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PubMed2006

Electronic structure of iron(II)-porphyrin nitroxyl complexes: molecular mechanism of fungal nitric oxide reductase (P450nor).

Density functional calculations are employed to investigate key intermediates of the catalytic cycle of fungal nitric oxide reductase (P450nor). The formal Fe(II)-nitroxyl species Fe(II)--NO/(-) can principally exist in the two spin-states S = 0 and S = 1. In the S = 0 case, a very covalent Fe--NO sigma bond is present, which leads to an electronic structure description that is actually intermediate between Fe(I)--NO and Fe(II)--NO(-). In contrast, the S = 1 case shows a ferrous Fe(II)--NO complex with the extra electron being stored in the pi system of the porphyrin ligand. Importantly, the Fe(II)--NO/(-) species are very basic. The electronic structures and spectroscopic properties of the corresponding N- and O-protonated forms are very different, and unequivocally show that the Mb-HNO adduct (Mb-Myoglobin) prepared by farmer and coworkers is in fact N-protonated. The presence of an axial thiolate ligand enables a second protonation leading to the corresponding Fe(IV)--NHOH- species, which is identified with the catalytically active intermediate I of P450nor. This species reacts with a second molecule of NO by initial electron transfer from NO to Fe(IV) followed by addition of NO+ forming an N--N bond. This is accompanied by an energetically very favorable intramolecular proton transfer leading to the generation of a quite stable Fe(III)--N(OH)(NOH) complex. This way, the enzyme is able to produce dimerized HNO under very controlled conditions and to prevent loss of this ligand from Fe(III). The energetically disfavoured tautomer Fe(III)--N(OH2)(NO) is the catalytically productive species that spontaneously cleaves the N--OH2 bond forming N2O and H2O in a highly exergonic reaction.

Fungi↗
PubMed2002

Spectroscopic and electronic structure studies of the mu(4)-sulfide bridged tetranuclear Cu(Z) cluster in N(2)O reductase: molecular insight into the catalytic mechanism.

Spectroscopic methods combined with density functional calculations are used to develop a detailed bonding description of the mu(4)-sulfide bridged tetranuclear Cu(Z) cluster in N(2)O reductase. The ground state of Cu(Z) has the 1Cu(II)/3Cu(I) configuration. The single electron hole dominantly resides on one Cu atom (Cu(I)) and partially delocalizes onto a second Cu atom (Cu(II)) via a Cu(I)-S-Cu(II) sigma/sigma superexchange pathway which is manifested by a Cu(II) --> Cu(I) intervalence transfer transition in absorption. The observed excited-state spectral features of Cu(Z) are dominated by the S --> Cu(I) charge-transfer transitions and Cu(I) based d-d transitions. The intensity pattern of individual S --> Cu(I) charge-transfer transitions reflects different bonding interactions of the sulfur valence orbitals with the four Cu's in the Cu(Z) cluster, which are consistent with the individual Cu-S force constants obtained from a normal coordinate analysis of the Cu(Z) resonance Raman frequencies and profiles. The Cu(I) d orbital splitting pattern correlates with its distorted T-shaped ligand field geometry and accounts for the observed low g( parallel ) value of Cu(Z) in EPR. The dominantly localized electronic structure description of the Cu(Z) site results from interactions of Cu(II) with the two additional Cu's of the cluster (Cu(III)/Cu(IV)), where the Cu-Cu electrostatic interactions lead to hole localization with no metal-metal bonding. The substrate binding edge of Cu(Z) has a dominantly oxidized Cu(I) and a dominantly reduced Cu(IV). The electronic structure description of Cu(Z) provides a strategy to overcome the reaction barrier of N(2)O reduction at this Cu(I)/Cu(IV) edge by simultaneous two-electron transfer to N(2)O in a bridged binding mode. One electron can be donated directly from Cu(IV) and the other from Cu(II) through the Cu(II)-S-Cu(I) sigma/sigma superexchange pathway. A frontier orbital scheme provides molecular insight into the catalytic mechanism of N(2)O reduction by the Cu(Z) cluster.

