Accurate dissociation energies were determined for gas-phase complexes between 1-naphthol and benzene, d₆-benzene and cyclohexane, using the stimulated emission pumping resonant two-photon ionization spectroscopy technique in supersonic jets. The dissociation energies obtained for the electronic ground state are surprisingly large being D₀ = 5.07±0.07 kcal/mol for 1-naphthol · benzene, 5.08±0.06 kcal/mol for 1-naphthol · d₆-benzene, and 6.92±0.03 kcal/mol for 1-naphthol · cyclohexane, respectively. The dissociation energies scale well with the parallel molecular polarizabilities.

Molecular modelling and site-directed mutagenesis were used to identify eleven amino acid residues which may be involved in antagonist binding of the human tachykinin NK1 receptor. Recombinant receptors were expressed in mammalian cells using the Semliki Forest virus system. Wild type and mutant receptors showed similar expression levels in BHK and CHO cells, verified by metabolic labelling. Binding affinities were determined for a variety of tachykinin NK1 receptor antagonists in SFV-infected CHO cells. The binding affinity for GR203040, CP 99,994 and CP 96,345 was significantly reduced by mutant Q165A. The mutant F268A significantly reduced the affinity for GR203040 and CP 99,994 and the mutant H197A had reduced affinity for CP 96,345. All antagonists seemed to bind in a similar region of the receptor, but do not all rely on the same binding site interactions. Functional coupling to G-proteins was assayed by intracellular Ca2+ release in SFV-infected CHO cells. The wild type receptor and all mutants except A162L and F268A responded to substance P stimulation.

The tetranuclear complexes {(μ₄-TCNX)[Ru(NH₃)₅]₄}(A)₈ and (μ₄-TCNX)[Mn(CO)₂(C₅Me₅)]₄ [A = PF₆ or CF₃SO₃; TCNX = TCNE (tetracyanoethene), TCNQ (7,7,8,8-tetracyano-p-quinodimethane), or TCNB (1,2,4,5-tetracyanobenzene)] were studied by variable-temperature (2−300 K) SQUID susceptometry. Mono- and dinuclear species [(PhCN)Ru(NH₃)₅](PF₆)₂ (PhCN = benzonitrile) and {(μ-L)[Ru(NH₃)₅]₂}(PF₆)₄ (L = 1,4-dicyanobenzene (terephthalodinitrile) or pyrazine) were also investigated for comparison and were found to be essentially diamagnetic. Despite the even electron count, both the ruthenium and manganese tetranuclear complexes are paramagnetic, albeit with different spin−spin exchange coupling patterns. The manganese systems are characterized by exchange-coupled S = 1 states at the individual metal centers, whereas the magnetic behavior of the tetranuclear ruthenium compounds results from an exchange-coupling interaction between two S = ¹/₂ sites, identified as Ru^III/Ru^II mixed-valence pairs.

A full configuration interaction study on the BH molecule is presented. The potential energy curves of 20 different electronic states have been calculated correlating the four valence electrons. On the two most important states, i.e. the X1Sigma+ and A1Pi states, a complete study has been performed. This includes the effect of core electron correlation, estimated via truncated configuration interaction techniques. The dissociation energy of the molecule in the two states and the height of the predissociative barrier in the A1Pi state have been determined with basis sets of increasing quality.

We present a method for the direct generation of the lists of strings, suited for integral-driven full-CI (FCI) algorithms. This method generates the string lists each time they are used, and hence sensibly reduces the memory requirements, compared to our previous method that precalculates the lists. It was also extended to permit a truncation of the string space, according to the level of excitation.

Polymeric two- and three-dimensional, homo- and heterometallic oxalatebridged coordination compounds offer exciting opportunities, mainly in the fields of molecular magnetism and photophysics. Given that a large variety of magnetic phenomena have been reported so far from these molecular magnets, very limited experience is gained from elastic neutron scattering experiments. Therefore, with two examples, we will address the topic of the elucidation of magnetic structures by means of the neutron scattering technique. In addition, due to the possibility of the variation of different metal ions in varying oxidation states, interesting photophysical processes can be observed within the extended three-dimensional host/guest systems.

We present results of a first-principles molecular-dynamics simulation of the vibrational spectrum of a model semiconductor surface where, close to the bulk melting temperature TM, the top bilayer becomes diffusive. The specific example chosen is Ge(111). In place of the ordinary surface vibrations, we obtain a spectrum more akin to that of a confined liquid. In particular, we predict a dramatic decrease in the intensity of high-frequency (bond-stretching) surface mode intensity, associated with a local melting-induced breaking of hard covalent bonds in the top bilayer.

It is shown that whereas the spherical and spheroidal jellium models are inadequate to describe lithium clusters, only the ellipsoidal jellium model is adequate. The corresponding result, obtained by Yannouleas and Landman, was unpublished at the time of submission of our paper.

