Physical Sciences and Mathematics Commons^™

Tetrakis(N-Ethyl-9-Oxo-4-Azonia-5-Aza-9h-Fluorene) Tetra-Μ3-Iodo-Hexa-Μ2-Iodo-Dodecaiodohexabismuthate, Meredith A. Tershany, Andrea M. Goforth, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

The new iodobismuthate compound (C₁₃H₁₁N₂O)₄[Bi₆I₂₂] has been synthesized solvothermally by reacting BiI₃, Zn(NO₃)₂·6H₂O and 4,5-diazafluoren-9-one in a water/ethanol solvent mixture. The asymmetric unit of the compound contains two independent [N-ethyl-4,5-dafo]⁺ cations and one-half of a centrosymmetric [Bi₆I₂₂]^4- anion. The average terminal Bi-I, Bi-₂-I and Bi-₃-I bond lengths in the anion are 2.8923 (2), 3.1403 (2) and 3.3022 (2) Å, respectively.

Tetrakis[2-(2-Pyridyl)Pyridinium] Tetra-Μ3-Iodo-Hexa-Μ2-Iodo-Dodecaiodohexabismuthate And Bis[Tris(2,2'-Bipyridine)Ruthenium(Ii)] Di-Μ4-Iodo-Octa-Μ2-Iodo-Dodecaiodohexabismuthate, Andrea M. Goforth, Meredith A. Tershansy, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

Crystals of the title compounds were grown solvothermally in an ethanol-water solvent mixture using ruthenium triiodide, 2,2'-bipyridine and bismuth triiodide as starting materials. Tetrakis[2-(2-pyridyl)pyridinium] tetra-₃-iodo-hexa-₂-iodo-dodecaiodohexabismuthate, (C₁₀H₉N₂)₄[Bi₆I₂₂], crystallizes in the triclinic space group P and is the major reaction product. The asymmetric unit of this compound consists of half a centrosymmetric [Bi₆I₂₂]^4- anion and two independent 2,2'-bipyridinium cations. The minor product of the reaction is bis[tris(2,2'-bipyridine)ruthenium(II)] di-₄-iodo-octa-₂-iodo-dodecaiodohexabismuthate, [Ru(C₁₀H₈N₂)₃] …

Semiclassical Nonadiabatic Dynamics Based On Quantum Trajectories For The O(3P,1D)+H2 System, Sophya Garashchuk, Vitaly A. Rassolov, George C. Schatz

Faculty Publications

The O(³P,¹D)+H₂→OH+H reaction is studied using trajectory dynamics within the approximate quantum potential approach. Calculations of the wave-packet reaction probabilities are performed for four coupled electronic states for total angular momentum J = 0 using a mixed coordinate/polar representation of the wave function. Semiclassical dynamics is based on a single set of trajectories evolving on an effective potential-energy surface and in the presence of the approximate quantum potential. Population functions associated with each trajectory are computed for each electronic state. The effective surface is a linear combination of the electronic states with the contributions …

Semiclassical Nonadiabatic Dynamics Using A Mixed Wave-Function Representation, Sophya Garashchuk, Vitaly A. Rassolov, George C. Schatz

Faculty Publications

Nonadiabatic effects in quantum dynamics are described using a mixed polar/coordinate space representation of the wave function. The polar part evolves on dynamically determined potential surfaces that have diabatic and adiabatic potentials as limiting cases of weak localized and strong extended diabatic couplings. The coordinate space part, generalized to a matrix form, describes transitions between the surfaces. Choice of the effective potentials for the polar part and partitioning of the wave function enables one to represent the total wave function in terms of smooth components that can be accurately propagated semiclassically using the approximate quantum potential and small basis sets. …

Catena-Poly[[Bis(Α-Thenoyltrifluoroacetonato)Copper(Ii)]-Μ-1,4-Di-4-Pyridyl-2,3-Diazabuta-1,3-Diene], William J. Perkins, Tamara Maxwell, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

In the one-dimensional title polymer, [Cu(C₈H₄F₃O₂S)₂(C₁₂H₁₀N₄)]_n or [Cu(L)₂(tta)₂] [tta is -thenoyltrifluoroacetonato and L is 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene], Cu²⁺ lies on a center of inversion. It is axially coordinated by two pyridyl N atoms from two different L ligands and equatorially coordinated by four O atoms from two chelating tta ligands. The ligand L propagates the one-dimensional chain structure by serving as a bridging ligand between two Cu octahedra via Cu-N coordinate bonds.

