Oscillator strengths and transition probabilities for the W xlv ion

In this paper we present oscillator strengths and transition probabilities for W xlv transitions between levels arising from configurations 3d¹⁰4s²,4p²,4d², 3d¹⁰4k4l (k = s,p,d,f and l = p,d,f), 3d⁹4s²4l (l = p,d,f) and 3d⁹4s4p². The model used to calculate these contained all configurations which can be constructed from the available orbitals (up to n = 4), with either a 3d¹⁰ or 3d⁹ core. The calculations were performed with the configuration interaction CIV3 program with the inclusion of relativistic effects achieved through the use of the Breit-Pauli approximation. We compare our ab initio energy levels, oscillator strengths and transition rates with other experimental and theoretical values available in the literature. There is generally good agreement when only levels with 3d¹⁰ cores are considered. The literature is sparse for levels in which the 3d-subshell is opened: for the majority of the fine-structure lines considered, there is either no comparison data available or substantial differences are found. This paper also investigates how the inclusion of relativistic effects can result in a significant redistribution of the oscillator strength from the LS calculations.

Identifying the distinct features of geometric structures for hole trapping to generate radicals on rutile TiO2(110) in photooxidation using density functional theory calculations with hybrid functional

Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.

Radiative rates for E1, E2, M1, and M2 transitions in the Br-like ions Sr IV, Y V, Zr VI, Nb VII, and Mo VIII

Energies and lifetimes are reported for the lowest 375 levels of five Br-like ions, namely SrIV, YV, ZrVI, NbVII, and MoVIII, mostly belonging to the 4s²4p⁵, 4s²4p⁴4ℓ, 4s4p⁶, 4s²4p⁴5ℓ, 4s²4p³4d², 4s4p⁵4ℓ, and 4s4p⁵5ℓ configurations. Extensive configuration interaction has been included and the general-purpose relativistic atomic structure package (grasp) has been adopted for the calculations. Additionally, radiative rates are listed among these levels for all E1, E2, M1, and M2 transitions. From a comparison with the measurements, the majority of our energy levels are assessed to be accurate to better than 2%, although discrepancies between theory and experiment for a few are up to 6%. An accuracy assessment of the calculated radiative rates (and lifetimes) is more difficult, because no prior results exist for these ions.

Radiative rates for E1, E2, M1, and M2 transitions among the 3s23p5, 3s3p6, and 3s23p43d configurations of Cl-like W LVIII

We report calculations of energy levels, radiative decay rates, and lifetimes for transitions among the 3s²3p⁵, 3s3p⁶, and 3s²3p⁴3d configurations of Cl-like W LVIII. The general-purpose relativistic atomic structure package (GRASP) has been adopted for our calculations. Comparisons are made with the most recent results of Mohan et al. (Can. J. Phys. 92, 177 (2014). doi:10.1139/cjp-2013-0348) and discrepancies in lifetimes are noted, up to four orders of magnitude in some instances. Our energy levels are estimated to be accurate to better than 0.5%, whereas results for radiative rates and lifetimes should be accurate to better than 20%.

Assessment of Atomic Data: Problems and Solutions

For the reliable analysis and modeling of astrophysical, laser-produced, and fusion plasmas, atomic data are required for a number of parameters, including energy levels, radiative rates, and electron impact excitation rates. Such data are desired for a range of elements (H to W) and their many ions. However, measurements of atomic data, mainly for radiative and excitation rates, are not feasible for many species, and therefore, calculations are needed. For some ions (such as of C, Fe, and Kr), there is a variety of calculations available in the literature, but often, they differ significantly from one another. Therefore, there is a great demand from the user community to have data "assessed" for accuracy so that they can be confidently applied to the modeling of plasmas. In this paper we highlight the difficulties in assessing atomic data and offer some solutions for improving the accuracy of calculated results.

Electron impact excitation of Be-like ions: a comparison of DARC and ICFT results

Emission lines of Be-like ions are frequently observed in astrophysical plasmas, and many are useful for density and temperature diagnostics. However, accurate atomic data for energy levels, radiative rates (A-values) and effective electron excitation collision strengths ($\Upsilon$) are required for reliable plasma modelling. In general it is reasonably straightforward to calculate energy levels and A- values to a high level of accuracy. By contrast, considerable effort is required to calculate $\Upsilon$, and hence it is not always possible to assess the accuracy of available data. Recently, two independent calculations (adopting the $R$-matrix method) but with different approaches (DARC and ICFT) have appeared for a range of Be-like ions. Therefore, in this work we compare the two sets of $\Upsilon$, highlight the large discrepancies for a significant number of transitions and suggest possible reasons for these.