IR spectra of anthracene and pyrene derivatives, serving as models for isolated, linear and isolated, compact PAHs, respectively, have been calculated using ab-initio quantum mechanical methods. The separate and combined effects of ionization and multiple dehydrogenation have been studied. This study confirms and refines the trends of our preliminary paper on the smallest possible PAH, naphthalene. If small PAHs are responsible for any UIR bands, they should be ionized and partially dehydrogenated, with a few triple bonds at the periphery of the carbon skeleton. In the appendix are given the complete IR spectra of all the isomers of the derivatives of anthracene and pyrene calculated for the purpose of this study. Tables I are for anthracene and Tables II for pyrene. Positions of the the missing hydrogens in the dehydrogenated species are referred as in Figures 1 and 2 of the original publication.

In orthorhombic Ba6Mg7F26, the Ba2+ ion can be partially replaced by Sr2+ to form a mixed, disordered compound. This new compound has a refined composition of Ba5.24 (4)Sr0.76 (4)Mg7F26. The volume decreases after the partial substitution from 1074.64 (10) to 1064.31 (11) Å3. The structure has two barium sites, Ba1 on Wyckoff site 8(l) with Cs symmetry and a coordination number of 12 + 1, and Ba2 on site 4(j) with C2v symmetry and a coordination number of 12; only the Ba2+ on site 4(j) is partially replaced by Sr2+. The distorted octahedral fluoride environment around magnesium shows a tendency to become more irregular in the Sr-substituted compound.

The crystal structures of cubic and tetragonal NiCr2O4 and of tetragonal CuCr2O4 have been refined and their cell parameters have been measured, using single-crystal and powder X-ray diffraction. It has been observed that the differences in the Jahn–Teller distortions in both compounds are reflected in their M2+ –O tetrahedral environments and in their cell parameters. A calculation of the atomic shifts during the tetragonal–cubic phase transition showed that the average shifts for the oxygen atoms are 0.10(1) and 0.04(1) Å for the nickel and chromium atoms, respectively. Crystals of both compounds jump when they go through the phase transition. This behaviour is especially spectacular for NiCr2O4 since the phase transition takes place at 320 K, this temperature being reached when the crystals are illuminated. A comparison with organic jumping crystals is presented, and characteristics of the chromite crystals are discussed.

In order to provide a possible explanation for the lack of detection of both HSiN and HNSi in the interstellar medium, an ab initio study of the Si+ + NH3 reaction is presented: it includes accurate energetic considerations and sketches dynamics discussions as well. It is unambiguously concluded that the X1A1 ground state of the SiNH2+ cation is the only exit channel of this reaction assuming interstellar conditions. The rotational and vibrational constants of this species are reported to stimulate its experimental and astrophysical searches. Upon dissociative recombination, it is likely that SiNH2+ can evolve toward HNSi: unfortunately, the dramatic weakness of the dipole moment of the latter species (0.05 D) makes it an unlikely candidate for today's radiotelescopes. At variance with HNSi, the high dipole moment value of HSiN (4.5 D) would make it a much more attractive candidate for astrophysical searches, but under interstellar conditions, we show that it can derive neither from the unimolecular HNSi ↔ HSiN equilibration nor from the Si+ + NH3, N + SiH3+ or N+ + SiH3 reactions as sometimes incorrectly stated in the astrophysical models that deduce interstellar silicon chemistry from that of carbon. Throughout this study, the very hazardous character of conclusions deduced from isoelectronic considerations should be considered as the leading feature: the finishing stroke to such isoelectronic analogies is given by our study of the H+ + HNSi ↔ HSiN + H+ reactions which leads to the conclusion that HSiN might be unlikely to survive interstellar hydrogenation processes.

A helium gas pressure cell for pressures up to 1 kbar (0.1 GPa) has been developed in conjunction with a closed-cycle He refrigerator allowing variable temperatures between 15 and 300 K. Both cell and refrigerator are equipped with optical windows suitable for photophysical measurements, such as temperature- and pressure-dependent absorption spectroscopy or laser flash photolysis. Examples of measurements on iron(II) spin-crossover systems are given. In these compounds, comparatively small external pressures induce significant changes in the thermodynamic equilibrium as well as in the relaxation dynamics.

The interaction of H2 with the Si(111)-(7 × 7) surface is investigated by means of density functional slab calculations on a (4 × 2) reconstructed model surface. A viable mechanism for β1 desorption is identified, which involves thermally activated SiH2 units at adatom sites. This mechanism leads to adsorption and desorption barriers of 1.0 and 2.4 eV, respectively, in agreement with experiment. An explanation for the two components observed in the β1 peak of temperature-programmed desorption spectra is proposed. The lattice deformation energy at the transition state for desorption is large (not, vert, similar0.6 eV). If we assume that this remains in the surface after H2 desorption, the low translational energy of desorbing molecules which has been observed experimentally can in part be explained.

A local density functional study of Si41O( Al31, H1)-substituted offretites is presented. Proton siting and dynamical properties are investigated within the First-Principles Molecular Dynamics method, using a periodically repeated unit cell. Results for monoaluminated offretites, e.g., with one Al per unit cell, show that the proton is located inside the channel of the zeolite, where it is accessible to incoming molecules for reaction. Calculated vibrational spectra of the framework, extracted from a dynamical simulation, reproduce experimental data well. The determined OH stretching frequencies show a rather weak dependence on the H1 position. A comparison of these frequencies with those of offretites containing three Al per unit cell does not indicate a significative chan

The crystal structure of the title compound, [Pd2Br2(C25H34P)2], a new binuclear phospha-alkene compound containing a trivalent P atom shows a centrosymmetric dimeric arrangement. The Pd2Br2 core is planar and adopts an irregular diamond shape. The coordination of the Pd atom is square planar. No stacking interactions were observed in the molecular packing.