Catalysis↗
PubMed2004

Synthesis and characterization of hypoelectronic rhenaboranes. Analysis of the geometric and electronic structures of species following neither borane nor metal cluster electron-counting paradigms.

The reaction of (CpReH(2))(2)B(4)H(4) with monoborane leads to the sequential formation of (CpRe)(2)B(n)()H(n)() (n = 7-10, 1-4). These species adopt closed deltahedra with the same total connectivities as the closo-borane anions [B(n)()H(n)()](2)(-), n = 9-12, but with flattened geometries rather than spherical shapes. These rhenaborane clusters are characterized by high metal coordination numbers, Re-Re cross-cluster distances within the Re-Re single bond range, and formal cluster electron counts three skeletal electron pairs short of that required for a canonical closo-structure of the same nuclearity. An open cluster, (CpReH)(2)B(7)H(9) (5), is isolated that bears the same structural relationship to arachno-B(9)H(15) as 1-4 bear to the closo-borane anions. Chloroborane permits the isolation of (CpReH)(2)B(5)Cl(5) (6), an isoelectronic chloro-analogue of known open (CpWH(2))(2)B(5)H(5) and (CpRe)(2)B(6)H(4)Cl(2) (7), a triple-decker complex containing a planar, six-membered 1,2-B(6)H(4)Cl(2) ring. Both are putative five- and six-boron intermediates in the formation of 1. Electronic structure calculations (extended Hückel and density functional theory) yield geometries in agreement with the structure determinations, large HOMO-LUMO gaps in accord with the high stabilities, and (11)B chemical shifts accurately reflecting the observed shifts. Analyses of the bonding in 1-4 reveal that the CpRe.CpRe interaction generates fragment orbitals that are able to contribute the "missing" three skeletal electron pairs required for skeletal bonding. The necessity of a Re.Re interaction for strong cluster bonding requires a borane fragment shape change to accommodate it, thereby explaining the noncanonical geometries. Application of the debor principle of borane chemistry to the shapes of 1-4 readily rationalizes the observed geometries of 5 and 6. This evidence of the scope of transition metal fragment control of borane geometry suggests the existence of a large class of metallaboranes with structures not found in known borane or metal clusters.

Journal Article↗
PubMed2000

Azido derivatives of low-valent group 14 elements: synthesis, characterization, and electronic structure of [(n-Pr)2ATI]GeN3 and [(n-Pr)2ATI]SnN3 featuring heterobicyclic 10-pi-electron ring systems.

Treatment of THF solutions of [(n-Pr)2ATI]MCl (where [(n-Pr)2ATI]- = N-(n-propyl)-2-(n-propylamino)troponiminate; M = Ge and Sn) with sodium azide affords the compounds [(n-Pr)2ATI]MN3 in excellent yield. X-ray analyses revealed that these Ge(II) and Sn(II) compounds feature linear azide moieties and planar heterobicyclic C7N2M ring systems. Germanium and tin atoms adopt a pyramidal geometry. IR spectra of [(n-Pr)2ATI]GeN3 and [(n-Pr)2ATI]SnN3 display a nu asym(N3) band at 2048 and 2039 cm-1, respectively. DFT calculations on the corresponding methyl-substituted species demonstrate that the geometrical and electronic structure of these two species are very similar, and the dominant canonical form of the metal-azide moiety is M-N-N identical to N. The tin system is, as expected, slightly more ionic. A comparative CASSCF/DFT study on the model system H-Sn-N3 illustrates that the DFT approach is viable for the calculation of the structures of these species.

Journal Article↗
PubMed2005

Molecular and electronic structure of square-planar nickel II, nickel III and nickel III pi-cation radical complexes with a tetradentate o-phenylenedioxamidate redox-active ligand.