Tris(1,10-Phenanthroline)Cobalt(Ii) Triiodide, Meredith A. Tershany, Andrea M. Goforth, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

The asymmetric unit of the title compound, [Co(C₁₂H₈N₂)₃](I₃)₂, contains one [Co(1,10-phenanthroline)₃]²⁺ cation, half each of two centrosymmetric triiodide anions, and one complete triiodide anion. The title compound was synthesized solvothermally from Co(NO₃)₂, 1,10-phenanthroline, and SnI₂, where the SnI₂ reagent serves only as a source of I atoms.

Tris(Ethylenediamine)Cobalt(Iii) Nonaiododibismuthate, Andrea M. Goforth, Rachael E. Hipp, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

The asymmetric unit of the title compound, [Co(C₂H₈N₂)₃][Bi₂I₉], crystallizes in the orthorhombic space group Cmc2₁. The asymmetric unit contains half of a [Co(en)₃]³⁺ cation (en is ethylenediamine) and half of a [Bi₂I₉]^3- anion. Both species are located on mirror planes, requiring the [Co(en)₃]³⁺ cation to be present as a statistically disordered mixture of both enantiomeric forms. Crystals were grown solvothermally from an ethanol-water solvent mixture using rac-[Co(en)₃]I₃ and bismuth triiodide …

Sm2Nairo6, A Monoclinically Distorted Double Perovskite, Samuel J. Mugavero Iii, Irina V. Puzdrjakova, Mark D. Smith, Hans-Conrad Zur Loye

Faculty Publications

Single crystals of the lanthanide-containing iridate, disamarium sodium iridium hexaoxide, Sm₂NaIrO₆, were prepared via high-temperature flux growth and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2₁/n and is a double perovskite, consisting of a 1:1 ordered rock-salt-type lattice of corner-shared NaO₆ and IrO₆ distorted octahedra. Samarium occupies the eightfold coordination site generated by the connectivity of the octahedra.

Modified Quantum Trajectory Dynamics Using A Mixed Wave Function Representation, Sophya Garashchuk, Vitaly A. Rassolov

Faculty Publications

Dynamics of quantum trajectories provides an efficient framework for description of various quantum effects in large systems, but it is unstable near the wave function density nodes where the quantum potential becomes singular. A mixed coordinate space/polar representation of the wave function is used to circumvent this problem. The resulting modified trajectory dynamics associated with the polar representation is nonsingular and smooth. The interference structure and the nodes of the wave function density are described, in principle, exactly in the coordinate representation. The approximate version of this approach is consistent with the semiclassical linearized quantum force method [S. Garashchuk and …

Resonance-Enhanced Multiphoton Ionization For Real-Time Monitoring Of Trichloroethylene Formed By Degradation Of Tetrachloroethylene Using Zero-Valent Zinc, Kui Chen, Jack E. Pender, John L. Ferry, S. Michael Angel

Faculty Publications

Resonance-enhanced multiphoton ionization (REMPI) is investigated as a potential technique for real-time monitoring of selected volatile organochloride compounds (VOCs). In a proof-of-concept experiment, the progress of the reductive-degradation of tetrachloroethylene (PCE) to trichloroethylene (TCE) by zero-valent zinc was monitored by REMPI measurements performed in the headspace above the PCE solution. Two-photon resonant REMPI spectra of TCE and PCE were recorded over the wavelength range 305–320 nm. The concentrations of PCE and TCE in the headspace were monitored by measurement of the ionization signal with 315.64- and 310.48-nm excitation for PCE and TCE, respectively. Calibration curves yielded a linear range of …

Geminal Model Chemistry Ii. Perturbative Corrections, Vitaly A. Rassolov, Feng Xu, Sophya Garashchuk

Faculty Publications

We introduce and investigate a chemical model based on perturbative corrections to the product of singlet-type strongly orthogonal geminals wave function. Two specific points are addressed (i) Overall chemical accuracy of such a model with perturbative corrections at a leading order; (ii) Quality of strong orthogonality approximation of geminals in diverse chemical systems. We use the Epstein–Nesbet form of perturbation theory and show that its known shortcomings disappear when it is used with the reference Hamiltonian based on strongly orthogonal geminals. Application of this model to various chemical systems reveals that strongly orthogonal geminals are well suited for chemical models, …

Bohmian Dynamics On Subspaces Using Linearized Quantum Force, Vitaly A. Rassolov, Sophya Garashchuk