An hybrid functional which includes a larger amount of pure exchange has been specially designed for the description of hydrogen-only systems. Both the H abstraction by H2 and the H2n + 1+ clusters have been investigated. Comparison with experimental values shows that the proposed functional gives dissociation energies and vibrational frequencies better than previous ab initio calculations. The results compare favorably with those obtained by a coupled clusters method [CCSD(T)], also performed in this work for sake of reference data.

Temperature-dependent Raman measurements between 190 and 358 K yield conformational enthalpy differences between 550 and 690 cal mol⁻¹ for racemic liquid 2-butanol. The conformational properties of 2-butanol were also studied using MM2 and MM3 calculations. The conformer 1, where C1 and C4 are in anti position, was found to be the most stable comformer with the MM3 calculations. Conformer 2, which has C1 and O5 in anti arrangement, has ca. 500 cal mol⁻¹ higher energy than 1. Comparisons of the calculated MM3 vibrational frequencies with the Raman spectra suggest that the most stable conformer in the liquid phase also adopts a Cl,C4 anti conformation.

The present investigation is concerned with the possible effects of material-related properties (molecular mass, glass transition and melting temperatures, crystallinity, tacticity) and particle-related properties (shape, size, specific surface area) on the compression characteristics of the chosen model polymer powder: poly(vinyl chloride) (PVC). Four grades were selected known in literature for providing compacts of varied mechanical strength. The compression characteristics were determined using an instrumented single-punch tableting machine. The differences in tableting characteristics could not be ascribed to any of the material-related properties, but a direct relationship was observed between the compact strength and the specific surface area of the particles, as measured by nitrogen adsorption. The compact hardness was thus only dependent on the inter- and the intraparticulate contact area, which in turn is dictated by the very peculiar morphology of the grains of the PVC powders, whether prepared by emulsion or suspension polymerization.

Based on a synthetic strategy, extended anionic, homo and bimetallic oxalato-bridged transition-metal compounds with two (2D) and three-dimensional (3D) connectivities can be synthesized and crystallized. Thereby, the choice of the templating counterions will determine the crystal chemistry. Since the oxalato bridge is a mediator for both antiferro and ferromagnetic interactions between similar and dissimilar metal ions, long-range magnetic ordering will occur. Examples of the determination of magnetic structures in 2D and 3D compounds by means of elastic neutron scattering methods will be discussed. In addition, due to the possibility of the variation of different metal ions in varying oxidation states, interesting photophysical processes can be observed within the extended three-dimensional host/guest systems.

A mechanism for SiCl2 formation and desorption in the etching of Si(100)-(2×1) at low chlorine coverages is analyzed using first-principles calculations. We find that the two monochlorinated Si atoms of a surface dimer can rearrange into a metastable SiCl2(a) adsorbed species plus a Cl-free Si atom. Desorption of SiCl2 occurs via a two-step mechanism, in which the adsorbed species is preliminarily stabilized by the diffusion away of the free Si atom. The energy barrier to form SiCl2(a) is lower on a dimer next to a dimer vacancy than in an undamaged region of the surface, consistent with recent STM observation of preferential linear growth of etch pits along dimer rows.

The growth of thin films made from Samarium-doped alkaline earth fluoro halides (AEFH) of composition SrxCa1−xFCl:Sm2+ (0 ⩽ x ⩽ 1) is presented and the possibilities are studied to increase significantly the inhomogeneous width of the Sm2+ optical zero phonon transitions. The best films were obtained when grown with a molecular beam deposition (MBD) method involving two separate molecular beams: one for the alkaline earth fluoride, the other one for the alkaline earth halide (Cl or Br). The results demonstrate that the double beam MBD technique employed is able to produce pure and mixed Matlockite films with targeted composition. The results of mainly optical studies of the samarium f–f transitions and of other complementary techniques are used to assess the composition and homogeneity of the films. With the aid of a model the composition dependence of the positions of specific optical f–f emission lines is established. Their inhomogeneous linewidth is compared with that of corresponding emission lines obtained from bulk samples of the same chemical composition. The linewidths of the films are only slightly larger ( ∼ 1.5–2 times). Thus, the film morphology cannot be exploited to increase substantially the inhomogeneous broadening of the luminescence lines. A novel approach to increase this broadening was devised, theoretically modeled and successfully tested by using multilayered sandwich-type thin films in conjunction with interdiffusion. Films with cation disorder of composition SrxCa1−xFCl (x = 0.5 /0/ 0.5/ 0/..) were grown. The 5D1→7F0 Sm2+ emission linewidth is thereby increased to 70 cm−1 full width half maximum. A width of 100cm−1 may be obtained within the composition range x = 0, x = 1. This represents an enhancement by a factor of 3–5 in comparison with the largest values obtained in appropriate mixed bulk AEFH of constant composition. A factor >50 is gained in comparison with pure bulk AEFH hosts. The room temperature (RT) homogeneous linewidths, on the other hand, are similar to those found in bulk mixed crystals of constant composition. The intrafilm host cation diffusion during film growth of the sandwich structures was further studied. A diffusion constant of 2⋅10−19m2s−1 for the Sr and Ca ions was deduced from this observation. These films are among the most promising materials for optical mass data storage through RT hole-burning.

