NDDO-based CI methods for the prediction of electronic spectra and sum-over-states molecular hyperpolarization

NDDO-based (AM1) configuration interaction (CI) calculations have been used to calculate the wavelength and oscillator strengths of electronic absorptions in organic molecules and the results used in a sum-over-states treatment to calculate second-order-hyperpolarizabilities. The results for both spectra and hyperpolarizabilities are of acceptable quality as long as a suitable CI-expansion is used. We have found that using an active space of eight electrons in eight orbitals and including all single and pair-double excitations in the CI leads to results that agree well with experiment and that do not change significantly with increasing active space for most organic molecules. Calculated second-order hyperpolarizabilities using this type of CI within a sum-over-states calculation appear to be of useful accuracy.

Ab initio calculations of differential cross sections for single charge transfer in He-3(2+)+He-4 collisions

The single charge transfer process in He-3(2+)+He-4 collisions is investigated using the quantum-mechanical molecular-orbital close-coupling method, in which the adiabatic potentials and radial couplings are calculated by using the ab initio multireference single- and double-excitation configuration interaction methods. The differential cross sections for the single charge transfer are presented at the laboratorial energies E = 6 keV and 10 keV for the projectile He-3(2+). Comparison with the existing data shows that the present results are better in agreement with the experimental measurements than other calculations in the dominant small angle scattering, which is attributed to the accurate calculations of the adiabatic potentials and the radial couplings.

A combined neutralization-reionization mass spectrometric and theoretical study of oxyallyl and other elusive [C3,H4,O] neutrals

Five different anionic [C3′H4′O]•- isomers, i.e. the radical anions of acrolein, acetyl carbene, formyl methyl carbene, methoxy vinylidene, and oxyallyl are generated in an ion beam mass spectrometer and subjected to neutralization-reionization (NR) mass spectrometric experiments including neutral and ion decomposition difference (NIDD) mass spectrometry; the latter allows for the examination of the neutrals' unimolecular reactivity. Further, the anionic, the singlet and triplet neutral, and the cationic [C3′H4′O] •-/0/•+ potentialenergy surfaces are calculated at the B3LYP/6-311++G(d,p) level of theory. For some species, notably the singlet state of oxyallyl, the theoretical treatment is complemented by G2, CASSCF, and MR-CI calculations. Theory and experiment are in good agreement in that at the neutral stage (i) acrolein does not react within the μsec timescale, (ii) acetyl and formyl methyl carbenes isomerize to methyl ketene, (iii) methoxy vinylidene rearranges to methoxy acetylene, (iv) singlet 1A1 oxyallyl undergoes ring closure to cyclopropanone, and (v) triplet 3B2 oxyallyl may have a lifetime sufficient to survive a NR experiment.

Cresols - An investigation into their electronic structure and spectra

The three isomeric cresols were subjected to the all-valence-electron CNDO/2 andPPP-CI calculations. Results from this study were used: (i) to compare the electronic structures of these isomers vis-Ã-vis parent compounds-phenol and toluene, (ii) to obtain a quantitative picture of their chemical reactivities and electronic absorption spectra. Using the sgr-core charges derived from CNDO/2 calculations and subsequently revising the valence-state ionisation potential and one-center-two-electron repulsion integrals, thePPP-CI calculations were performed on the title compounds according toNishimoto andForster scheme. In these calculations the pseudo-unsaturated nature of the methyl group has been given due consideration. In spectral assignment, compared to the conventionalPPP approach, the CNDO/2-basedPPP-CI method gave a better agreement with the experimental data.