The molecular and electronic structures of the electron transfer series of four-coordinate square-planar nickel complexes with the ligand o-phenylenebis(N'-methyloxamidate), [NiL]z (z = 2-, 1-, 0), have been evaluated by DFT and TDDFT calculations, and most of their experimentally available structural and spectroscopic properties (X. Ottenwaelder et al., Dalton Trans., 2005, DOI: 10.1039/b502478a) have been reasonably reproduced at the B3LYP level of theory. The anionic species [NiL]2- and [NiL]- are genuine low-spin nickel II and nickel III complexes with diamagnetic singlet (S = 0) and paramagnetic doublet (S = 1/2) states, respectively. The nickel III complex presents shorter Ni-N(amidate) bond distances (1.85-1.90 A) than the parent nickel II complex (1.88-1.93 A) and characteristic LMCT bands in the NIR region (lambda max = 794 and 829 nm) while the analogous MLCT bands for the nickel(II) complex are in the UV region (lambda max = 346 and 349 nm). The neutral species [NiL] is a nickel III o-benzosemiquinonediimine pi-cation radical complex with a diamagnetic singlet (S = 0) and a paramagnetic triplet (S = 1) states fairly close in energy but fundamentally different in orbital configuration. The singlet metal-radical ground state results from the antiferromagnetic coupling between the 3d(yz) orbital of the Ni III ion (S(M) = 1/2) and the pi(b) orbital of the benzosemiquinone-type radical ligand (S(L) = 1/2), which have a large overlap and thus strong covalent bonding. The triplet metal-radical excited state involves the ferromagnetic coupling between the Ni III 3d(zx) orbital and the benzosemiquinone-type pi(b) orbital, which are orthogonal to each other. The singlet and triplet states of the nickel III pi-cation radical complex possess characteristic quinoid-type short-long-short alternating sequence of C-C bonds in the benzene ring, as well as intense MLCT transitions in the VIS (lambda max = 664 nm) and NIR (lambda max = 884 nm) regions, respectively.

Cations↗
PubMed2006

Microscopic and electronic structure of semimetallic Sb and Semiconducting AlSb fabricated by nanoscale electrodeposition: An in situ scanning probe investigation.

The nanoscale electrocrystallization of pure Sb and the compound semiconductor AlSb on Au(111) has been studied by in situ scanning probe techniques (STM and STS) employing an ionic liquid electrolyte, {AlCl3-[C4mim]+Cl-} (1:1) containing SbCl3. The characteristic changes of the electronic structures with varying potentials have been probed for the first time by normalized differential conductance spectra, (dI/dU)/(I/U). In the underpotential deposition range of Sb the formation of two layers is observed. For the first monolayer a (square root 3 x square root 3)R30 degrees structure is determined from atomically resolved STM images. During the deposition and dissolution of the Sb monolayers characteristic wormlike or spinodal structures appear indicating surface alloying of antimony with the gold substrate. Under overpotential conditions two different Sb structures have been observed. If the deposition potential is continuously stepped to -0.1 V, Sb nanostripes form. On the other hand, randomly dispersed small clusters occur if the potential is jumped from 0.0 to -0.3 V vs Al/Al(III). Both modifications exhibit typical semimetallic behavior as shown by the STS spectra. At -1.1 V the cyclic voltammogram shows a clear reduction wave that is assigned to AlSb compound formation. Deposits in this potential range are characterized by a homogeneous distribution of clusters with diameters of approximately 20 nm. Conductance spectra of these clusters exhibit the main features of the electronic structure of the bulk semiconductor AlSb, with a band gap of 2.0 +/- 0.2 eV. Electrodeposition experiments on both sides of the compound deposition potential show a strong doping effect that is manifest in the corresponding conductance spectra.

Journal Article↗
PubMed2003

Spectroscopic and electronic structure studies of 2,3-dihydroxybiphenyl 1,2-dioxygenase: O2 reactivity of the non-heme ferrous site in extradiol dioxygenases.

The extradiol dioxygenase, 2,3-dihydroxybiphenyl 1,2-dioxygenase (DHBD, EC 1.13.11.39), has been studied using magnetic circular dichroism (MCD), variable-temperature variable-field (VTVH) MCD, X-ray absorption (XAS) pre-edge, and extended X-ray absorption fine structure (EXAFS) spectroscopies, which are analogous to methods used in earlier studies on the extradiol dioxygenase catechol 2,3-dioxygenase [Mabrouk et al. J. Am. Chem Soc. 1991, 113, 4053-4061]. For DHBD, the spectroscopic data can be correlated to the results of crystallography and with the results from density functional calculations to obtain detailed geometric and electronic structure descriptions of the resting and substrate (DHB) bound forms of the enzyme. The geometry of the active site of the resting enzyme, square pyramidal with a strong Fe-glutamate bond in the equatorial plane, localizes the redox active orbital in an orientation appropriate for O(2) binding. However, the O(2) reaction is not favorable, as it would produce a ferric superoxide intermediate with a weak Fe-O bond. Substrate binding leads to a new square pyramidal structure with the strong Fe-glutamate bond in the axial direction as indicated by a decrease in the (5)E(g) and increase in the (5)T(2g) splitting. Electronic structure calculations provide insight into the relative lack of dioxygen reactivity for the resting enzyme and its activation upon substrate binding.

