Theoretical study of the electronic structure of CnS (n=1-6) thiocumulenes

Linear sulfur-carbon chains C(n)S (n=1-6) of astronomical interest were examined by means of several theoretical methods. The three smallest compounds of the series were chosen to evaluate the performance of several computational models, including Hartree-Fock theory, density functional theory with the Becke's three parameter exchange functional and the correlation functional of Lee, Yang, and Parr (B3LYP), and electron-correlated methods (second-order Moller-Plesset perturbation method (MP2), configuration interaction method including single and double excitations (CISD), and quadratic configuration interaction method including single and double excitations (QCISD) in combination with a large variety of basis sets. The systematic comparison between the experiment and theory indicates that the B3LYP/6-311G** method can be considered suitable for the study of the electronic structures of the C(n)S compounds. The electronic ground states of the C(n)S molecules alternate between 1Sigma and 3Sigma for odd and even values of n, respectively. The B3LYP/6-311G** wave functions for these electronic ground states were analyzed by means of the atoms in molecules (AIM) and natural bond orbital (NBO) methods. Both approaches suggest that the electronic structures for the singlet and triplet compounds must be considered separately. According to the NBO method, singlet compounds can be properly represented by acetylenic structures with alternating single and triple bonds (S[triple bond]C-C[triple bond]C...). However, triplet compounds are better described by means of double bond-double bond cumulenic structures (S=C=C=C=C...) as a consequence of the average between different alpha and beta electronic densities. AIM delocalization indexes and NBO interactions between localized orbitals also indicate that these structures are strongly pi delocalized. Finally, the different singlet and triplet structures proposed provide a consistent explanation for the geometries, dipole moments, and spin-density values of the C(n)S compounds studied.     

Supramolecular helical mesomorphic polymers. Chiral induction through H-bonding

The work described here concerns a challenge of general interest in supramolecular chemistry: the achievement of chiral helical organizations with controlled structures. This work provides a strategy to obtain supramolecular polymers in which a chiral helical conformation has been induced by a noncovalent association, that is, through hydrogen bonding. Polycatenar 2,4,6-triarylamino-1,3,5-triazines, which organize into columnar mesophases and are susceptible to H-bonding interactions, were chosen as a starting point to build up the chiral supramolecular structure. The stacking of these mesogens has been forced to wind in a helical way by means of H-bond association with (R)-3-methyladipic acid, within the mesophase. The optically active columnar organization has been studied in depth by optical microscopy, differential scanning calorimetry (DSC), X-ray diffraction, and circular dichroism. Formation of stable complexes between the triazine units and (R)-3-methyladipic acid has also been investigated by means of NMR diffusion-ordered spectroscopy (DOSY) experiments in chloroform.     

Broad-band spectroscopy of a vanadyl porphyrin: a model electronuclear spin qudit

We explore how to encode more than a qubit in vanadyl porphyrin molecules hosting a S = 1/2 electronic spin coupled to a I = 7/2 nuclear spin. The spin Hamiltonian and its parameters, as well as the spin dynamics, have been determined via a combination of electron paramagnetic resonance, heat capacity, magnetization and on-chip magnetic spectroscopy experiments performed on single crystals. We find low temperature spin coherence times of micro-seconds and spin relaxation times longer than a second. For sufficiently strong magnetic fields (B > 0.1 T, corresponding to resonance frequencies of 9–10 GHz) these properties make vanadyl porphyrin molecules suitable qubit realizations. The presence of multiple equispaced nuclear spin levels then merely provides 8 alternatives to define the ‘1’ and ‘0’ basis states. For lower magnetic fields (B < 0.1 T), and lower frequencies (<2 GHz), we find spectroscopic signatures of a sizeable electronuclear entanglement. This effect generates a larger set of allowed transitions between different electronuclear spin states and removes their degeneracies. Under these conditions, we show that each molecule fulfills the conditions to act as a universal 4-qubit processor or, equivalently, as a d = 16 qudit. These findings widen the catalogue of chemically designed systems able to implement non-trivial quantum functionalities, such as quantum simulations and, especially, quantum error correction at the molecular level.

We show that a sizeable electronuclear entanglement of the S = 1/2 and I = 7/2 spins of a vanadyl porphyrin provides the conditions to act as a universal 4-qubit processor, and thus implement quantum error correction at the molecular level.     

