Explicitly correlated composite thermochemistry of transition metal species.

Atomization energies were calculated using explicitly correlated coupled cluster methods with correlation consistent basis sets for a series of 19 small molecules containing 3d transition metal atoms. The atomization energies were calculated using a modified Feller-Peterson-Dixon approach in which CCSD(T) complete basis set (CBS) limits were obtained using extrapolations of aVTZ∕aVQZ CCSD(T)-F12b correlation energies, and then a series of additive contributions for relativity, core correlation, higher order correlation, and zero-point vibrations were included. The frozen-core CBS limits calculated with F12 methods closely matched the more computational expensive conventional awCVQZ∕awCV5Z CBS extrapolations, with a mean unsigned deviation of just 0.1 kcal∕mol. In particular, the CCSD(T∗)-F12b∕aVDZ and aVTZ atomization energies were more accurate on average than the conventional CCSD(T)∕aVQZ and aV5Z results, respectively. In several cases the effects of higher order correlation beyond CCSD(T), as judged by CCSDT and CCSDT(Q)Λ calculations, were greater than 1 kcal∕mol, reaching 4.5 kcal∕mol for CrO3. For the 16 molecules of this study with experimental uncertainties of ∼3.5 kcal∕mol or less, the final composite heats of formation have a mean unsigned deviation (MUD) from experiment of just 1.3 kcal∕mol, which is slightly smaller than the average of the experimental uncertainties, 1.8 kcal∕mol. The root mean square deviation (RMS) is only slightly larger at 1.7 kcal∕mol. Without the contributions due to higher order correlation effects, the MUD and RMS rise to 2.1 and 2.8 kcal∕mol, respectively. To facilitate the F12 calculations, new (aug-)cc-pVnZ∕MP2Fit (n = Q, 5) and (aug-)cc-pwCVTZ∕MP2Fit auxiliary basis sets were also developed for the transition metal atoms.

Effect of rotational energy on the reaction Li + HF(upsilon = 0,j)-->LiF + H: an experimental and computational study.

In a crossed molecular-beam study we have measured angular and time-of-flight distributions of the product LiF from the reaction Li + HF(upsilon = 0)-->LiF + H at various collision energies ranging from 97 to 363 meV for three markedly different rotational state distributions of HF obtained at nozzle temperatures close to 315, 510, and 850 K. Particularly, for the low and intermediate collision energies we observe significant effects of the varying j-state populations on the shape of the product angular distributions. At 315 K an additional feature appears in the angular distributions which is interpreted as being due to scattering from HF dimers. The experimental data are compared with simulations of the monomer reaction based on extensive quasiclassical trajectory calculations on a new state-of-the-art ab initio potential energy surface. We find an overall good agreement between the theoretical simulations and the experimental data for the title reaction, especially at the highest HF nozzle temperature.

Differential cross sections from quantum calculations on coupled Ab initio potential energy surfaces and scattering experiments for Cl(2P)+H2 reactions.

To assess the relative reactivity of the spin-orbit excited state of atomic Cl with molecular hydrogen, we have measured differential cross sections using an atomic Cl beam with a known concentration of the ground and excited spin-orbit states. These are compared with the first determination of the cross sections from quantum mechanical scattering calculations on a set of coupled ab initio potential energy surfaces. The comparison suggests that these surfaces may underestimate the degree of rotational excitation of the HCl products and that the excited spin-orbit state plays a minor role in the reaction.

Experimental and theoretical studies of the d8-d10 interaction between Pd(II) and Au(I): bis(chloro[(phenylthiomethyl)diphenylphosphine]gold(I))- dichloropalladium(II) and related systems.

The reaction between thioether phosphine gold(I) precursors such as [AuCl(Ph2PCH2SPh)], 1, or [Au(Ph2PCH2SPh)2]CF3SO3 and PdCl2(NCPh)2 affords the new compounds [(AuCl(Ph2PCH2SPh)2PdCl2], 2, and [AuPdCl2(Ph2PCH2SPh)2]CF3SO3, 3. The crystal structure of complex 2 has the sterically unhindered Pd(II) and Au(I) at a distance of 314 pm. Quasirelativistic pseudopotential calculations on [AuPdCl3(PH2CH2SH)(SH2)] models give short Au-Pd distances at the second-order Møller-Plesset (MP2) level and long Au-Pd distances at Hartree-Fock (HF) level. A detailed analysis of the Au-Pd interaction shows dominant dispersion, some ionic contributions, and no net charge transfer between the metals.

Relationship between structural parameters, bone mineral density and fracture load in lumbar vertebrae, based on high-resolution computed tomography, quantitative computed tomography and compression tests.