Binding Sites↗
PubMed2000

Molecular and electronic structures of bis(pyridine-2,6-diimine)metal complexes [ML2](PF6)n (n = 0, 1, 2, 3; M = Mn, Fe, Co, Ni, Cu, Zn).

A series of mononuclear, octahedral first-row transition metal ion complexes mer-[M(II)L0(2)](PF6)2 containing the tridentate neutral ligand 2,6-bis[1-(4-methoxyphenylimino)ethyl]pyridine (L0) and a Mn(II), Fe(II), Co(II), Ni(II), Cu(II), or Zn(II) ion have been synthesized and characterized by X-ray crystallography. Cyclic voltammetry and controlled potential coulometry show that each dication (except those of Cu(II) and Zn(II)) can be reversibly one-electron-oxidized, yielding the respective trications [M(III)L0(2)]3+, and in addition, they can be reversibly reduced to the corresponding monocations [ML2]+ and the neutral species [ML2]0 by two successive one-electron processes. [MnL2]PF6 and [CoL2]PF6 have been isolated and characterized by X-ray crystallography; their electronic structures are described as [Mn(III)L1(2)]PF6 and [Co(I)L0(2)]PF6 where (L1)1- represents the one-electron-reduced radical form of L0. The electronic structures of the tri-, di-, and monocations and of the neutral species have been elucidated in detail by a combination of spectroscopies: UV-vis, NMR, X-band EPR, Mossbauer, temperature-dependent magnetochemistry. It is shown that pyridine-2,6-diimine ligands are noninnocent ligands that can be coordinated to transition metal ions as neutral L0 or, alternatively, as monoanionic radical (L1)1-. All trications are of the type [M(III)L0(2)]3+, and the dications are [M(II)L0(2)]2+. The monocations are described as [Mn(III)L1(2)]+ (S = 0), [Fe(II)L0L1]+ (S = 1/2), [Co(I)L0(2)]+ (S = 1), [Ni(I)L0(2)]+ (S = 1/2), [Cu(I)L0(2)]+ (S = 0), [Zn(II)L1L0]+ (S = 1/2) where the Mn(II) and Fe(II) ions are low-spin-configurated. The neutral species are described as [Mn(II)L1(2)]0, [Fe(II)L1(2)]0, [Co(I)L0L1]0, [Ni(I)L0L1]0, and [Zn(II)L1(2)]0; their electronic ground states have not been determined.

Journal Article↗
PubMed2001

Dual nature of the electronic structure of (La(2--x--y)Nd(y)Sr(x))CuO(4) and La(1.85)Sr(0.15)CuO(4).

High resolution angle-resolved photoemission measurements have been carried out on (La(1.4--x)-Nd(0.6)Sr(x))CuO(4), a model system with static one-dimensional (1D) charge ordering (stripe), and (La(1.85)-Sr(0.15))CuO(4), a high temperature superconductor (T(c) = 40 K) with possible dynamic stripes. In addition to the straight segments near ( pi,0) and ( 0,pi) antinodal regions, we have identified the existence of spectral weight along the [1,1] nodal direction in the electronic structure of both systems. This observation of nodal state, together with the straight segments near antinodal regions, reveals the dual nature of the electronic structure of stripes due to the competition of order and disorder.

Journal Article↗
PubMed1987

7,12-Dimethylbenz[a]anthracene: refined structure, electron density distribution and endo-peroxide structure.