Computational Methods for Studies of Quantum Dots and Boson Condensates

This thesis presents ab initio studies of two kinds of physical systems, quantum dots and bosons, using two program packages of which the bosonic one has mainly been developed by the author. The implemented models, \emph{i.e.}, configuration interaction (CI) and coupled cluster (CC) take the correlated motion of the particles into account, and provide a hierarchy of computational schemes, on top of which the exact solution, within the limit of the single-particle basis set, is obtained. The theory underlying the models is presented in some detail, in order to provide insight into the approximations made and the circumstances under which they hold. Some of the computational methods are also highlighted. In the final sections the results are summarized. The CI and CC calculations on multiexciton complexes in self-assembled semiconductor quantum dots are presented and compared, along with radiative and non-radiative transition rates. Full CI calculations on quantum rings and double quantum rings are also presented. In the latter case, experimental and theoretical results from the literature are re-examined and an alternative explanation for the reported photoluminescence spectra is found. The boson program is first applied on a fictitious model system consisting of bosonic electrons in a central Coulomb field for which CI at the singles and doubles level is found to account for almost all of the correlation energy. Finally, the boson program is employed to study Bose-Einstein condensates confined in different anisotropic trap potentials. The effects of the anisotropy on the relative correlation energy is examined, as well as the effect of varying the interaction potential.}

Hyperfine quenching of the 3s3p P-3(0) level in Mg-like ions

Hyperfine quenching rates of the 3s3p P-3(0) level in Mg-like ions were calculated using the GRASP2K package based on the multi-configuration Dirac-Hartree-Fock method. Valence and core-valence correlation effects were accounted for in a systematic way. Breit interactions and QED effects were included in the subsequent relativistic CI calculations. Calculated rates were compared with other theoretical values and with experiment, and a good agreement with the latest experimental value for the Al-27(+) ion (Rosenband et al 2007 Phys. Rev. Lett. 98 220801) was found. Furthermore, we showed in detail the contributions from Breit interaction and QED effects to concerned physical properties. Finally, electronic data were presented in terms of a general scaling law in Z that, given isotopic nuclear spin and magnetic moment, allows hyperfine-induced decay rates to be estimated for any isotope along the isoelectronic sequence.

Using triazine as coupling unit for intramolecular ferromagnetic coupling of multiradicals

Novel high spin tri-, tetra-, pentaradicals, composed of triazine coupling units and cationic amino radical spin centers (+ . NH) under various configurations and linkages, are predicted from AM1-CI calculations. It is found that for charged planar multiradicals the stability of high spin ground states depends on both the molecular configuration and the number of end groups. Generally, cyclic 1,3-bridged charged multiradicals (S less than or equal to 5/2) possess more stable high spin ground states than their isomers under the branched 1,3,5,-bridged configuration. Therefore, it is suggested that in the design of planar high spin molecules with stable high spin ground states, less end groups and all the supposed spin centers and/or the coupling units should be under the same structural situation. (C) 1999 Elsevier Science B.V. All rights reserved.

Modelo de solvatação teórica de flavonóis

Neste trabalho, nós usamos uma combinação da simulação Monte Carlo e o modelo quântico INDO/S-CI para investigar os efeitos de solvente nos espectros de absorção eletrônica dos flavonols quercetina e kaempferol solvatados em metanol. O estudo foi conduzido realizando cálculos ao nível de INDO/S-CI em várias configurações estatisticamente relevantes produzidas pela simulação Monte Carlo. Usando a função de autocorrelação da energia, nós reduzimos de forma segura o número necessário de cálculos quânticos a serem realizados para se obter o valor médio da energia de transição π --- π* da quercetina e kaempferol em metanol usando diferentes camadas de solvatação. Além disso, uma cuidadosa investigação das pontes de hidrogênio formadas no curso da simulação Monte Carlo foi realizada. Como poderá ser notado mais adiante, nossos resultados estão de muito bom acordo com os resultados experimentais disponíveis.

Field measurement of beef pen manure methane and nitrous oxide reveals a surprise for inventory calculations