Faculty Publications

In the de Broglie–Bohm formulation of quantum mechanics the time-dependent Schrödinger equation is solved in terms of quantum trajectories evolving under the influence of quantum and classical potentials. For a practical implementation that scales favorably with system size and is accurate for semiclassical systems, we use approximate quantum potentials. Recently, we have shown that optimization of the nonclassical component of the momentum operator in terms of fitting functions leads to the energy-conserving approximate quantum potential. In particular, linear fitting functions give the exact time evolution of a Gaussian wave packet in a locally quadratic potential and can describe the dominant …

Energy Conserving Approximations To The Quantum Potential: Dynamics With Linearized Quantum Force, Sophya Garashchuk, Vitaly A. Rassolov

Faculty Publications

Solution of the Schrödinger equation within the de Broglie–Bohm formulation is based on propagation of trajectories in the presence of a nonlocal quantum potential. We present a new strategy for defining approximate quantum potentials within a restricted trial function by performing the optimal fit to the log-derivatives of the wave function density. This procedure results in the energy-conserving dynamics for a closed system. For one particular form of the trial function leading to the linear quantum force, the optimization problem is solved analytically in terms of the first and second moments of the weighted trajectory distribution. This approach gives exact …

Pyridoxamine Traps Intermediates In Lipid Peroxidation Reactions In Vivo: Evidence On The Role Of Lipids In Chemical Modification Of Protein And Development Of Diabetic Complications, Thomas O. Metz, Nathan L. Alderson, Mark E. Chachich, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Maillard or browning reactions between reducing sugars and protein lead to formation of advanced glycation end products (AGEs) and are thought to contribute to the pathogenesis of diabetic complications. AGE inhibitors such as aminoguanidine and pyridoxamine (PM) inhibit both the formation of AGEs and development of complications in animal models of diabetes. PM also inhibits the chemical modification of protein by advanced lipoxidation end products (ALEs) during lipid peroxidation reactions in vitro. We show here that several PM adducts, formed in incubations of PM with linoleate and arachidonate in vitro, are also excreted in the urine of PM-treated animals. The …

Bis[Μ-1,2-Bis(2-Pyridyl)Ethyne-K2N:N']Bis[Aquadinitratocadmium(Ii)], Badruz Zaman Md., Matthew J. Davis, Mark D. Smith, Hans Conrad Zur Loye

Faculty Publications

Two twisted 1,2-bis(2-pyridyl)ethyne ligands bridge two Cd²⁺ centers in the C₂-symmetric title complex, [Cd₂(NO₃)₄(-C₁₂H₈N₂)₂(H₂O)₂]. The bridging ligands arch across one another creating a `zigzag loop' molecular geometry. Two nitrate ions and a water molecule complete the irregular seven-coordinate Cd-atom environment. The dihedral angles between the equivalent pyridyl ring planes of the two independent ligands are 67.2 (1)°. O_water-HO_nitrate hydrogen bonding creates two-dimensional layers parallel to the ab plane.

Formula: [Cd₂(NO₃)₄(C …

Sr3Mgpto6, Mark D. Smith, Hans Conrad Zur Loye

Faculty Publications

Single crystals of the mixed alkaline earth platinate, tristrontium magnesium platinum hexaoxide, Sr₃MgPtO₆, were grown from a KOH flux at 1273 K. The compound adopts the rhombohedral K₄CdCl₆ structure type, featuring chains of face-shared, distorted MgO₆ trigonal prisms (Mg site symmetry 32) and PtO₆ octahedra (Pt site symmetry ) surrounded by columns of Sr²⁺ ions (Sr site symmetry 2).

Semiclassical Dynamics With Quantum Trajectories: Formulation And Comparison With The Semiclassical Initial Value Representation Propagator, Sophya Garashchuk, Vitaly A. Rassolov

Faculty Publications

We present a time-dependent semiclassical method based on quantum trajectories. Quantum-mechanical effects are described via the quantum potential computed from the wave function density approximated as a linear combination of Gaussian fitting functions. The number of the fitting functions determines the accuracy of the approximate quantum potential (AQP). One Gaussian fit reproduces time-evolution of a Gaussian wave packet in a parabolic potential. The limit of the large number of fitting Gaussians and trajectories gives the full quantum-mechanical result. The method is systematically improvable from classical to fully quantum. The fitting procedure is implemented as a gradient minimization. We also compare …