Single crystal X-ray diffraction analysis was performed on crystals with composition Ba_{1 − δ}Sr_δMgF₄ (δ ≤ 0.55). The complete structure was analyzed for single domain crystals with nominal (refined) values of δ = 0.25 (0.27(2)) and 0.5 (0.55(2)). Interatomic distances vary in a characteristic manner, when smaller strontium ions replace the barium ions. Optical studies of Sm(II) doped samples show significant inhomogeneous line broadening and confirm the disorder On the Ba Site.

Laser flash photolysis experiments were performed on the mixed crystal [Zn_1−xFe_x(6-mepy)₃tren](PF₆)₂ (x=0.00025) at 10 K in the pressure range between 1 bar and 20 kbar. An external pressure of 20 kbar accelerates the low-temperature tunneling process by almost eight orders of magnitude.

Applicability of the approximate kinetic energy functionals to study hydrogen-bonded systems by means of the formalism of Kohn–Sham equations with constrained electron density (KSCED) [Cortona, Phys. Rev. B 44, 8454 (1991); Wesołowski and Warshel, J. Phys. Chem. 97, 8050 (1993); Wesołowski and Weber, Chem. Phys. Lett. 248, 71 (1996)] is analyzed. In the KSCED formalism, the ground-state energy of a molecular complex is obtained using a “divide-and-conquer” strategy, which is applied to the Kohn–Sham-like equations to obtain the electron density of a fragment embedded in a larger system. The approximate kinetic energy functional enters into the KSCED formalism in two ways. First, the effective potential in which the electrons of each fragment move contains a component which is expressed by means of a functional derivative of an approximate kinetic energy functional (functional derivative of the non-additive kinetic energy). Second, the KSCED energy functional contains a component (non-additive kinetic energy) which is expressed using the approximate kinetic energy functional. In this work, the KSCED energies and densities of (H₂O)₂, (HF)₂, (HCl)₂, and HFNCH are compared to the ones obtained using the standard supermolecule Kohn–Sham approach. The following factors determining the agreement between the KSCED and supermolecule Kohn–Sham results are analyzed: the analytical form of the gradient-dependent terms in the approximate kinetic energy functional and the number of atom-centered orbitals used to expand electron density of fragments. The best agreement between the supermolecule Kohn–Sham and the KSCED results is obtained with the kinetic energy functional derived following the route of Lee, Lee, and Parr [Lee et al., Phys. Rev. A 44, 768 (1991)] from the exchange functional of Perdew and Wang [Perdew and Wang, in Electronic Structure of Solids ’91, edited by P. E. Ziesche and H. Eschrig (Academie Verlag, Berlin, 1991), p. 11]. The difference between the KSCED and the supermolecule Kohn–Sham energies of studied complexes amounts to less than 0.35 kcal/mol at the equilibrium geometry.

The edge-bridged tetrahedral geometry of five-coordinate d0 complexes [MD2L3] with strong π-donors D is analyzed with extended Hückel methodology as well as density functional theory. It is shown that this geometry, also encountered in bent metallocene systems [MCp2L3], can be considered as a distortion of a regular trigonal bipyramid arising from a second-order Jahn−Teller distortion of e‘ symmetry (in D3h) and corresponds to a deformation along a reversed-Berry pathway. This model was tested with a structure-correlation analysis of all experimentally determined [MD2L3] structures, thus allowing a mapping of the reversed-Berry pathway. The catalytic potential of these complexes and their isolobal relationship to [MCp2L3] are emphasized.

