Comparative study of DFT methods applied to small titanium/oxygen compounds

The performance of a number of different local and nonlocal density functional theory (DFT) methods has been investigated for some small titanium—oxygen systems. Equilibrium geometries, ionization potentials, dipole moments, atomization energies, and harmonic vibrational frequencies have been calculated for the TiO, TiO₂, and Ti₂ molecules, and the results are compared with experimental data and ab initio calculations. It is shown that most DFT methods perform much better than the ab initio Hartree—Fock (HF), second-order perturbation theory (MP2), and configuration interaction including single and double excitations (CISD) treatments. For good agreement with experimental data, gradient corrections to the exchange part of the DFT functional are needed, as well as some type of correction for the errors in the calculated energy splittings between different atomic states of titanium. Hybrid methods including a mixture of HF exchange with DFT exchange correlation do not perform as well as “pure” DFT methods for the studied systems. © 1996 John Wiley & Sons, Inc.     

Modulation of the lowest metal-to-ligand charge-transfer state in [Ru(bpy)2(N-N)]2+ systems by changing the N-N from hydrazone to azine: photophysical consequences

Two Ru(II) complexes, [Ru(bpy)2L](ClO4)2 (1) and [Ru(bpy)2L'](BF4)2 (2), where bpy is 2,2'-bipyridine, L is diacetyl dihydrazone, and L' 1:2 is the condensate of L and acetone, are synthesized. From X-ray crystal structures, both are found to contain distorted octahedral RuN(6)(2+) cores. NMR spectra show that the cations in 1 and 2 possess a C2 axis in solution. They display the expected metal-to-ligand charge transfer (1MLCT) band in the 400-500 nm region. Complex 1 is nonemissive at room temperature in solution as well as at 80 K. In contrast, complex 2 gives rise to an appreciable emission upon excitation at 440 nm. The room-temperature emission is centered at 730 nm (lambda(em)(max)) with a quantum yield (Phi(em)) of 0.002 and a lifetime (tau(em)) of 42 ns in an air-equilibrated methanol-ethanol solution. At 80 K, Phi(em) = 0.007 and tau(em) = 178 ns, with a lambda(em)(max) of 690 nm, which is close to the 0-0 transition, indicating an 3MLCT excited-state energy of 1.80 eV. The radiative rate constant (5 x 10(4) s(-1)) at room temperature and 80 K is almost temperature independent. From spectroelectrochemistry, it is found that bpy is easiest to reduce in 2 and that L is easiest in 1. The implications of this are that in 2 the lowest (3)MLCT state is localized on a bpy ligand and in 1 it is localized on L. Transient absorption results also support these assignments. As a consequence, even though 2 shows a fairly strong and long-lived emission from a Ru(II) --> bpy CT state, the Ru(II) --> L CT state in 1 shows no detectable emission even at 80 K.     

Recoil spectrometry: Ion accelerator based elemental characterisation of surface layers

Recoil Spectrometry covers a group of techniques that are very similar to the well known Rutherford backscattering Spectrometry technique, but with the important difference that one measures the recoiling target atom rather than the projectile ion. This makes it possible to determine both the identity of the recoil and its depth of origin from its energy and velocity, using a suitable detector system. The incident ion is typically high-energy (30–100MeV)³⁵C1,⁸¹Br or¹²⁷I. Low concentrations of light elements such as C, O and N can be profiled in a heavy matrix such as Fe or GaAs. Here we present an overview of mass and energy dispersive recoil Spectrometry and illustrate its successful use in some typical applications.     

Molecularly imprinted capillary electrochromatography for selective determination of thiabendazole in citrus samples

In this work, the suitability of the combination of molecular imprinting and capillary electrochromatography (MIP-CEC) to be used as powerful tool in environmental or food analysis has been for the first time studied and successfully demonstrated. A molecularly imprinted monolith (MIM) has been synthesised and evaluated as stationary phase for the selective determination of the fungicide thiabendazole (TBZ) in citrus samples by non-aqueous capillary electrochromatography. The influence of the mobile phase composition, the voltage of the power supply and the separation temperature on the recognition of TBZ by the imprinted polymer has been evaluated, and the imprint effect in the MIM was clearly demonstrated. Once optimum recognition conditions were established, other variables affecting mechanical properties and chromatographic performance of MIM were adjusted using computational approach. The high selectivity achieved by the MIP-CEC developed procedure allowed unambiguous detection and quantification of TBZ in citrus samples by direct injection of the crude sample extracts, without any previous clean-up, in less than 6 min. The developed method was properly validated and the calculated detection limits were below the established maximum residue limits (MRLs), clearly demonstrating the suitability of the method to be used for the control of the selected fungicide.     

Phase modulation in dipolar-coupled A2 spin systems: effect of maximum state mixing in H NMR in vivo

Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (A_n system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time.     

Megavariate Analysis of Environmental QSAR Data. Part II – Investigating Very Complex Problem Formulations Using Hierarchical, Non-Linear and Batch-Wise Extensions of PCA and PLS

Summary Three extensions of the basic PCA and PLS methodologies are described. These extensions are hierarchical, non-linear and batch-based in nature. The objectives of these methods are to assist in problem understanding and problem solving in very complex (QSAR) problem formulations. The method extensions are illustrated using two example QSAR data sets containing many X- and Y-variables.     

Measurements of γ-γ and γ-electron directional correlations in119Sb

The directional correlations ofγ-γ andγ-electron cascades in¹¹⁹Sb are measured, in the decay of^119mTe. Bothγ-γ andγ-electron directional correlation coefficients are determined for the cascades (energies in keV): 153.5-1212.7, 942.3-270.5, (976.2+979.3)-270.5, 1095.7-270.5 and 1136.8-270.5. For the cascades 912.6-1366.2, 2013.4-270.5 and 2089.9-270.5γ-γ directional correlations are measured. The mixing ratios evaluated are:δ(M2/E1, 153.5 keV)=0.0003±0.0023,δ(E2/M1, 270.5 keV)=-0.39±0.29,δ(E2/M1, 942.3 keV)= ?0.26±0.12,δ(E3/M2,1095.7 keV)=?0.01±0.07, andδ(M3/E2,1212.7 keV) =0.004±0.007. The result is compared with theoretical predictions.     

Thermometric analysis of blood metabolites in ICU patients

Journal of Thermal Analysis and Calorimetry - Real-time monitoring of patient’s blood metabolites, such as glucose and lactate, could potentially improve surgery and recovery outcomes for...