A Post-Amadori Inhibitor Pyridoxamine Also Inhibits Chemical Modification Of Proteins By Scavenging Carbonyl Intermediates Of Carbohydrate And Lipid Degradation, Paul A. Voziyan, Thomas O. Metz, John W. Baynes, Billy G. Hudson

Faculty Publications

Reactive carbonyl compounds are formed during autoxidation of carbohydrates and peroxidation of lipids. These compounds are intermediates in the formation of advanced glycation end products (AGE) and advanced lipoxidation end products (ALE) in tissue proteins during aging and in chronic disease. We studied the reaction of carbonyl compounds glyoxal (GO) and glycolaldehyde (GLA) with pyridoxamine (PM), a potent post-Amadori inhibitor of AGE formation in vitro and of development of renal and retinal pathology in diabetic animals. PM reacted rapidly with GO and GLA in neutral, aqueous buffer, forming a Schiff base intermediate that cyclized to a hemiaminal adduct by intramolecular …

“[Cu(Pyrazine-2-Carboxylate)2]2Cd4I8: Unprecedented 1-D Serpentine Chains And Regular 2-D Regular Metal-Organic Square Grids In A 3-D Framework., Delia M. Ciurtin, Mark D. Smith, Hans Conrad Zur Loye

Faculty Publications

A novel three-dimensional coordination polymer containing
an unprecedented one-dimensional serpentine motif conjoined
with a two-dimensional square grid motif is presented.

Three Unique Coordination Geometries Involving 1,2-Dimethoxy-4,5-Bis(2-Pyridylethynyl)Benzene, Jeffrey E. Fiscus, Sandra Shotwell, Ralph C. Layland, Mark D. Smith, Hans Conrad Zur Loye, Uwe H. F. Bunz

Faculty Publications

Reaction of the new ligand 1,2-dimethoxy-4,5-bis(2-pyridylethynyl) benzene with different metal centers under similar reaction conditions led to three distinct structure formation processes: molecular ring closure, dimerization, and polymer formation.

Ca4Iro6, Ca3Mgiro6 And Ca3Zniro6, Matthew J. Davis, Mark D. Smith, Hans Conrad Zur Loye

Faculty Publications

Single crystals of tetracalcium iridium hexaoxide, Ca₄IrO₆, tricalcium magnesium iridium hexaoxide, Ca₃MgIrO₆, and tricalcium zinc iridium hexaoxide, Ca₃ZnIrO₆, were prepared via high-temperature flux growth and structurally characterized by single-crystal X-ray diffraction. The three compounds are isostructural and adopt the K₄CdCl₆ structure type, comprised of chains of alternating face-shared [CaO₆], [MgO₆] or [ZnO₆] trigonal prisms and [IrO₆] octahedra, surrounded by columns of Ca²⁺ ions.

Formula: Ca₄IrO₆, Ca_3.34Mg_0.66IrO₆ and …

Two Different One-Dimensional Structural Motifs In The Same Coordination Polymer: A Novel Interpenetration Of Infinite Ladders By Bundles Of Infinite Chains, Badruz Zaman, Mark D. Smith, Hans Conrad Zur Loye

Faculty Publications

A coordination polymer with a novel structural motif
consisting of stacks of infinite ladders interpenetrated by
bundles of infinite chains is described; geometrical arguments
are made for the requirements that can lead to such
interpenetration as a function of ligand dimensions.

Crystal Growth, Structure Determination And Magnetism Of A New Hexagonal Rhodate: Ba9rh8o24, Katharine E. Stitzer, M. D. Smith, J. Darriet, Hans Conrad Zur Loye

Faculty Publications

Single crystals of Ba9Rh8O24, grown from a molten potassium carbonate flux, crystallize in the spacegroup R¯3c with lattice parameters of a = 10.0899(4) and c = 41.462(2) Å. Magnetic measurements on oriented single crystals reveal the existence of magnetic anisotropy

Sr3Znpto6 And Sr3Cdpto6, Mark D. Smith, Hans Conrad Zur Loye

Faculty Publications

The flux synthesis of single crystals of the isostructural compounds tristrontium zinc platinum hexaoxide, Sr₃ZnPtO₆, and tristrontium cadmium platinum hexaoxide, Sr₃CdPtO₆, is reported. The compounds adopt the pseudo-one-dimensional rhombohedral K₄CdCl₆ structure type, and feature chains of face-shared distorted ZnO₆ or CdO₆ trigonal prisms and PtO₆ octahedra, surrounded by columns of Sr²⁺ ions. All transition metals are located on the threefold axis of symmetry, while the Sr²⁺ cations lie on twofold axes.