Different noninvasive techniques for the assessment of the individual fracture risk in osteoporosis are introduced, and the relation between structural properties of high-resolution computed tomography (HR-CT) images of vertebral bodies, their bone mineral density (BMD) and the fracture load is analyzed. In 24 unfractured lumbar vertebrae with different degrees of demineralization from six specimens, the trabecular and cortical BMD was determined using quantitative CT. A lateral X-ray image revealed the number of fractures in the entire spine. A structural analysis of spongy and cortical bone was performed based on the HR-CT images. In the spongiosa, the fractal dimension was calculated as a function of the threshold value. In the cortical shell, the maximum number of clusters of low BMD was determined at varying threshold values. After the CT measurements the vertebrae were excised and compressed until fractured. On the basis of the spongiosa BMD and the number of fractures, 3 cases were found to be severely osteoporotic; the other 3 cases showed osteopenia. The average fracture loads were determined as 3533 N for the non-osteoporotic cases (range 2602-5802 N) and 1725 N for the osteoporotic cases (range 1311-2490 N). The parameters were determined as follows: average spongiosa BMD 115.2 mg/ml (101.8-135.3 mg/ml) for the non-osteoporotic cases, 46.2 mg/ml (34.8-57.6 mg/ml) for the osteoporotic cases; average cortical BMD 285.1 mg/ml (216.4-361.9 mg/ml) for the non-osteoporotic cases, 136. 1 mg/ml (142.5-215.2 mg/ml) for the osteoporotic cases; spongiosa structure: average 0.5 (range 0.32-0.75) for the non-osteoporotic cases, average 1.05 (range 0.87-1.24) for the osteoporotic cases; cortical structure: average 81 (range 55-104) for the non-osteoporotic cases), average 136 (range 102-159) for the osteoporotic cases. Single parameters (BMD and structure) and weighted sums of these parameters were correlated with the fracture load, resulting in correlation coefficients of r(sBMD) = 0.82 (spongiosa BMD), r(cBMD) = 0.82 (cortical BMD), r(sStr) = -0.75 (spongiosa structure) and r(cStr) = -0.86 (cortical structure). The weighted sum of cortical and spongiosa BMD resulted in r(BMD) = 0.86, of cortical and spongiosa structure in r(Str) = -0.86. A weighted combination of all four parameters correlates with the fracture load at r(4) = 0.89, all correlations being statistically significant (p<0.0001). The four individual parameters show only a slight overlap between non-osteoporotic and osteoporotic subjects. The high correlation of the cortical BMD and the structural parameter in cortical bone indicates the important contribution of the cortical shell to vertebral stability. A weighted sum of multiple parameters results in a higher correlation with the fracture load and does not show an overlap between the two groups. It is best suited to estimate the individual fracture risk. The presented methods are generally applicable in vivo; and allow an improvement of the diagnosis of osteoporosis compared with the measurement of the BMD alone.

Contribution of the cortical shell of vertebrae to mechanical behaviour of the lumbar vertebrae with implications for predicting fracture risk.

In the diagnosis of osteoporosis using single energy quantitative CT (SE-QCT) on the axial skeleton, only spongy bone mineral density (BMD) is used at present. Although the density of cortical bone is also determined by most QCT methods, it is not used for evaluation. The objective of this study was to determine the extent to which the cortical bone of the lumbar vertebral bodies accounts for their load-bearing capacity and failure behaviour, and to use this information to suggest improvements in the differential diagnosis of osteoporosis. Investigations were conducted in a clinical, theoretical-numerical and biomechanical-experimental context. Cortical (BMDC) and spongy (BMDS) bone mineral density was measured by SE-QCT/85 kV on 179 patients (68 males, 111 females). These bone densities were matched with the vertebral body fractures previously determined from conventional X-rays. A finite element model was used to study the variation in structural and material parameters of the vertebral body. 19 vertebral bodies that had been removed post-mortem were available for the biomechanical-experimental investigations. Spongy and cortical bone densities were also determined by SE-QCT on these vertebral bodies. Their failure load was then measured in the axial compression test. These investigations show that, in addition to the spongiosa, the cortical shell plays an important role in the load-bearing capacity of the vertebral body. If the spongiosa is weakened due to a loss of BMD, the residual load-bearing capacity of the vertebral bodies is increasingly shouldered by the cortical bone. The lower susceptibility to fracture in men compared with women when spongy bone mineral density is reduced can thus be attributed to the lack of a reduction in cortical bone mineral density. It is recommended that the BMDC also be evaluated in future, especially in the diagnosis of bone mass losses in women, to improve the estimation of the individual fracture risk.

Three electronic state model of the primary phototransformation of bacteriorhodopsin.