The crystal structure of 7,12-dimethylbenz[a]anthracene (DMBA) has been refined from new X-ray diffraction data collected at low temperature (180 K). This has allowed the location of the hydrogen atom positions not previously reported in earlier structure determinations and refinements; a more precise molecular geometry is therefore now presented. In addition, an analysis of the electron density in this carcinogenic molecule has been made by multipole refinement. These two types of studies give information on the amount of strain in the bay region and the distribution of electron density in the molecule. The molecule is highly distorted in the bay region as a result of steric overcrowding between hydrogen atoms (minimum H ... H 2.06 A) so that torsion angles of 18 degrees and 22 degrees occur in this area. The bonds in the bay region and to the two methyl groups appear to be electron-rich; however, while the K-region of DMBA has a high pi-bond density computed from interatomic distances, the multipole analysis does not indicate that it is highly electron-rich. The 7- and 12-positions (equivalent to the 9- and 10-positions of anthracene) are highly reactive and appear to show a deficiency of electron density. Molecular dioxygen can add across these positions to give a peroxy compound. The crystal structure of such an endo-peroxide of DMBA has also been studied at 180 K although not to the high precision obtained for the parent compound. Some distortions are apparent in this molecule; in particular small CH3-C-O angles (101-104 degrees) are observed, indicative of some strain in the molecule. A computer graphics analysis of the diol epoxides of DMBA, generated from X-ray coordinates of DMBA and reported values for a diol epoxide of benzo[a]pyrene, show that steric overcrowding may affect the conformation of certain isomers of the diol epoxides.

9,10-Dimethyl-1,2-benzanthracene↗
PubMed1988

An electron nuclear double resonance investigation of redox-induced electronic structural change at CuA2+ in cytochrome c oxidase.

We measured an electronic change at cysteine ligand(s) of the CuA2+ center brought on by reduction of other metal centers within cytochrome c oxidase, notably cytochrome a. This change specifically manifested itself as a modification in magnetic hyperfine coupling to the beta-protons of the beta-carbons adjacent to the cysteine sulfur in the CuA2+ coordination sphere. The electron nuclear double resonance ENDOR signals of these beta-protons had previously been assigned through study of selectively deuterated yeast oxidase. In the present study the ENDOR signals of the CuA2+ center were compared from the following forms of oxidase: resting (a3+.CuA2+.a3+3.CuB2+); mixed valence, 2-electron-reduced CO-ligated oxidase (a3+.CuA2+.a2+3CO.CuB+), and a more completely reduced mixed-valence CO-ligated oxidase. In agreement with previous studies on 3-electron-reduced oxidase, the latter more completely reduced oxidase showed cytochrome a preferentially reduced with respect to CuA, implying that the majority of paramagnetic CuA2+ centers had reduced cytochrome a partners. The ENDOR-resolved splitting of the beta-proton hyperfine features substantially decreased in going from the first two more oxidized forms to the more fully reduced latter form. Thus, the electronic structure of the CuA2+ center specifically monitored by hyperfine couplings to cysteine protons changed in response to a reductive event elsewhere in the protein. This structural change may correlate with the anticooperative redox interaction recently reported between cytochrome a and CuA.

Animals↗
PubMed2004

High energy-resolution electron energy-loss spectroscopy study of the electronic structures of Li- and Mg-doped alpha-rhombohedral boron.

Electron-doped alpha-rhombohedral boron (alpha-r-B) crystals were synthesized by Li- and Mg-dopings. The doped alpha-r-B particles showed a shiny metallic colour, though non-doped alpha-r-B crystals showed a dark red colour (red boron). The electronic structures of doped alpha-r-B single crystals were examined by a high energy-resolution electron energy-loss spectroscopy microscope. Boron 1s electron-excitation spectra, which show the density of states of the conduction bands, of Li-doped alpha-r-B showed a chemical shift toward a smaller binding-energy side, indicating a charge transfer from the doped atoms to alpha-r-B. These spectra also showed a sharp intensity increase at the onset with a width of an energy resolution of the experiment. The sharp intensity increase may be assigned to a Fermi edge produced by the electron doping. The spectra of Mg-doped alpha-r-B showed a chemical shift indicating an electron doping, but did not show the presence of a Fermi edge.

