Photoionization cross section calculations for the halogen-like ions Kr + and Xe +

Photoionization cross section calculations on the halogen-like ions; Kr + and Xe + have been performed for a photon energy range from each ion threshold to 15 eV, using large-scale close-coupling calculations within the Dirac--Coulomb R -matrix approximation. The results from our theoretical work are compared with recent measurements made at the ASTRID merged-beam set-up at the University of Aarhus in Denmark and from the Fourier transform ion cyclotron resonance trap method at the SOLEIL synchrotron radiation facility in Saint-Aubin, France Bizau et al (2011 J. Phys. B: At. Mol. Opt. Phys. 44 055205) and the advanced light source M{ü}ller (2012 private communication), Aguliar et al (2012 J. Phys.: Conf. Ser . at press). For each of these complex ions our theoretical cross section results over the photon energy range investigated are seen to be in excellent agreement with experiment. Resonance energy positions and quantum defects of the prominent Rydberg resonances series identified in the spectra are compared with experiment for these complex halogen-like ions.

PAMOP: Petascale atomic, molecular and optical collision calculations

Petaflop architectures are currently being utilized efficiently to perform large scale computations in Atomic, Molecular and Optical Collisions. We solve the Schr\"odinger or Dirac equation for the appropriate collision problem using the R-matrix or R-matrix with pseudo-states approach. We briefly outline the parallel methodology used and implemented for the current suite of Breit-Pauli and DARC codes. In this report, various examples are shown from our theoretical results compared with experimental results obtained from Synchrotron Radiation facilities where the Cray architecture at HLRS is playing an integral part in our computational projects.

Dirac R -matrix calculations of electron-impact excitation of neon-like krypton

We have employed the Dirac R -matrix method to determine electron-impact excitation cross sections and effective collision strengths in Ne-like Kr 26+ . Both the configuration-interaction expansion of the target and the close-coupling expansion employed in the scattering calculation included 139 levels up through n = 5. Many of the cross sections are found to exhibit very strong resonances, yet the effects of radiation damping on the resonance contributions are relatively small. Using these collisional data along with multi-configuration Dirac–Fock radiative rates, we have performed collisional-radiative modeling calculations to determine line-intensity ratios for various radiative transitions that have been employed for diagnostics of other Ne-like ions.

Collisional-radiative calculations of He line emission in low-temperature plasmas

We present spectral modeling results for neutral helium. Our underlying atomic data contains radiative transition rates that are generated from atomic structure calculations and electron-impact excitation rates, that are determined from both the standard R-matrix method and the R-matrix with pseudostates RMPS method. In this paper, we focus on transitions of particular importance to diagnostic line ratios. For example, our calculated rate coefficient for the electron-impact transition 1s3s 1S→1s3p 1P, which has a pronounced effect on the 728.1 nm diagnostic spectral line, is found to be in good agreement with previous experimental mea- surements. We also consider transitions from the 1s2 1S ground and 1s2s 3S terms to terms of the n=4 shell. They are found to be affected significantly by coupling of the bound states to the target continuum continuum coupling, which is included in our RMPS calculation, but not in our standard R-matrix calculation. We perform collisional-radiative calculations to determine spectral line intensity ratios for three ratios of particular interest, namely the 504.8 nm/471.3 nm, 492.2 nm/471.3 nm, and 492.2 nm/504.8 nm line ratios. Comparing our results determined from the RMPS excitation rates with those from the standard R-matrix excitation rates, we find that continuum coupling affects the rate coefficients significantly, leading to different values for all three line ratios. We also compare our modeling results with spectral measurements taken recently on the Auburn Helicon plasma device, finding that the ground and metastable populations are not in equilibrium, and that the experimental measurements are more consistent with the 1s2s 3S metastable term populations being short lived in the plasma.

Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

Irrigation scheduling for Sovereign Coronation grapevine based upon evapotranspiration calculations and crop coefficients /

Several irrigation treatments were evaluated on Sovereign Coronation table grapes at two sites over a 3-year period in the cool humid Niagara Peninsula of Ontario. Trials were conducted in the Hippie (Beamsville, ON) and the Lambert Vineyards (Niagara-on-the-Lake, ON) in 2003 to 2005 with the objective of assessing the usefulness of the modified Penman-Monteith equation to accurately schedule vine irrigation needs. Data (relative humidity, windspeed, solar radiation, and temperature) required to precisely calculate evapotranspiration (ETq) were downloaded from the Ontario Weather Network. One of two ETq values (either 100 or 150%) were used in combination with one of two crop coefficients (Kc; either fixed at 0.75 or 0.2 to 0.8 based upon increasing canopy volume) to calculate the amount of irrigation water required. Five irrigation treatments were: un irrigated control; (lOOET) X Kc =0.75; 150ET X Kc =0.75; lOOET X Kc =0.2-0.8; 150ET X Kc =0.2-0.8. Transpiration, water potential (v|/), and soil moisture data were collected each growing seasons. Yield component data was collected and berries from each treatment were analyzed for soluble solids (Brix), pH, titratable acidity (TA), anthocyanins, methyl anthranilate (MA), and total volatile esters (TVE). Irrigation showed a substantial positive effect on transpiration rate and soil moisture; the control treatment showed consistently lower transpiration and soil moisture over the 3 seasons. Transpiration appeared accurately reflect Sovereign Coronation grapevines water status. Soil moisture also accurately reflected level of irrigation. Moreover, irrigation showed impact of leaf \|/, which was more negative throughout the 3 seasons for vines that were not irrigated. Irrigation had a substantial positive effect on yield (kg/vine) and its various components (clusters/vine, cluster weight, and berries/cluster) in 2003 and 2005. Berry weights were higher under the irrigated treatments at both sites. Berry weight consistently appeared to be the main factor leading to these increased yields, as inconsistent responses were noted for some yield variables. Soluble solids was highest under the ET150 and ET100 treatments both with Kc at 0.75. Both pH and TA were highest under control treatments in 2003 and 2004, but highest under irrigated treatments in 2005. Anthocyanins and phenols were highest under the control treatments in 2003 and 2004, but highest under irrigated treatments in 2005. MA and TVE were highest under the ET150 treatments. Vine and soil water status measurements (soil moisture, leaf \|/, and transpiration) confirmed that irrigation was required for the summers of 2003 and 2005 due to dry weather in those years. They also partially supported the hypothesis that the Penman-Monteith equation is useful for calculating vineyard water needs. Both ET treatments gave clear evidence that irrigation could be effective in reducing water stress and for improving vine performance, yield and fruit composition. Use of properly scheduled irrigation was beneficial for Sovereign Coronation table grapes in the Niagara region. Findings herein should give growers some strong guidehnes on when, how and how much to irrigate their vineyards.

Molecular mechanics calculations of tin-bis (triphenylphosphine oxide) complexes

The capability of molecular mechanics for modeling the wide distribution of bond angles and bond lengths characteristic of coordination complexes was investigatecl. This was the preliminary step for future modeling of solvent extraction. Several tin-phosphine oxide COrnI)le:){es were selected as the test groUl) for t.he d,esired range of geometry they eX!libi ted as \-vell as the ligands they cOD.tained r Wllich were c\f interest in connection with solvation. A variety of adjustments were made to Allinger's M:M2 force·-field ill order to inl.prove its performance in the treatment of these systems. A set of u,nique force constants was introduced for' those terms representing the metal ligand bond lengths, bond angles, and, torsion angles. These were significantly smaller than trad.itionallY used. with organic compounds. The ~1orse poteIlt.ial energ'Y function was incorporated for the M-X l')ond lE~ngths and the cosine harmonic potential erlerg-y function was invoked for the MOP bond angle. These functions were found to accomodate the wide distribution of observed values better than the traditional harmonic approximations~ Crystal packing influences on the MOP angle were explored thr"ollgh ttle inclusion of the isolated molecule withil1 a shell cc)ntaini11g tl1e nearest neigl1'bors duri.rlg energy rninimization experiments~ This was found to further improve the fit of the MOP angle.