The hexaaqua complex of ruthenium(II) represents an ideal starting material for the synthesis of isostructural compounds with a [Ru(H2O-ax)(H2O-eq)4L]2+ general formula. We have studied a series of complexes, where L = H2O, MeCN, Me2SO, H2CCH2, CO, and F2CCH2. We have evaluated the effect of L on the cyclic voltammetric response, on the rate and mechanism of exchange reaction of the water molecules, and on the structures calculated with the density functional theory (DFT). As expected, the formal redox potential, E°‘(+2/+3), increases with the π-accepting capabilities of the ligands. For L = N2, the oxidation to Ru(III) is followed by a fast substitution of dinitrogen by a solvent molecule, revealing the poor stability of the Ru(III)−N2 bond. The water exchange reactions have been followed by 17O NMR spectroscopy. The variable-pressure and variable-temperature kinetic studies made on selected examples are all in accordance with a dissociative activation mode for exchange. The positive activation volumes obtained for the axial and equatorial water exchange reactions on [Ru(H2O)5(H2CCH2)]2+ (ΔVax and ΔVeq = +6.5 ± 0.5 and +6.1 ± 0.2 cm3 mol-1) are the strongest evidence of this conclusion. The increasing cis-effect series was established according to the lability of the equatorial water molecules and is as follows: F2CCH2 CO < Me2SO < N2 < H2CCH2 < MeCN < H2O. The increase of the lability is accompanied by a decrease of the E°‘ values, but no change was found in the calculated Ru−H2Oeq bond lengths. The increasing trans-effect series, established from the lability of the axial water molecule, is the following: N2 MeCN < H2O < CO < Me2SO < H2CCH2 < F2CCH2. A variation of the Ru−H2Oax bond lengths is observed in the calculated structures. However, the best correlation is found between the lability and the calculated Ru−H2Oax bond energies. It appears, also, that a decrease of the electronic density along the Ru−Oax bond and the increase of the lability can be related to an increase of the π-accepting capability of the ligand. For L = N2, the calculations have shown that the Ru(II)−N2 bond is weak. Consequently, the water exchange reaction proceeds through a different mechanism, where first the N2 ligand is substituted by one water molecule to produce the hexaaqua complex of Ru(II). The water exchange takes place on this compound before re-formation of the [Ru(H2O)5N2]2+ complex.

As recently reported by Klopper and Lüthi, there is a discrepancy between experiment and high-level quantum chemical calculations as to the value of the heterolytic metal–ligand bond disruption enthalpy of ferrocene. Indeed their ab initio calculations lead to a best estimate of 655 kcal/mol, whereas the experimental value is 635 kcal/mol. We report here results obtained using density functional theory. In addition to ferrocene, other metallocenes such as vanadocene, manganocene, nickelocene and ruthenocene, have also been investigated. Gradient-based corrections are crucial for a quantitative description of bond dissociation, our best estimate for ferrocene being 663 kcal/mol.

We have used density functional theory, both within the local density (LDA) and generalized gradient (GGA) approximations, to study the structure, energetics, and vibrational properties of zeolite offretite in the presence of different monovalent cations (H+, Na+, K+, and Cu+). We find that the spatial locations of the most favorable cation-binding sites are similar for the different cations, being related to the minima of the electrostatic potential. However, the relative stability of the sites does depend on the nature of the counterion, as well as on the Al/Si ratio and on the mutual interactions between cations. At low Al/Si ratios, the preferred site for H+ is in the channel, where it is accessible for reaction with incoming molecules. For both Na+ and Cu+, the most stable site is within the 6-fold ring of the gmelinite cage, but for Na+, two other sites are present within a few tenths of a kilocalorie/mole from the lowest site (small site selectivity). For K+, two sites, one inside the cancrinite cage and the other near the 8-fold ring of the gmelinite cage, are very close in energy, consistent with the X-ray experiments on natural hydrated and dehydrated offretites. Dynamical simulations have been carried out for H− and Na−offretite. The vibrational spectrum of the framework agrees well with the available experiment. OH stretching frequencies calculated for a number of different H+ locations show that more "open" positions, e.g., in the channel, have higher frequencies, in agreement with experiment.

Although density functional theory (DFT) is more and more commonly used as a very efficient tool for the study of molecules and bulk materials, its applications to weakly bonded systems remain rather sparse in the literature, except studies that consider hydrogen bonding. It is, however, of essential interest to be able to correctly describe weaker van der Waals complexes. This prompted us to investigate more precisely the reliability of several widely-used functionals. The equilibrium geometries and the binding energies of C₆H₆···X (X = O₂, N₂, or CO) complexes are determined within the standard Kohn−Sham approach of DFT using different exchange−correlation functionals and at the MP2 level of theory for comparison. It is comprehensively concluded that extreme care must be taken in the choice of the functional since only those that behave properly at large and intermediate values of the reduced density gradient s give relevant results. The PW91 exchange functional, the enhancement factor of which does not diverge at increasing s, appears as the most reliable for the studied systems. It is furthermore demonstrated that the quality of the DFT results is determined by the exchange energy component of the total energy functional.

Quantum chemical calculations have been performed using density functional theory to model the mechanism of selective catalytic reduction of NO by NH3 on vanadium oxide. The reaction is initiated by NH3 adsorption on a Brønsted site modeled as a dimer cluster model representative of vanadium oxide, containing a terminal VO adjacent to a V−OH group. The calculations indicate that the adsorbed NH3 behaves as NH4+, which is supported by calculated IR spectra. Subsequently NO reacts with this activated NH3 to yield NH2NO and finally the reaction products N2 and H2O. The present results give support to a dual-site Eley−Rideal-type mechanism involving a Brønsted site and agree with isotopic labeling studies.