Boron↗
PubMed1994

Molecular and electronic structures of two (anticonvulsant) diphenylhydantoin derivatives.

1-Benzyl-5,5-diphenyl-2,4-dioxo-3-imidazolidineacetic acid (AC), M(r) = 400.434, triclinic, P1, a = 8.7640 (3), b = 11.112 (1), c = 11.323 (2) A, alpha = 102.10 (2), beta = 95.44 (5), gamma = 109.12 (1)., V = 1002.65 (30) A3, Z = 2, Dx = 1.33 g cm-3, F(000) = 420, mu(Mo K alpha) = 0.852 cm-1, T = 293 K, R = 0.066 for 5551 unique observed reflections. The compound crystallizes from ethanol at room temperature in the form of colourless prism. 3-(2,4-Dichlorobenzyl)-5,5-diphenyl-2,4-dioxo-1-imidazolidineacetic++ + acid (AD), M(r) = 469.323, monoclinic, P2(1), a = 8.0399 (7), b = 9.7237 (6), c = 26.9768 (12) A, beta = 94.281 (4)., V = 2102.92 (96) A3, Z = 4, Dx = 1.48 g cm-3, F(000) = 968, mu(Mo K alpha) = 3.417 cm-1, T = 293 K, R = 0.066 for 5677 unique observed reflections. The compound crystallizes from ethanol at room temperature in the form of colourless prisms. Two approaches are employed in trying to understand the known differences in pharmacological activity: an analysis of the molecular geometries, and electronic structure calculations. A detailed analysis is made of the molecular geometries both from the X-ray diffraction results, and following energy minimization with molecular mechanics. The ab initio calculations employ the energy-minimized conformations. Several electronic properties are intercompared for AC, AD and their common parent molecule diphenylhydantoin (DPH). The analyses of geometry and electronic structure indicate dissimilarities between active and inactive compounds which may be linked to differences in the activity.

Anticonvulsants↗
PubMed2004

Electronic structures of exohedral lanthanide-C60 clusters.

We have studied the electronic structures of several gas phase exohedral lanthanide (Ln)-C(60) clusters, Ln(n)C(60) (Ln=Pr, Ho, Tb, Tm, Eu, and Yb) with n=1-4, by photoionization spectroscopy of the neutrals and photoelectron spectroscopy of their anions. Both of the spectroscopic analyses reveal that most of the Ln atoms preferably take +3 oxidation states, while Eu atoms alone assume +2 oxidation states, and that C(60) accepts up to twelve donated electrons in Ln(n)C(60). An additional photoionization examination of the oxygen atom mixing into the Ln(n)C(60) clusters demonstrated that each oxygen atom reduces two electrons from C(60). This result implies that the number of accepted electrons in C(60) can be varied by a suitable choice of the number of Ln atoms and O atoms.

Journal Article↗
PubMed2005

Theoretical description of the electronic structure of the alkali hydride cation NaH+.

A theoretical determination of the electronic structure of NaH+ is presented. Potential energy curves and dipole moments have been computed for 48(2)Lambda(+) electronic states (i.e., correlated adiabatically up to Na(6s) + H+) through a model-potential-type method over a wide range of R. Equilibrium distances, transition energies, depths of wells, and/or heights of humps predicted at short and large interatomic separations are reported and compared with available experimental and theoretical values. Variations of the static dipole polarizabilities versus internuclear distance have been determined for the two lowest states.

Journal Article↗
PubMed2005

Probing the electronic structure of [2Fe-2S] clusters with three coordinate iron sites by use of photoelectron spectroscopy.