Seasonal and geographical differences in aflatoxin exposures in Senegal

The aim of the study was to determine the geographical and seasonal variations in aflatoxin dietary exposure levels in adults from Senegal. A total of 168 adults (50% male) were recruited from three districts: Nioro du Rip (n=90), located in the Sudan Savannah agro-ecological zone where rainfall is sufficient for groundnut growth; Saint-Louis (n=40) and Mboro (n=38), located in the Sahel zone where groundnuts are produced under irrigated conditions. Diet information and samples were collected at groundnut harvest and post-harvest seasons. Plasma aflatoxin-albumin adducts (AF-alb) and total aflatoxin in household groundnut samples were measured by ELISA and a quantitative thin layer chromatography method, respectively. The blood AF-alb geometric mean was 45.7 pg/mg albumin (range 5.5-588.2 pg/mg). Nioro du Rip had a higher AF-alb level at harvest than Saint-Louis and Mboro (80.0 vs 15.6 and 33.3 pg/mg, P<0.001). Similar trends were observed at post-harvest (P<0.05). Seasonal trends were not consistent across the districts as Nioro du Rip had a higher AF-alb level at harvest than post-harvest (80.0 vs 58.6 pg/mg, P=0.026), whereas Saint-Louis had a higher level at post-harvest than harvest (25.6 vs 15.6 pg/mg, P=0.032). It is clear that aflatoxin exposure is prevalent in adults from Senegal and that season and geographical location are strong determinants of aflatoxin exposure.

Electron-impact excitation of open d-shell ions

Astrophysics is driven by observations, and in the present era there are a wealth of state-of-the-art ground-based and satellite facilities. The astrophysical spectra emerging from these are of exceptional quality and quantity and cover a broad wavelength range. To meaningfully interpret these spectra, astronomers employ highly complex modelling codes to simulate the astrophysical observations. Important input to these codes include atomic data such as excitation rates, photoionization cross sections, oscillator strengths, transition probabilities and energy levels/line wavelengths. Due to the relatively low temperatures associated with many astrophysical plasmas, the accurate determination of electron-impact excitation rates in the low energy region is essential in generating a reliable spectral synthesis. Hence it is these atomic data, and the main computational methods used to evaluate them, which we focus on in this publication. We consider in particular the complicated open d- shell structures of the Fe-peak ions in low ionization stages. While some of these data can be obtained experimentally, they are usually of insufficient accuracy or limited to a small number of transitions.

Electron impact excitation of the Fe-peak ions Ni III and Ni IV

Accurate determination of electron excitation rates for the Fe-peak elements is complicated by the presence of an open 3d-shell in the description of the target ion, which can lead to hundreds of target state energy levels. Furthermore, the low energy scattering region is dominated by series of Rydberg resonances, which require a very fine energy mesh for their delineation. These problems have prompted the development of a suite of parallel R-matrix codes. In this work we report recent applications of these codes to the study of electron impact excitation of Ni III and Ni IV.

Bacterial Biomass along the Kuroshio Extension

Senior thesis written for Oceanography 445

Regulation of gene expression by SnRK1 kinases and miRNAs during the plant stress response

Dissertation presented to obtain the Ph.D degree in Plant Physiology

Large amplitude motions in the S1 state of formic acid /

A detailed theoretical investigation of the large amplitude motions in the S, excited electronic state of formic acid (HCOOH) was done. This study focussed on the the S, «- So electronic band system of formic acid (HCOOH). The torsion and wagging large amplitude motions of the S, were considered in detail. The potential surfaces were simulated using RHF/UHF ab-initio calculations for the two electronic states. The energy levels were evaluated by the variational method using free rotor basis functions for the torsional coordinates and harmonic oscillator basis functions for the wagging coordinates. The simulated spectrum was compared to the slit-jet-cooled fluorescence excitation spectrum allowing for the assignment of several vibronic bands. A rotational analysis of certain bands predicted that the individual bands are a mixture of rotational a, b and c-type components.The electronically allowed transition results in the c-type or Franck-Condon band and the electronically forbidden, but vibronically allowed transition creates the a/b-type or Herzberg-Teller components. The inversion splitting between these two band types differs for each band. The analysis was able to predict the ratio of the a, b and c-type components of each band.

The near ultraviolet absorption spectrum of phosgene /

The near ultraviolet absorption of phosgene has been assigned to a * 1 1 ~.--n, A;-- Al electronic transition from vapour phase spectra recorded under conditions of high resolution and low_t~mperature. Progressions in Vi, v2' V3' V4 and V4 ha\1e been identified in the spectrum and have been analyzed in terms of vibronic transitions between a planar ground and a nonplanar excited state. A ba~rier height of 3170 cm~l:and a nona planar equilibrium angle of 32.5 were calculated for the upper state from a fit of the energy levels of a Lorentzian-guadratic potential func- ~ion to the observed levels of V 4 . ' ~he false ori- 3in, 41 0 , of the spectrum has been assigned to the band at 33,631 cm -1 . An oscillator strength of -3 1 . 1 f = 1. a x 10 has been obtained for the A - A 2 1 transition.

Rotation-electronic interaction in the 3p-complex Rydberg state of water

An energy theory is formulated for the rotational energy levels in a p-complex Rydberg state of an asymmetric top molecule of symmetry C2v. The effective Hamiltonian used consists of the usual rigid rotor Hamiltonian augmented with terms representing electronic spin and orbital angular momentum effects. Criteria for assigning symmetry species to the rotational energy levels, following Houganfs scheme that uses the full molecular group,are established and given in the form of a table. This is particularly suitable when eigenvectors are calculated on a digital computer. Also, an intensity theory for transitions to the Rydberg p-complex singlet states is presented and selection rules in terms of symmetry species of energy states are established. Finally, applications to HpO and DpO are given.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.