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PubMed2000

Electronic structure studies of oxomolybdenum tetrathiolate complexes: origin of reduction potential differences and relationship to cysteine-molybdenum bonding in sulfite oxidase.

Electronic absorption, magnetic circular dichroism, and resonance Raman spectroscopies have been used to determine the nature of oxomolybdenum-thiolate bonding in (PPh4)[MoO(SPh)4] (SPh = phenylthiolate) and (HNEt3)[MoO(SPh-PhS)2] (SPh-PhS = biphenyl-2,2'-dithiolate). These compounds, like all oxomolybdenum tetraarylthiolate complexes previously reported, display an intense low-energy charge-transfer feature that we have now shown to be comprised of multiple S-->Mo dxy transitions. The integrated intensity of this low-energy band in [MoO(SPh)4]- is approximately twice that of [MoO(SPh-PhS)2]-, implying a greater covalent reduction of the effective nuclear charge localized on the molybdenum ion of the former and a concomitant negative shift in the Mo(V)/Mo(IV) reduction potential brought about by the differential S-->Mo dxy charge donation. However, this is not observed experimentally; the Mo(V)/Mo(IV) reduction potential of [MoO(SPh)4]- is approximately 120 mV more positive than that of [MoO(SPh-PhS)2]- (-783 vs -900 mV). Additional electronic factors as well as structural reorganizational factors appear to play a role in these reduction potential differences. Density functional theory calculations indicate that the electronic contribution results from a greater sigma-mediated charge donation to unfilled higher energy molybdenum acceptor orbitals, and this is reflected in the increased energies of the [MoO(SPh-PhS)2]- ligand-to-metal charge-transfer transitions relative to those of [MoO(SPh)4]-. The degree of S-Mo dxy covalency is a function of the O identical to Mo-S-C dihedral angle, with increasing charge donation to Mo dxy and increasing charge-transfer intensity occurring as the dihedral angle decreases from 90 to 0 degree. These results have implications regarding the role of the coordinated cysteine residue in sulfite oxidase. Although the O identical to Mo-S-C dihedral angles are either approximately 59 or approximately 121 degrees in these oxomolybdenum tetraarylthiolate complexes, the crystal structure of the enzyme reveals an O identical to Mo-SCys-C angle of approximately 90 degrees. Thus, a significant reduction in SCys-Mo dxy covalency is anticipated in sulfite oxidase. This is postulated to preclude the direct involvement of coordinated cysteine in coupling the active site into efficient superexchange pathways for electron transfer, provided the O identical to Mo-SCys-C angle is not dynamic during the course of catalysis. Therefore, we propose that a primary role for coordinated cysteine in sulfite oxidase is to statically poise the reduced molybdenum center at more negative reduction potentials in order to thermodynamically facilitate electron transfer from Mo(IV) to the endogenous b-type heme.

Binding Sites↗
PubMed2005

Field emission patterns from first-principles electronic structures: application to pristine and cesium-doped carbon nanotubes.

A general approach is introduced to calculate field emission properties of any kind of nanostructure based on the first-principles local density of states (LDOS) and effective potentials. The experimental field emission spectroscopy images are explained as LDOS at the structure-vacuum barrier, weighted by the probability of electron tunneling. The method excellently reproduces the experimental field emission patterns of pristine capped carbon nanotubes. We show that cesium adsorbates even with a low doping ratio of one dopant per nanotube increase the emission current around 2.5 times, due to a generated dipole field.

Journal Article↗
PubMed2000

1,2-bis(pyridine-2-carboxamido)benzenate(2-), (bpb)2-: a noninnocent ligand. Syntheses, structures, and mechanisms of formation of [(n-Bu)4N][FeIV2(mu-N)(bpb)2(X)2] (X = CN-, N3-) and the electronic structures of [MIII(bpbox1)(CN)2] (M = Co, Fe).