Formula: Sr₃ZnPtO₆ and Sr₃CdPtO₆

Semiclassical Application Of The Mo”Ller Operators In Reactive Scattering, Sophya Garashchuk, John C. Light

Faculty Publications

Mo\ller operators in the formulation of reaction probabilities in terms of wave packet correlation functions allow us to define the wave packets in the interaction region rather than in the asymptotic region of the potential surface. We combine Mo\ller operators with the semiclassical propagator of Herman and Kluk. This does not involve further approximations and can be used with any initial value representation (IVR) semiclassical propagator. Time propagation in asymptotic regions of the potential due to Mo\ller operators reduces the oscillations of the propagator integrand and improves convergence of the results with respect to the number of trajectories. The effectiveness …

Structure Determination Of Ba8Corh6O21, A New Member Of The 2h-Perovskite Related Oxides, Hans Conrad Zur Loye, M. D. Smith, K. E. Stitzer, A. El Abed, J. Darriet

Faculty Publications

Single crystals of Ba₈CoRh₆O₂₁ were grown out of a potassium carbonate flux. The structure was solved by a general method using the superspace group approach. The superspace group employed was R3m(00γ)0s with a = 10.0431(1) Å, c₁ = 2.5946(1) Å and c₂ = 4.5405(1) Å, V = 226.60(1) ų. Ba₈CoRh₆O₂₁ represents the first example of an m = 5, n = 3 member of the A_3n+3mA'_nB_3m+nO_9m+6n family of 2H hexagonal perovskite related oxides and contains chains consisting of six …

Self-Assembly Of A Bis-Urea Macrocycle Into A Columnar Nanotube, Linda S. Shimizu, Mark D. Smith, A. D. Hughes, Ken D. Shimizu

Faculty Publications

A bis-urea macrocycle 1 was synthesized and shown to form extended nanotubular columns byX-ray crystallography.

Simplified Calculation Of The Stability Matrix For Semiclassical Propagation, Sophya Garashchuk, John C. Light

Faculty Publications

We present a simple method of calculation of the stability (monodromy) matrix that enters the widely used semiclassical propagator of Herman and Kluk and almost all other semiclassical propagators. The method is based on the unitarity of classical propagation and does not involve any approximations. The number of auxiliary differential equations per trajectory scales linearly rather than quadratically with the system size. Just the first derivatives of the potential surface are needed. The method is illustrated on the collinear H[sub 3] system.

Effect Of Collagen Turnover On The Accumulation Of Advanced Glycation End Products, Nicole Verzijl, Jeroen Degroot, Suzanne R. Thorpe, Ruud A. Bank, J. Nikki Shaw, Timothy J. Lyons, Johannes Wj Bijlsma, Floris Pjg Lafeber, John W. Baynes, Johan M. Tekoppele

Faculty Publications

Collagen molecules in articular cartilage have an exceptionally long lifetime, which makes them susceptible to the accumulation of advanced glycation end products (AGEs). In fact, in comparison to other collagen-rich tissues, articular cartilage contains relatively high amounts of the AGE pentosidine. To test the hypothesis that this higher AGE accumulation is primarily the result of the slow turnover of cartilage collagen, AGE levels in cartilage and skin collagen were compared with the degree of racemization of aspartic acid (% D-Asp, a measure of the residence time of a protein). AGE (Ne- (carboxymethyl)lysine, Ne-(carboxyethyl)lysine, and pentosidine) and % D-Asp concentrations increased …

Pyridoxamine, An Inhibitor Of Advanced Glycation Reactions, Also Inhibits Advanced Lipoxidation Reactions: Mechanism Of Action Of Pyridoxamine, Joelle M. Onorato, Alicia J. Jenkins, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Maillard or browning reactions lead to formation of advanced glycation end products (AGEs) on protein and contribute to the increase in chemical modification of proteins during aging and in diabetes. AGE inhibitors such as aminoguanidine and pyridoxamine (PM) have proven effective in animal model and clinical studies as inhibitors of AGE formation and development of diabetic complications. We report here that PM also inhibits the chemical modification of proteins during lipid peroxidation (lipoxidation) reactions in vitro, and we show that it traps reactive intermediates formed during lipid peroxidation. In reactions of arachidonate with the model protein RNase, PM prevented modification …