The primary all-trans --> 13-cis photoisomerization of retinal in bacteriorhodopsin has been investigated by means of quantum chemical and combined classical/quantum mechanical simulations employing the density matrix evolution method. Ab initio calculations on an analog of a protonated Schiff base of retinal in vacuo reveal two excited states S1 and S2, the potential surfaces of which intersect along the reaction coordinate through an avoided crossing, and then exhibit a second, weakly avoided, crossing or a conical intersection with the ground state surface. The dynamics governed by the three potential surfaces, scaled to match the in situ level spacings and represented through analytical functions, are described by a combined classical/quantum mechanical simulation. For a choice of nonadiabatic coupling constants close to the quantum chemistry calculation results, the simulations reproduce the observed photoisomerization quantum yield and predict the time needed to pass the avoided crossing region between S1 and S2 states at tau1 = 330 fs and the S1 --> ground state crossing at tau2 = 460 fs after light absorption. The first crossing follows after a 30 degrees torsion on a flat S1 surface, and the second crossing follows after a rapid torsion by a further 60 degrees. tau1 matches the observed fluorescence lifetime of S1. Adjusting the three energy levels to the spectral shift of D85N and D212N mutants of bacteriorhodospin changes the crossing region of S1 and S2 and leads to an increase in tau1 by factors 17 and 10, respectively, in qualitative agreement with the observed increase in fluorescent lifetimes.

The loss of stiffness as osteoporosis progresses.

The routine diagnosis of osteoporosis is based on radiological measurements of bone mineral content. An osteoporotic failure is influenced both by a loss of mineralized bone and internal bone structure. The structure cannot be estimated by bone reconstruction based on standard radiological equipment. To investigate the influence of structure on cancellous bone stiffness, a new finite element model of cancellous bone is developed. The model describes a cancellous bone unit as an open-celled structure. Trabecular length, trabecular thickness, diameter of trabecular connections, relative lattice disorder and relative bone loss determine the real architecture. Using this model, the loss of stiffness as a result of trabecular thinning and loss of trabecular connections is estimated. The volume fraction as a scalar value for a volume can not be a marker for orthotropic stiffness changes. A formula in the form Y = e(a *1 n(X) + b) can describe the correlation between cancellous bone stiffness and volume fraction. These formulas are appropriate for those cases, when the loss of bone mineral (decrease in trabecular thickness) is closely connected to a loss of structure (increasingly perforated trabecular network).

The transition state of the f + h2 reaction.

The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively.

Intravenous treatment of chronic peripheral occlusive arterial disease: a double-blind, placebo-controlled, randomized, multicenter trial of pentoxifylline.

A multicenter, prospective, placebo-controlled, double-blind trial was conducted to investigate the efficacy of intravenous infusion therapy with pentoxifylline over fourteen days in patients suffering from angiographically confirmed chronic peripheral occlusive arterial disease, Fontaine stage II, with at least a six-month history. After a washout phase of one week, the patients received in accordance with a randomization scheme either an i.v. infusion of 300 mg of pentoxifylline (15 mL ampoules) or 15 mL of a 0.9% NaCl solution in 250 mL of 5% laevulose, administered over three hours twice daily. The main efficacy parameters were treadmill-assessed initial claudication distance (ICD) and absolute claudication distance (ACD). Baseline testing revealed a mean ICD of 131 m in the pentoxifylline group and 126 m in the placebo cohort; mean ACD values were 239 m and 225 m respectively. The group of patients treated with pentoxifylline (n = 75) displayed a significantly greater improvement (p less than 0.0001) in ICD (+70%) and ACD (+60%) than the placebo group did (+33%) and 32%, respectively) (n = 79). The infusions were well tolerated in both groups.

Observation on the capping of spleen lymphocytes from scrapie infected mice after treatment with anti Ig.

Staining of lymphocytes from scrapie-infected STU mice with FITC-labelled anti-mouse Ig revealed disturbances in the capping process when compared with lymphocytes from mock-infected animals. Quantitative evaluation indicates that 10-15% of cells from scrapie-infected animals show an altered capping behaviour. These phenomena are discussed with special reference to the role of the lymphoreticular system in early scrapie agent replication.

Electron transfer and spin exchange contributing to the magnetic field dependence of the primary photochemical reaction of bacterial photosynthesis.

The yield phiT of triplet products "PR" generated in reaction centers of Rhodopseudomonas sphaeroides in which the "primary" acceptor is reduced had been found to depend on external magnetic fields. The magnetic field dependence varies, however, between different reaction center preparations. By means of a theoretical description of the primary electron transfer processes and hyperfine coupling-induced electron spin motion the factors influencing the magnetic field behaviour of the triplet products are studied. The following quantities characteristic of the primary electron transfer in photosynthesis have a strong effect on phiT: (1) the rate constants of reversible electron transfer between the initially excited singlet state of the reaction center and an intermediate radical ion pair state; (2) the rate constants of irreversible electron transfer of the radical pair to the ground and excited triplet state of the reaction center; (3) the electron exchange interactions between the radical pair and the "primary" acceptor. From the observed magnetic field dependence of phiT estimates for these quantities are obtained. A temperature dependence of the magnetic field behaviour of phiT and a magnetic field effect on the fluorescence quantum yield of the reaction center are predicted.