The well-known tetradentate ligand 1,2-bis(pyridine-2-carboxamido)benzenate(2-), (bpb)2-, and its 4,5-dichloro analogue, (bpc)2-, are shown to be "noninnocent" ligands in the sense that in coordination compounds they can exist in their radical one- and diamagnetic two-electron-oxidized forms (bpbox1)- and (bpbox2)0 (and (bpcox1)- and (bpcox2)0), respectively. Photolysis of high-spin [(n-Bu)4N][FeIII(bpb)(N3)2] and its (bpc)2- analogue in acetone solution at room temperature generates the diamagnetic dinuclear complex [(n-Bu)4N][FeIV2(mu-N)(bpb)2(N3)2] and its (bpc)2- analogue; the corresponding cyano complex [(n-Bu)4N][FeIV2(mu-N)(bpb)2(CN)2] has been prepared via N3- substitution by CN-. Photolysis in frozen acetonitrile solution produces a low-spin ferric species (S = 1/2) which presumably is [FeIII(bpbox2)(N)(N3)]-, as has been established by EPR and Mössbauer spectroscopy. The mononuclear complexes [(n-Bu)4N][FeIII(bpb)(CN2)] (low spin), [Et4N][CoIII(bpb)(CN)2] and Na[CoIII(bpc)-(CN)2].3CH3OH can be electrochemically or chemically one-electron-oxidized to give [FeIII(bpbox1)(CN)2]0 (S = 0), [CoIII(bpbox1)(CN)2]0 (S = 1/2), and [CoIII(bpcox1)(CN)2]0 (S = 1/2). All complexes have been characterized by UV-vis, EPR, and Mössbauer spectroscopy, and their electro- and magnetochemistries have been studied. The crystal structures of [(n-Bu)4N][FeIII(bpb)(N3)2].1/2C6H6CH3, Na[FeIII(bpb)(CN)2], Na[CoIII(bpc)(CN)2].3CH3OH, [(n-Bu)4N][FeIV2(mu-N)(bpb)2(CN)2], and [(n-Bu)4N][FeIV2(mu-N)(bpb)(N3)2] have been determined by single-crystal X-ray diffraction.

Journal Article↗
PubMed2006

Jahn-Teller distortion geometries and electronic structures of Ga3Ge, GaGe3, and their ions.

Computational studies on the geometric, electronic, and spectroscopic properties of electronic states are presented for GaGe3, Ga3Ge, and their ions using the CASSCF and DFT(B3LYP)/CCSD(T)/QCISD(T) techniques. The optimized geometries of electronic states, vibrational frequencies, energy separations, Mulliken populations, ionization energies, electron affinities, binding energies are obtained. The anion photoelectron spectra of GaGe3- and Ga3Ge- are predicted. In addition, the results from the low-lying states of GaGe3 and Ga3Ge are compared with those of GaSi3 and Ga3Si. Results demonstrate that the equilibrium geometries of most electronic states of GaGe3, Ga3Ge, and their ions exhibit Jahn-Teller distortion. It is interesting to find that there is not charge transfer between Ga and Ge atoms upon an electron attachment to the ground states of GaGe3 and Ga3Ge, while the amount of charge transfer between Ga and Ge atoms significantly increases upon an electron ionization from the ground state of Ga3Ge.

Crystallography↗
PubMedDate not supplied

The electronic structures and properties of open-ended and capped carbon nanoneedles.

The existence of a family of very thin carbon needlelike nanostructures is predicted: the geometry and stability of several carbon nanoneedles (CNNs) formed by C4 and C6 units have been studied by quantum chemistry computational modeling methods. The structures of carbon nanoneedles are tighter than even the smallest single wall nanotubes (SWNTs) based on (4, 0) naphthacene. The electronic properties, energetic stability of geometrical structures with various terminal units are investigated. The relatively large band gaps, the strong bonding, and additional orbital interactions within the C4 rings and between the C4 layers make the H4(C4)(n)H4 type molecules nonmetallic. We have found indications that if the CNN (3, 0) structures are very long (in the limit of infinite-length), then they are likely to have semiconducting properties and could possibly be used as actual semiconductors. The studied families of CNNs can be considered as carbon nanostructures with unique structural and chemical properties and with possible potential for unusual electronic properties, with likely practical applications as nanomaterials and nanostructure devices.

Journal Article↗
PubMed2006

An exploration of electronic structure and nuclear dynamics in tropolone. I. The X 1A1 ground state.