The enantioselective hydrogenation of ketopantolactone toR-(−)-pantolactone was investigated on 5 wt% Pt/Al2O3chirally modified with cinchonidine. The influence of catalyst pretreatment conditions, hydrogen pressure, temperature, solvent polarity, and catalyst, reactant, and modifier concentrations was studied in a slurry reactor. An enantiomeric excess (ee) of 79% at full conversion was achieved in toluene after optimization of pressure, temperature, and amount of modifier. Good ee could be obtained only after rigorous removal of traces of oxygen and water during catalyst pretreatment and from the hydrogenation reaction mixture. Molecular modeling studies (performed using molecular mechanics, semiempirical, andab initiomethods) provided a feasible structure for the diastereomeric transition complex formed between cinchonidine and ketopantolactone and an explanation for the observed enantiodifferentiation in apolar medium. The calculations indicate that formation of the complex affordingR-(−)-pantolactone is energetically favored with cinchonidine, whereas the near enantiomer cinchonine favorsS-pantolactone, in agreement with experimental observations. Interestingly, in apolar solvents, where the alkaloid modifier is not protonated, the modeling suggests similar structures for the diastereomeric transition complexes for the hydrogenation of ketopantolactone and methyl pyruvate.

QSAR concerning the anti-HIV and cytotoxic activities of a series of HEPT analogues has been established using a Hansch-type approach (TSAR™), a neural network approach (TSAR) and a pharmacophore search method (CATALYST™). The techniques employed allowed reliable activity predictions and confirmed the heterogeneity of this series of compounds, which was previously established in biochemical experiments.

Quantum chemical calculations using the density functional theory were performed to model the mechanism of selective catalytic reduction of NO by NH3 on a supported vanadium oxide monolayer. In the first step, the adsorption of NH3 on a bimetallic cluster representative of vanadium oxide, containing a terminal VO adjacent to a VOH group, was investigated. The calculations indicate that NH3 may be strongly adsorbed on VOH (Brönsted acid site) as NH+4(ads); subsequently, NO reacts with this activated NH3 to yield the reaction products N2 and H2O. The present results give support to a dual-site Eley-Rideal-type mechanism involving a Brönsted site.

The purpose of the present work was to develop a method allowing one to extract the information needed for the construction of the internal chemical hardness tensor at the molecular orbital level from standard density functional calculations. This method is based on the Janak theorem and on the extension of the Slater transition-state concept. A detailed discussion of the current ideas about the validity of the Janak theorem is presented as well as of the established relations of this subject with the ensemble V-representability problem. The internal chemical hardness tensor has been obtained for water molecule as an example system. Its structure is consistent with the criteria for the internal molecular stability.

The antimalarial activity of a series of synthetic 1,2,4-trioxanes is correlated with molecular structure by using a pharmacophore search method (CATALYST). The technique is shown to have predictive accuracy and confirms that docking between an active trioxane and the receptor, heme, is the crucial step for drug action.

We analyze differences between ground-state electron densities of a model molecular complex obtained by solving the Kohn-Sham equations with constrained electron density (KSCED) [Wesolowski and Warshel, J. Phys. Chem. 97, 8050 (1993)] and as a solution of the standard Kohn-Sham equations applied to the whole complex. The differences between KSCED and KS electron densities which result from the inaccuracy of the kinetic energy functional applied in the KSCED equations are discussed. The model molecular complex consists of collinear H₂ and HCN molecules separated by a short distance. Several kinetic energy functional approximations are applied within the KSCED framework and the differences between resulting electron densities are studied. The KSCED electron densities depend directly on the functional derivative of the kinetic energy functional applied in the KSCED equations. Among the studied functionals, the one proposed by Zhao et al. [Phys. Rev. A 47, 918 (1993)] and the gradient-dependent functional proposed by Perdew and Wang [Phys. Rev. B 33, 8800 (1986)] led to the smallest differences between KS and KSCED electron densities, thus having the most accurate functional derivative. Both functionals allow one to extend the range of applicability of the KSCED equations to system geometries where an overlap of electron densities of the partners of the complex is significant.

The iron(II) spin-crossover compound [Fe(ptz)₆](PF₆)₂ (ptz = 1-propyltetrazole) crystallizes in the triclinic space group P†, with a = 10.6439(4) Å, b = 10.8685(4) Å, c = 11.7014(4) Å, α = 75.644(1)°, β = 71.671(1)°, γ = 60.815(1)°, and Z = 1. In [Fe(ptz)₆](PF₆)₂, the thermal spin transition is extremely steep because of cooperative effects of elastic origin. The transition temperature at ambient pressure is 74(1) K. An external pressure of 1 kbar shifts the transition temperature to 102(1) K, corresponding to a stabilization of the low-spin state, which is smaller in volume. The volume difference between the high-spin and the low-spin state, ΔV°_HL, is 24(2) ų/molecule. The interaction constant Γ, as a measure of cooperativity, is within experimental error independent of external pressure and has a value of 101(5) cm^-1. In contrast to the case of the related compound [Fe(ptz)₆](BF₄)₂ (Decurtins et al. Inorg. Chem. 1985, 24, 2174), there is no hysteresis due to a first-order crystallographic phase transition, nor is there a hysteresis induced by external pressure as in the mixed crystal [Zn_1-xFe_x(ptz)₆](BF₄)₂, x = 0.1 (Jeftić et al. J. Phys. Chem. Solids 1996, 57, 1743). However, in [Fe(ptz)₆](PF₆)₂, the interaction constant Γ is found to be very close to the critical value above which a hysteresis solely due to the cooperative effects is expected. In addition, high-spin → low-spin relaxation measurements were performed under external pressures of up to 1 kbar in the temperature interval between 50 and 60 K. An external pressure of 1 kbar accelerates the high-spin → low-spin relaxation by 1 order of magnitude.