Five series of [2Fe-2S] complexes, [Fe(2)S(2)Cl(2)(-)(x)(CN)(x)](-), [Fe(2)S(2)(SEt)(2)(-)(x)Cl(x)](-), [Fe(2)S(2)(SEt)(2)(-)(x)(CN)(x)](-), [Fe(2)S(2)Cl(2)(-)(x)(OAc)(x)](-) (OAc = acetate), and [Fe(2)S(2)(SEt)(2)(-)(x)(OPr)(x)](-) (OPr = propionate) (x = 0-2), were produced by collision-induced dissociation of the corresponding [4Fe-4S] complexes, and their electronic structures were studied by photoelectron spectroscopy. All the [2Fe-2S] complexes contain a [Fe(2)S(2)](+) core similar to that in reduced [2Fe] ferredoxins but with different coordination geometries. For the first three series, which only involve tricoordinated Fe sites, a linear relationship between the measured binding energies and the substitution number (x) was observed, revealing the independent ligand contributions to the total electron binding energies. The effect of the ligand increases in the order SEt --> Cl --> CN, conforming to their electron-withdrawing ability in the same order. The carboxylate ligands in the [Fe(2)S(2)Cl(2)(-)(x)(OAc)(x)](-) and [Fe(2)S(2)(SEt)(2)(-)(x)(OPr)(x)](-) complexes were observed to act as bidentate ligands, giving rise to tetracoordinated iron sites. This is different from their monodentate coordination behavior in the [4Fe-4S] cubane complexes, reflecting the high reactivity of the unsatisfied three-coordinate iron site in the [2Fe-2S] complexes. The [2Fe-2S] complexes with tetracoordinated iron sites exhibit lower electron binding energies, that is, higher reductive activity than the all tricoordinate planar clusters. The electronic structures of all the [2Fe-2S] complexes were shown to conform to the "inverted energy level scheme".

Electrons↗
PubMed2006

Interaction of diatomic germanium with lithium atoms: electronic structure and stability.

Quantum chemical calculations were applied to investigate the electronic structure of mono-, di-, and trilithiated digermanium (Ge2Lin) and their cations (n=0-3). Computations using a multiconfigurational quasidegenerate perturbation approach based on complete active space self-consistent-field wave functions, and density functional theory reveal that Ge2Li has a 2B1 ground state with a doublet-quartet energy gap of 33 kcal/mol. Ge2Li2 has a singlet ground state with a 3Au-1A1 gap of 29 kcal/mol, and Ge2Li3 a doublet ground state with a 4B2-2A2 separation of 22 kcal/mol. The cation Ge2Li+ has a 3B1 ground state, being 13 kcal/mol below the open-shell 1B1 state. The computed electron affinities for diatomic germanium are EA(1)=1.9 eV, EA(2)=-2.5 eV, and EA(3)=-6.0 eV, for Ge2-, Ge2 (2-), and Ge2 (3-), respectively, indicating that only the monoanion is stable with respect to electron detachment, in such a way that Ge2Li is composed by Ge2-Li+ ions. An "atoms-in-molecules" analysis shows the absence of a ring critical point in Ge(2)Li. An electron localization function analysis on Ge2Li supports the view that the Ge-Li bond is predominantly ionic; however, a small covalent character could be anticipated from the analysis of the Laplacian at the Ge-Li bond critical point. The ionic picture of the Ge-Li bond is further supported by a natural-bond-order analysis and the Laplacian of the electron density. The calculated Li affinity value for Ge2 is 2.08 eV, while the Li+ cation affinity value for Ge2- is 5.7 eV. The larger Li+ cation affinity value of Ge2- suggests a Ge2-Li+ interaction and thus supports the ionic nature of Ge-Li bond. In GeLi4 and Ge2Li, the presence of trisynaptic basins indicates a three-center bond connecting the germanium and lithium atoms.

Journal Article↗
PubMed2005

Structural, electronic, and bonding properties of zeolite Sn-beta: a periodic density functional theory study.

The structural, electronic, and the bonding properties of the zeolite Sn-beta (Sn-BEA) have been investigated by using the periodic density functional theory. Each of the nine different T-sites in BEA were substituted by Sn atoms and all the nine geometries were completely optimized by using the plane-wave basis set in conjunction with the ultra-soft pseudopotential. On the basis of the structural and the electronic properties, it has been demonstrated that the substitution of Sn atoms in the BEA framework is an endothermic process and hence the incorporation of Sn in the BEA is limited. The lowest unoccupied molecular orbitals (LUMO) energies have been used to characterize the Lewis acidity of each T-site. On the basis of the relative cohesive energy and the LUMO energy, the T2 site is shown to be the most favorable site for the substitution Sn atoms in the BEA framework.

Journal Article↗