The ground electronic state (X 1A1) of tropolone has been examined theoretically by exploiting extensive sets of basis functions [e.g., 6-311++G(d,p) and aug-cc-pVDZ] in conjunction with the high levels of electron correlation made possible by density functional (DFT/B3LYP), Moller-Plesset perturbation (MP2), and coupled-cluster [CCSD and CCSD(T)] methods. Unconstrained MP2 and CCSD optimization procedures performed with the reference 6-311++G(d,p) basis predict a slightly nonplanar equilibrium structure characterized by a small barrier to skeletal inversion (< or =10 cm(-1) magnitude). Complementary harmonic frequency analyses have shown this nonplanarity to be a computational artifact arising from adversely tuned carbon d-orbital exponents embodied in the standard definitions of several Pople-type basis sets. Correlation-consistent bases such as Dunning's aug-cc-pVDZ are less susceptible to these effects and were employed to confirm that the X 1A1 hypersurface supports a rigorously planar global minimum. The fully optimized geometries and vibrational force fields obtained by applying potent coupled-cluster schemes to the relaxed-equilibrium (Cs) and transition-state (C2v) conformers of tropolone afford a trenchant glimpse of the key features that mediate intramolecular hydron exchange in this model system. By incorporating perturbative triples corrections at the substantial CCSD(T) level of theory, an interoxygen distance of r(O...O)=2.528 A was determined for the minimum-energy configuration, with the accompanying proton-transfer reaction being hindered by a barrier of 2557.0 cm(-1) height. The potential energy landscape in tropolone, as well as the nature of the attendant hydron migration process, is discussed within the framework of the encompassing G4 molecular symmetry group.

Chemistry, Physical↗
PubMed2001

Electron spin resonance and electronic structure of vanadyl-porphyrin in heavy crude oils.

A study of vanadyl-porphyrin by electron spin resonance (ESR) was carried out looking for answers about the role that the central V=O ion plays when these kinds of molecules are present in heavy crude oils. The eigenvalues of the linear combination of atomic orbitals (LCAO) were obtained from the experimental values of g and parameters (ESR). The contributions to the molecular orbitals that describe the various energy levels of vanadyl ion were also obtained for the porphyrin species. The trends of the degree of covalent character of the metal-ligand bonds and the length of the vanadium-oxygen chemical bond are discussed. It is interesting to note that the Fermi contact term, K(eff), is essentially constant for all samples investigated, and it was found to be independent of the calculated electron delocalization (1 - delta(2)) and shows only little variation among the three different samples of oil. The orbital energies derived from our ESR study qualitatively agree with those predicted from MO theory for synthetic vanadyl-porphyrins.

Algorithms↗
PubMed1999

The Electronic Structure of CaCl: Calculation by R Matrix and Generalized Quantum Defect Theory.

The electronic spectrum of CaCl has been calculated using the variational eigenchannel R-matrix method combined with generalized multichannel quantum defect theory. The motion of the unpaired (Rydberg) electron is represented as a double scattering process on the closed-shell Ca(++) and Cl(-) core ions. Electron penetration into Ca(++) is taken into account as well as polarization effects. The partial saturation of the Cl(-) free-ion polarizability is evaluated on the basis of an ab initio calculation of the dipole and quadrupole moments of the CaCl(+) ion core. The calculations reproduce the effective principal quantum numbers nu of the experimentally known states (including the ground state) to within approximately 0.04. States with high-orbital angular momentum up to l = 6 are predicted. Copyright 1999 Academic Press.

Journal Article↗
PubMed2002

Classical description of electron structure near a positive ion.

A single positive ion is imbedded in an electron gas with overall charge neutrality. A classical statistical mechanics is considered using an electron-ion Coulomb potential regularized at distances within the de Broglie length. The electron charge density and electric field distribution at the ion are studied as a function of ion-electron coupling using molecular dynamics simulation and theoretical models. Agreement between theory and simulation is quite good in general, although differences are observed for very strong ion-electron coupling due to the enhanced importance of close electron-ion configurations.

Journal Article↗
PubMed2003

Electronic structure of linear thiophenolate-bridged heteronuclear complexes [LFeMFeL](n)(+) (M = Cr, Co, Fe; n = 1-3): a combination of kinetic exchange interaction and electron delocalization.