In the iron(II) spin-crossover compound [Fe(ptz)₆](BF₄)₂, the thermal spin transition is accompanied by a crystallographic phase transition showing a hysteresis with T_c^↓ = 128 K and T_c^↑ = 135 K at ambient pressure [Franke, P. L.; Haasnot, J. G.; Zuur, A. P. Inorg. Chim. Acta 1982, 59, 5]. The hysteresis is due to an interplay between the spin-transition and the R³ → P† crystallographic phase transition with a large low-spin fraction stabilizing the P† phase at low temperatures. In the mixed crystal [Zn_1-xFe_x(ptz)₆](BF₄)₂, x = 0.1, with the iron complexes imbedded into the isomorphous zinc lattice, the crystallographic phase transition can be induced by an external pressure [Jeftić, J.; Romstedt, H.; Hauser, A. J. Phys. Chem. Solids 1996, 57, 1743]. Thus the P† phase is additionally stabilized by external pressure. The interaction constant Γ, which describes cooperative effects between the spin-changing complexes, differs for the two crystallographic phases. Values for Γ(P†) of 144(8) cm^-1 and the volume difference ΔV⁰_HL of 29(4) ų are determined from a simultaneous fit to a series of transition curves for different pressures and iron content x in the P† phase. These values are compared to the corresponding values for the R³ phase, viz. Γ(R³) of 170(9) cm^-1 and ΔV⁰_HL(R3) of 26(3) ų. Surprisingly Γ(R³) is larger than Γ(P†) despite the fact that ΔV⁰_HL(R3) is smaller than ΔV⁰_HL(P1). The high-spin → low-spin relaxation at temperatures above ~80 K is thermally activated, while below ~40 K temperature independent tunnelling takes place. An external pressure of 1 kbar accelerates the high-spin → low-spin relaxation exponentially by 1 order of magnitude in the tunnelling region in both crystallographic phases and regardless of x. In the concentrated material the high-spin → low-spin relaxation is self-accelerating due a buildup of an internal pressure [Hauser, A. Chem. Phys. Lett. 1992, 192, 65]. Both cooperative effects and external pressure result in a shift of the maximum of the ¹A₁ → ¹T₁ absorption band.

A spectroscopic and kinetic study of the photoinduced electron transfer (ET) reaction between 9,10-dicyanoanthracene (DCA) and 1-methylnaphthalene (MNA) in acetonitrile using the transient grating technique is reported. Apart from the bands assigned to ¹DCA* and DCA^•-, the transient spectrum exhibits a band located at 580 nm and ascribed to MNA₂^•+. This species is generated upon reaction of a second donor molecule with a 1:1 complex to form a 1:2 complex (DCA^•-·MNA₂^•+). Using chloranil as electron acceptor, the rate constant of this reaction has been measured to be 6.8 × 10⁹ M^-1 s^-1. From the donor concentration dependence of the kinetics of DCA^•- diffraction intensity and of the free ion yield, the rates of back ET to the ground state within the 1:1 and the 1:2 complexes have been determined to be equal to 1.8 × 10⁸ and 16.9 × 10⁸ s^-1, respectively, while their rate constants of separation into free ions are 1.6 × 10⁸ and 1.1 × 10⁸ s^-1, respectively. These values have been obtained assuming a reaction scheme in which both forward and backward ET essentially take place at contact distance. In the case of the 1:1 complex, however, charge recombination within a loose ion pair cannot be ruled out.

The luminescence of the scorpion's outer shell has been shown to be due to fluorescence of very short lifetime (nanoseconds). The emission and excitation spectra have been determined, and the potential biological significance of this photoluminescence is discussed.

The reliability of the transient grating technique to determine the energetics of processes following second order kinetics, such as free ion recombination, is investigated theoretically. As the second order process takes place, the grating of the reactant population becomes anharmonic, complicating the determination of the population dynamics from the time profile of the diffracted intensity. However, the thermal phase grating is anharmonic from the beginning of the reaction, but is harmonic when the process is completed. As a consequence, the energetics of the reaction can be deduced accurately from the maximum amplitude of the diffracted intensity without having to take the anharmonicity of the grating into account, as long as thermal diffusion is slow. To achieve this, the crossing angle of the pump pulses on the sample has to be smaller than 1°. Otherwise, an arduous fitting procedure is required to extract the energetic parameters from the experimental data.