Determination of ageing time of spirits in oak barrels using a headspace–mass spectrometry (HS-MS) electronic nose system and multivariate calibration

The aromatic composition of sugar cane spirits and, in general, of alcoholic beverages, is mainly influenced by the ageing process in wood barrels. There are several factors that affect the quality of the final aged product, but the time of the storage in the barrel is perhaps the most important one. Ageing time must therefore be controlled in order to detect counterfeits; however, this parameter is very difficult to control and, at present, there is no analytical method available to determine it. We propose a quantitative method for determining the ageing time of sugar cane spirits in oak barrels by using an electronic nose based on coupling directly a headspace sampler to a mass spectrometer (HS-MS), and multivariate calibration. The method developed is simple and provides, in 5 min, the ageing time of spirits with an accuracy of about 1 month.     

Chemical, structural, and thermal properties of Zn(II)-Cr(III) layered double hydroxides intercalated with sulfated and sulfonated surfactants

Zn(II)-Cr(III)-LDHs (layered double hydroxides) containing sulfated or sulfonated surfactants as the interlamellar anion were synthesized by the coprecipitation method. The syntheses were conducted under various different experimental conditions, such as the Zn : Cr ratio, pH, and aging time. In each of the prepared materials, unlike previously reported data, the interlayer anion arrangement did not change, being consistent with a perpendicular monolayer. The thermal decomposition process of the prepared materials was studied by a set of analysis methods, such as TG/DTA, TG/MS, PXRD, and FT-IR. From the results obtained it was possible to conclude that, in an air atmosphere, the anions decomposed by a partial combustion, leading to the formation of sulfide. The results also showed that sulfonated surfactants containing LDHs are much more stable than those containing sulfated surfactants. A mechanism was proposed for the thermal decomposition of such LDHs based on the experimental results.     

Flexible ureasil hybrids with tailored optical properties through doping with metal nanoparticles

Hybrid organic-inorganic nanocomposites containing uniform distributions of metal nanoparticles have been prepared by mixing a preformed nanoparticle colloid with the precursors of a ureasil, prior to the sol-gel transition. These nanocomposites possess not only high optical quality and optical features dictated by the size and shape of the nanoparticle dopants but also a high degree of flexibility, which can largely enhance the range of applications in practical devices. The deposition of a uniform silica shell on the nanoparticle surface prior to the sol-gel transition was found to be required to maintain the colloidal stability during the process and, thus, to retain the optical properties in the final nanocomposite material. This method can be readily extended to other materials, such as semiconductor and magnetic nanoparticles.     

A study of two-electron quantum dot spectrum using discrete variable representation method

A variational method called discrete variable representation is applied to study the energy spectra of two interacting electrons in a quantum dot with a three-dimensional anisotropic harmonic confinement potential. This method, applied originally to problems in molecular physics and theoretical chemistry, is here used to solve the eigenvalue equation to relative motion between the electrons. The two-electron quantum dot spectrum is determined then with a precision of at least six digits. Moreover, the electron correlation energies for various potential confinement parameters are investigated for singlet and triplet states. When possible, the present results are compared with the available theoretical values.     

Comparison of liquid chromatography-mass spectrometry interfaces for the analysis of polar metabolites of benz[a]pyrene

 The performance of two liquid chromatography-mass spectrometry (LC/MS) interfacing techniques, thermospray (TSP) and atmospheric pressure chemical ionization (APCI), for the analysis of benzo[a]pyrene (BaP) metabolites (hydroxy, epoxy and quinone derivatives) was compared. Interface and detection parameters such as source temperature, eluent composition or flow rate were optimized using negative ion mode. In TSP, the main ions are mostly [M]^-, [M−H₂O]^- or [M+CH₃COO]^-, whereas APCI gives mainly the [M]^- and [M−H]^- ions. Quantification was carried out by flow injection. Calibration graphs were linear in the range of 10 ng to 1000 ng in TSP and 0.1 ng to 10 ng in APCI. Detection limits were in the range of 1 ng to 20 ng in TSP and 0.002 ng to 0.2 ng in APCI. The presence of BaP-1,6-dione, BaP-3,6-dione, and BaP-6,12-dione was confirmed in environmental samples of air particulate matter. Received: 6 January 1997/Accepted: 18 April 1997     

Determination of degree of conversion as a function of depth of a photo-initiated dental restoration composite—III application to commercial Prodigy Condensable™

In this third work, we evaluated the degree of conversion (DC) versus depth of dental filling composite named Prodigy Condensable™ using infrared spectroscopy. Confirming previous results, there was a gradual reduction of DC with increasing depth but the composite exhibited extreme values of DC, an upper value (45.9%) on the surface and a lower one (6.1%) at a depth of 5 mm. The composite presented the worst performance among materials studied. The composite formulation was 80% of inorganic fillers and BisfenolA/dimethacrylate (BisGMA) (18%)/triethyleneglycoldimethacrylate (TEGDMA) (2.0%) as monomers. As stated before, type/ratio/viscosity of monomers and type, amount, size and size distribution of fillers all together had an important role in the cure reaction contributing to the final performance of the composite.