Molecular mechanics calculations on some phosphine oxide metal complexes in aqueous and organic solvents

Molecular mechanics calculations were done on tetrahedral phosphine oxide zinc complexes in simulated water, benzene and hexane phases using the DREIDING II force field in the BIOGRAF molecular modeling program. The SUN workstation computer (SUN_ 4c, with SPARK station 1 processor) was used for the calculations. Experimental structural information used in the parameterization was obtained from the September 1989 version of the Cambridge Structural Database. 2 Steric and solvation energies were calculated for complexes of the type ZnCl2 (RlO)2' The calculations were done with and without inclusion of electrostatic interactions. More reliable simulation results were obtained without inclusion of charges. In the simulated gas phase, the steric energies increase regularly with number of carbons in the alkyl group, whereas they go through a maximum when solvent shells are included in the calculation. Simulated distribution ratios vary with chain length and type of chain branching and the complexes are found to be more favourable for extraction by benzene than by hexane, in accord with experimental data. Also, in line with what would be expected for a favorable extraction, calculations without electrostatics predict that the complexes are better solvated by the organic solvents than by water.

Reduced local energy calculations on X¹Sigmaâ ½gHâ and 1¹S He /|nGerald F. Thomas. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

The one-electron reduced local energy function, t ~ , is introduced and has the property < tL)=(~>. It is suggested that the accuracy of SL reflects the local accuracy of an approximate wavefunction. We establish that <~~>~ <~2,> and present a bound formula, E~ , which is such that where Ew is Weinstein's lower bound formula to the ground state. The nature of the bound is not guaranteed but for sufficiently accurate wavefunctions it will yield a lower bound. ,-+ 1'S I I Applications to X LW Hz. and ne are presented.

Experimental and Computational Studies on Copper and Hydrobenzoin Derivatives in Catalytic Asymmetric Reactions

The use of theory to understand and facilitate catalytic enantioselective organic transformations involving copper and hydrobenzoin derivatives is reported. Section A details the use of theory to predict, facilitate, and understand a copper promoted amino oxygenation reaction reported by Chemler et al. Using Density Functional Theory (DFT), employing the hybrid B3LYP functional and a LanL2DZ/6-31G(d) basis set, the mechanistic details were studied on a N-tosyl-o-allylaniline and a [alpha]-methyl-[gamma]-alkenyl sulfonamide substrate. The results suggest the N-C bond formation proceeds via a cisaminocupration, and not through a radical-type mechanism. Additionally, the origin of diastereoselection observed with [alpha]-methyl-[gamma]-alkenyl sulfonamide arises from avoidance of unfavourable steric interactions between the methyl substituent and the N -protecting group. Section B details the computationally guided, experimental investigation of two hydrobenzoin derivatives as ligands/ catalysts, as well as the attempted synthesis of a third hydrobenzoin derivative. The bis-boronic acid derived from hydrobenzoin was successful as a Lewis acid catalyst in the Bignielli reaction and the Conia ene reaction, but provided only racemic products. The chiral diol derived from hydrobenzoin successfully increased the rate of the addition of diethyl zinc to benzaldehyde in the presence of titanium tetraisopropoxide, however poor enantioinduction was obseverved. Notably, the observed reactivity was successfully predicted by theoretical calculations.

Calculations Regarding S.D. Woodruff's Property on Ontario Street

Calculations regarding S.D. Woodruff’s property on Ontario Street. 1 page of rough penciled calculations, n.d.

Calculations regarding quantities needed for cutting and ditching

Calculations regarding quantities needed for cutting and ditching (1 page, handwritten), March 19, 1884.

Page of scribbled notes and calculations, 1855

Page of scribbled notes and calculations, 1855.

Sketch of the bridge over Hurst’s Point and calculations about the bridge over the pond at Allenburgh

Sketch of the bridge over Hurst’s Point and calculations about the bridge over the pond at Allenburgh, n.d.

Calculations regarding the bridge crossing Chippawa

Calculations regarding the bridge crossing Chippawa (1 page, penciled calculations), n.d.