A study of the dynamics of ground-state recovery of the perylene radical cation (Pe^•+), of perylene radical anion (Pe^•-), and of anthraquinone radical anion (AQ^•-) is reported. In boric acid glass, the excited-state lifetime of Pe^•+ is 35 ± 3 ps, while in concentrated sulfuric acid, it is smaller than 15 ps, the time resolution of the experimental setup. The excited-state lifetime of Pe^•+, Pe^•-, and AQ^•- generated by photoinduced intermolecular electron-transfer reaction in MeCN is shorter than 15 ps. In the case of Pe^•-, the uncomplete ground-state recovery is ascribed to the occurrence of electron photoejection. The free ion yield in the intermolecular electron-transfer reaction between 9,10-dicyanoanthracene (DCA) and two electron acceptors was measured in a two-pulse experiment, where the second pulse excited the ensuing DCA^•-. This excitation has no influence on the magnitude of the free ion yield, indicating a short excited-state lifetime of DCA^•-* relative to the time scale of back electron transfer and ionic dissociation. A red emission, ascribed to the fluorescence of protonated Pe, was detected in boric acid glass and sulfuric acid. No fluorescence that could be clearly ascribed to Pe^•+* could be observed.

Cyclic voltammetry of phosphafulvene and dibenzophosphafulvene shows that in DMF these compounds are reduced at -1.200 and -1.349 V, respectively. The EPR spectra of the corresponding radical anions, formed by electrochemical reduction or by reaction on a potassium mirror, are Recorded between 110 K and room temperature. The g and 31P hyperfine tensors are measured and compared to those previously obtained for a phosphaalkene radical anion. Abinitio investigations on model phosphaalkene and phosphafulvene radical anions show that, in accord with the experimental results, the electronic structure of these two species are quite different: whereas the unpaired electron is delocalized on the whole PC(H)R moiety in the phosphaalkenic anion, it is markedly localized on the phosphorus atom in the phosphafulvene anion. Calculated spin densities and charge distributions for phosphafulvene and azafulvene anions are compared.

Two phosphaalkenes containing either a furane or a thiophene ring bound to the carbon atom of the −Pdouble bond; length as m-dashC < bond have been synthesized. The crystal structure of the furane derivative has been determined and the electrochemistry of both compounds has been investigated. THF solutions of these compounds react at 255 K with a potassium mirror to yield the corresponding radical anions which have been studied by EPR in both the liquid and solid states. The resulting hyperfine constants are compared with the values predicted by ab initio calculations on radical anions formed from model phosphaalkenes.

The isotropic hyperfine coupling constants of the diphosphaalkene radical cation have been measured by EPR spectroscopy after electrochemical oxidation of ArP]] C]] PAr (and ArP]] 13C]] PAr) in tetrahydrofuran (THF). The two 31P constants as well as the 13C coupling are close to 90 MHz. Taking HPCPH as a model compound, the structure has been assessed, by extensive ab initio calculations including correlation effects at the MP2 and MCSCF levels of theory. It is found that oxidation of the allenic ]P]] C]] P] structure leads to the formation of two rotamers with HPPH dihedral angles of 458 and 1358. These two structures are compatible with the Jahn–Teller distortion of allene. The calculated hyperfine constants support the EPR results.

Several radiation defects have been detected by EPR in a single-crystal of Pt(dmimt)4Cl2.4H2O (dmit = 1,3-dimethyl-imidazoline-2-thione). In order to identify these rediogenic species, the structure of the crystal has been resolved and the angular dependence of the EPR signals has been analysed. The resulting g tensors and 195Pt hyperfine tensors have been determined and the orientations of their principal axes have been compared to those of the bond directions of the precursor. It is shown that both Pt(I) and Pt(III) complexes are trapped, whereas Pd(dmimt)42+ present as an impurity, leads only to the Pd(I) species. The temperature dependende of the EPR spectra gives information about the relative stability of the paramagnetic species and shows that the formation of some species, especially the Pt(III) complexes, requires drastic modifications of the parent Pt(II) cation.

We study the ionic conductivity versus temperature and frequency of large Na²S single crystals by using a calibrated impedance apparatus. The experimental setup used for the ionic conductivity measurements up to 1350 K and its calibration are described. The apparatus allows to measure complex impedances between 0.1 Ω and 10 GΩ. The high temperature conductivity data were analyzed in terms of the conventional Frenkel defect model. We assume that cation vacancies and cation interstitials are the dominant intrinsic defects. The energy of motion was found to be 0.61 ± 0.05 eV for a cation vacancy. The energy of formation of a Frenkel defect pair is 2.51 ± 0.05 eV. Results are given that show clear evidence of a superionic behaviour close to the melting point, similar to the one found in alkaline earth fluorides and several halides. Furthermore, X-ray diffraction experiments on a high optical quality single crystal were performed. The cell parameter and the population parameter of Na⁺ were accurately determined (6.5373 Å and 0.988, respectively).

The results of a detailed optical and paramagnetic-resonance study performed on copper in CaF₂ and silver in BaF₂ are presented. Two different Ag⁺ centers were identified in BaF₂. One is associated with an interstitial F^- ion whereas the other one has a cubic surrounding. The Cu²⁺ ion in CaF₂ was shown to reorient at 4.2 K between 6 equivalent minima of D_2h symetry. This fact is interpreted with the aid of a T_2gx(T_2g+E_g) type Jahn-Teller effect. The nonlinear mixed coupling terms are shown to play an important role. The Cu⁺ impurity in CaF₂ is presumably off-center in the F^- sublattice without associated defect or impurity.