The electronic properties of the isostructural series of heterotrinuclear thiophenolate-bridged complexes of the general formula [LFeMFeL](n)(+) with M = Cr, Co and Fe where L represents the trianionic form of the ligand 1,4,7-tris(4-tertbutyl-2-mercaptobenzyl)-1,4,7-triazacyclononane, synthesized and investigated by a number of experimental techniques in the previous work(1), are subjected now to a theoretical analysis. The low-lying electronic excitations in these compounds are described within a minimal model supported by experiment and quantum chemistry calculations. It was found indeed that various experimental data concerning the magnetism and electron delocalization in the lowest states of all seven compounds are completely reproduced within a model which includes the electron transfer between magnetic orbitals at different metal centers and the electron repulsion in these orbitals (the Hubbard model). Moreover, due to the trigonal symmetry of the complexes, only the electron transfer between nondegenerate orbital, a(1), originating from the t(2g) shell of each metal ion in a pseudo-octahedral coordination, is relevant for the lowest states. An essential feature resulting from quantum chemistry calculations, allowing to explain the unusual magnetic properties of these compounds, is the surprisingly large value and, especially, the negative sign of the electron transfer between terminal iron ions, beta'. According to their electronic properties the series of complexes can be divided as follows: (1). The complexes [LFeFeFeL](3+) and [LFeCrFeL](3+) show localized valences in the ground electronic configuration. The strong antiferromagnetic exchange interaction and the resulting spin 1/2 of the ground-state arise from large values of the transfer parameters. (2). In the complex [LFeCrFeL](+), due to a higher energy of the magnetic orbital on the central Cr ion than on the terminal Fe ones, the spin 3/2 and the single unpaired a(1) electron are almost localized at the chromium center in the ground state. (3). The complex [LFeCoFeL](3+) has one ground electronic configuration in which two unpaired electrons are localized at terminal iron ions. The ground-state spin S = 1 arises from a kinetic mechanism involving the electron transfer between terminal iron ions as one of the steps. Such a mechanism, leading to a strong ferromagnetic interaction between distant spins, apparently has not been discussed before. (4). The complex [LFeFeFeL](2+) is characterized by both spin and charge degrees of freedom in the ground manifold. The stabilization of the total spin zero or one of the itinerant electrons depends on beta', i.e., corresponds to the observed S = 1 for its negative sign. This behavior does not fit into the double exchange model. (5). In [LFeCrFeL](2+) the delocalization of two itinerant holes in a(1) orbitals takes place over the magnetic core of chromium ion. Although the origin of the ground-state spin S = 2 is the spin dependent delocalization, the spectrum of the low-lying electronic states is again not of a double exchange type. (6). Finally, the complex [LFeCoFeL](2+) has the ground configuration corresponding to the electron delocalization between terminal iron atoms. The estimated magnitude of the corresponding electron transfer is smaller than the relaxation energy of the nuclear distortions induced by the electron localization at one of the centers, leading to vibronic valence trapping observed in this compound.

Journal Article↗
PubMed1999

o-, m-, and p-Carboranes and Their Anions: Ab Initio Calculations of Structures, Electron Affinities, and Acidities.

Ab initio geometry optimizations have been performed for o-, m-, and p-C(2)B(10)H(12) carborane cages and their mono- and dianions at the Hartree-Fock 3-21G, 6-31G, and 6-31G levels. The para-compound is the most stable with a calculated DeltaH(para-meta) value of -10 kJ/mol and a calculated DeltaG(975K)(para-meta) value of -3 kJ/mol. These small calculated energy differences disagree with the experimental heats of formation, which suggest DeltaH to be ca. -65 kJ/mol, but they agree with equilibrium gas mixture measurements at 975 K, which suggest a DeltaG value of ca. -1 kJ/mol. Electron distributions, electron affinities, and acidic properties of the carboranes are presented. The structures of the mono- and dianions were determined by optimization, starting from the three neutral carborane cages; we find three energy minima for the C(2)B(10)H(12)(2)(-) ion. The lowest-energy dianion is a nido-structure topped by a six-membered ring with the two C atoms in the meta position. The captured electrons become distributed over all the H atoms.

Journal Article↗