Few data exist on direct greenhouse gas emissions from pen manure at beef feedlots. However, emission inventories attempt to account for these emissions. This study used a large chamber to isolate N2O and CH4 emissions from pen manure at two Australian commercial beef feedlots (stocking densities, 13-27 m(2) head) and related these emissions to a range of potential emission control factors, including masses and concentrations of volatile solids, NO3-, total N, NH4+, and organic C (OC), and additional factors such as total manure mass, cattle numbers, manure pack depth and density, temperature, and moisture content. Mean measured pen N2O emissions were 0.428 kg ha(-1) d(-1) (95% confidence interval [CI], 0.252-0.691) and 0.00405 kg ha(-1) d(-1) (95% CI, 0.00114-0.0110) for the northern and southern feedlots, respectively. Mean measured CH4 emission was 0.236 kg ha(-1) d(-1) (95% CI, 0.163-0.332) for the northern feedlot and 3.93 kg ha(-1) d(-1) (95% CI, 2.58-5.81) for the southern feedlot. Nitrous oxide emission increased with density, pH, temperature, and manure mass, whereas negative relationships were evident with moisture and OC. Strong relationships were not evident between N2O emission and masses or concentrations of NO3- or total N in the manure. This is significant because many standard inventory calculation protocols predict N2O emissions using the mass of N excreted by the animal.

Propriedades estruturais e ópticas de filmes finos a-C:H:CI obtidos por deposição à vapor químico assistido por plasma e deposição e implantação iônica por imersão em plasma

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Mapping Intercellular CO2 Mole Fraction (Ci) in Rosa rubiginosa Leaves Fed with Abscisic Acid by Using Chlorophyll Fluorescence Imaging1 : Significance of Ci Estimated from Leaf Gas Exchange

Imaging of photochemical yield of photosystem II (PSII) computed from leaf chlorophyll fluorescence images and gas-exchange measurements were performed on Rosa rubiginosa leaflets during abscisic acid (ABA) addition. In air ABA induced a decrease of both the net CO2 assimilation (An) and the stomatal water vapor conductance (gs). After ABA treatment, imaging in transient nonphotorespiratory conditions (0.1% O2) revealed a heterogeneous decrease of PSII photochemical yield. This decline was fully reversed by a transient high CO2 concentration (7400 μmol mol−1) in the leaf atmosphere. It was concluded that ABA primarily affected An by decreasing the CO2 supply at ribulose-1,5-bisphosphate carboxylase/oxygenase. Therefore, the An versus intercellular mole fraction (Ci) relationship was assumed not to be affected by ABA, and images of Ci and gs were constructed from images of PSII photochemical yield under nonphotorespiratory conditions. The distribution of gs remained unimodal following ABA treatment. A comparison of calculations of Ci from images and gas exchange in ABA-treated leaves showed that the overestimation of Ci estimated from gas exchange was only partly due to heterogeneity. This overestimation was also attributed to the cuticular transpiration, which largely affects the calculation of the leaf conductance to CO2, when leaf conductance to water is low.

Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Sex offenders in denial : a study into a group of forensic psychologists' attitudes regarding the corresponding impact upon risk assessment calculations and parole eligibility

A considerable proportion of convicted sex offenders maintain a stance of innocence and thus do not engage in recommended treatment programs. As a result, such offenders are often deemed to have outstanding criminogenic needs which may negatively impact upon risk assessment procedures and parole eligibility. This paper reports on a study that aimed to investigate a group of forensic psychologists’ attitudes regarding the impact of denial on risk assessment ratings as well as parole eligibility. Participants completed a confidential open-ended questionnaire. Analysis indicated that considerable variability exists among forensic psychologists in regards to their beliefs about the origins of denial and what impact such denial should have on post-prison release eligibility. In contrast, there was less disparity regarding beliefs about the percentage of innocent yet incarcerated sex offenders. This paper also reviews current understanding regarding the impact of denial on recidivism as well as upon general forensic assessments.

Calculations of capacitive couplings in induction generators to analyse shaft voltage

This paper deals with the analysis of the parameters which are effective in shaft voltage generation of induction generators. It focuses on different parasitic capacitive couplings by mathematical equations, finite element simulations and experiments. The effects of different design parameters have been studied on proposed capacitances and resultant shaft voltage. Some parameters can change proposed capacitive coupling such as: stator slot tooth, the gap between slot tooth and winding, and the height of the slot tooth, as well as the air gap between the rotor and the stator. This analysis can be used in a primary stage of a generator design to reduce motor shaft voltage and avoid additional costs of resultant bearing current mitigation.