electron density functional theory with scalar relativistic corrections at the second-order Douglas-Kroll-Hess (DKH2) and zeroth-order regular approximation (ZORA) levels result in excellent agreement with the experimentally determined structures and electronic spectra. For the three neutral species a detailed analysis of the orbital structures reveals that the species may best be described as containing two strongly antiferromagnetically interacting ligand radicals. Furthermore, multiconfigurational ab initio calculations using the spectroscopy oriented configuration interaction (SORCI) approach including the ZORA correction were carried out. The calculations predict the position of the intervalence charge-transfer band well. Chemical trends in the diradical characters deduced from the multiconfigurational singlet ground-state wave function along a series of metals and ligands were discussed.
A series of mononuclear square-based pyramidal complexes of iron containing two 1,2-diaryl-ethylene-1,2-dithiolate ligands in various oxidation levels has been synthesized. The reaction of the dinuclear species [Fe(III)2(1L*)2(1L)2]0, where (1L)2- is the closed shell di-(4-tert-butylphenyl)-1,2-ethylenedithiolate dianion and (1L*)1- is its one-electron-oxidized pi-radical monoanion, with [N(n-Bu)4]CN in toluene yields dark green crystals of mononuclear [N(n-Bu)4][Fe(II)(1L*)2(CN)] (1). The oxidation of 1 with ferrocenium hexafluorophosphate yields blue [Fe(III)(1L*)2(CN)] (1ox), and analogously, a reduction with [Cp2Co] yields [Cp2Co][N(n-Bu)4][Fe(II)(1L*)(1L)(CN)] (1red); oxidation of the neutral dimer with iodine gives [Fe(III)(1L*)2I] (2). The dimer reacts with the phosphite P(OCH3)3 to yield [Fe(II)(1L*)2{P(OCH3)3}] (3), and [Fe(III)2(3L*)2(3L)2] reacts with P(OC6H5)3 to give [Fe(II)(3L*)2{P(OC6H5)3}] (4), where (3L)2- represents 1,2-diphenyl-1,2-ethylenedithiolate(2-). Both 3 and 4 were electrochemically one-electron oxidized to the monocations 3ox and 4ox and reduced to the monoanions 3red and 4red. The structures of 1 and 4 have been determined by X-ray crystallography. All compounds have been studied by magnetic susceptibility measurements, X-band EPR, UV-vis, IR, and Mössbauer spectroscopies. The following five-coordinate chromophores have been identified: (a) [Fe(III)(L*)2X]n, X = CN-, I- (n = 0) (1ox, 2); X = P(OR)3 (n = 1+) )3ox, 4ox) with St = 1/2, SFe = 3/2; (b) [Fe(II)(L*)2X]n, X = CN-, (n = 1-) (1); X = P(OR)3 (n = 0) (3, 4) with St = SFe = 0; (c) [Fe(II)(L*)(L)X]n <--> [Fe(II)(L)(L*)X]n, X = CN- (n = 2-) (1red); X = P(OR)3 (n = 1-) (3red, 4red) with St = 1/2, SFe = 0 (or 1). Complex 1ox displays spin crossover behavior: St = 1/2 <--> St = 3/2 with intrinsic spin-state change SFe = 3/2 <--> SFe = 5/2. The electronic structures of 1 and 1(ox) have been established by density functional theoretical calculations: [Fe(II)(1L*)2(CN)]1- (SFe = 0, St = 0) and [Fe(III)(1L*)2(CN)]0 (SFe = 3/2, St = 1/2).