Theoretical transition probabilities and lifetimes in nickel-like Se,Y and Sn ions

The 17 levels of the 3 d ¹⁰ , 3 d ⁹ 4 s and 3 d ⁹ 4 p configurations, and the electric-dipole transitions among these levels are calculated for the three nickel-like ions Se⁶⁺, Y¹¹⁺ and Sn²²⁺ by using large-scale multiconfiguration Dirac-Fock wavefunctions. From these computations, the excitation energies and transition probabilities as well as the lifetimes of 3 d ⁹ 4 p levels are derived, including all dominant effects of relativity, correlation and of the rearrangement of the electron density within the same framework. Comparison is made with the scarce number of experimental data and previous semi-empirical computations.     

Note on electron impact excitation for transition of Be-like isoelectronic sequence

Relativistic distorted-wave method was used to calculate the electron impact excitation collision strengths for transitions 2 s2 ¹ S0-2 s 2 p ³ P1 of Be-like isoelectronic ions. The target states were described, respectively, by 10-level, 46-level and 133-level MCDF configuration-expansion. The relativistic continuum orbitals were calculated in the potential field of frozen target-ion charge distribution with semi-classical exchange potential. The influence of the target states on this collision process along the isoelectronic sequence was investigated in the above three MCDF configuration-expansion modes. It was found that the configurations in the n =3 and the n =4 complexes have great influence on both the high and the low Z ions but the influence is relatively small for intermediate Z ions. The latter phenomenon was attributed to competition between opposing correlation and relativistic effects on the collision strengths. Received: 25 February 1998 / Received in final form: 18 June 1998     

Resonance Raman excitation and electronic structure of the single bonded dimers (C ¯60)2 and (C 59N)2

Raman spectra are presented for the single bonded dimeric fullerene (C ₆₀ ^- ) ₂ and compared to optical spectra and Raman spectra of the isostructural and isoelectronic heterofullerene (C₅₉N)₂. The spectra of both materials exhibit strong correlations with respect to splitting, line position, and line intensity. This holds for non resonant excitation with blue and green lasers as well as for the strong resonances observed with red lasers. The latter observation is consistent with a downshift for the electronic transition energies as compared to C₆₀. The absorption edge of thin films of (C₅₉N)₂ was found at 1.4 eV. The three intercage modes were observed at 82, 103, and 111, and at 88, 98, and 106 cm^-1 for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. A surprising difference was found for the position of the pentagonal pinch modes in the two materials as they were observed at 1461 and at 1451 cm^-1, for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. This is interpreted as a consequence of some characteristic differences in the electronic structure of the two compounds. Received 25 January 2000 and Received in final form 10 April 2000     

Relation between proteins tertiary structure, tryptophan fluorescence lifetimes and tryptophan S(o)→(1)L(b) and S(o)→(1)L(a) transitions. Studies on α1-acid glycoprotein and β-lactoglobulin

We measured fluorescence lifetimes and fluorescence spectra (excitation and emission) of tryptophan residues of α₁-acid glycoprotein (three Trp residues) and β-lactoglobulin (two Trp residues) in absence and presence of 450 μM progesterone. Progesterone binds only to α₁-acid glycoprotein. In absence of progesterone, each of the two proteins displays three fluorescence lifetimes. Addition of progesterone induces a partial inhibition of the S _o → ¹ L _a transition without affecting fluorescence lifetimes. The same experiments performed in presence of denatured proteins in 6 M guanidine show that addition of progesterone inhibits partially the S _o → ¹ L _a transition and its peak is 15 nm shifted to the red compared to that obtained for native proteins. However, the S _o → ¹ L _b transition position peak is not affected by protein denaturation. Thus, the tertiary structure of the protein plays an important role by modulating the tryptophan electronic transitions. Fluorescence emission decay recorded in absence and presence of progesterone yields three fluorescence lifetimes whether proteins are denatured or not. Thus, protein tertiary structure is not responsible for the presence of three fluorescence lifetimes. These characterize tryptophan substructures reached at the excited states and which population (pre-exponential values) depend on the tryptophan residues interaction with their microenvironment(s) and thus on the global conformation of the protein.     

Normal Unenhanced Raman Spectra of CO and CH4 Adsorbed on Cobalt(poly)

Abstract

Normal unenhanced Raman spectra (NURS) of low-polarizability CO molecules were observed for the first time on cobalt at R. T. and residual gas pressure. We assign five bands observed between 2030–2130 cm^?1 to linear chemisorbed CO species, while those observed between 1840–2010 cm^?1 have been ascribed to the 2-fold chemisorbed species. The three bands observed between 1740–1830 cm^?1 we believe are due to the 3-fold species. The corresponding fourteen Co-C stretches were observed and assigned. A model based upon electron backdonation is proposed for each of the three structures. NURS were also observed at R. T. for physisorbed CH₄ and assignments are made to the four frequencies of CH_4.     

Topological gauge theories and group cohomology

We show that three dimensional Chern-Simons gauge theories with a compact gauge groupG (not necessarily connected or simply connected) can be classified by the integer cohomology groupH ⁴(BG,Z). In a similar way, possible Wess-Zumino interactions of such a groupG are classified byH ³(G,Z). The relation between three dimensional Chern-Simons gauge theory and two dimensional sigma models involves a certain natural map fromH ⁴(BG,Z) toH ³(G,Z). We generalize this correspondence to topological spin theories, which are defined on three manifolds with spin structure, and are related to what might be calledZ ₂ graded chiral algebras (or chiral superalgebras) in two dimensions. Finally we discuss in some detail the formulation of these topological gauge theories for the special case of a finite group, establishing links with two dimensional (holomorphic) orbifold models.     

Fractional order vs. exponential fitting in UTE MR imaging of the patellar tendon

PurposeQuantification of the T₂¹ relaxation time constant is relevant in various magnetic resonance imaging applications. Mono- or bi-exponential models are typically used to determine these parameters. However, in case of complex, heterogeneous tissues these models could lead to inaccurate results. We compared a model, provided by the fractional-order extension of the Bloch equation with the conventional models.MethodsAxial 3D ultra-short echo time (UTE) scans were acquired using a 3.0 T MRI and a 16-channel surface coil. After image registration, voxel-wise T₂¹ was quantified with mono-exponential, bi-exponential and fractional-order fitting. We evaluated all three models repeatability and the bias of their derived parameters by fitting at various noise levels. To investigate the effect of the SNR for the different models, a Monte-Carlo experiment with 1000 repeats was performed for different noise levels for one subject. For a cross-sectional investigation, we used the mean fitted values of the ROIs in five volunteers.ResultsComparing the mono-exponential and the fractional order T₂¹ maps, the fractional order fitting method yielded enhanced contrast and an improved delineation of the different tissues. In the case of the bi-exponential method, the long T₂¹ component map demonstrated the anatomy clearly with high contrast. Simulations showed a nonzero bias of the parameters for all three mathematical models. ROI based fitting showed that the T₂¹ values were different depending on the applied method, and they differed most for the patellar tendon in all subjects.ConclusionsIn high SNR cases, the fractional order and bi-exponential models are both performing well with low bias. However, in all observed cases, one of the bi-exponential components has high standard deviation in T₂¹. The bi-exponential model is suitable for T₂¹ mapping, but we recommend using the fractional order model for cases of low SNR.     

Conformational Analysis of 2-Methylhexane and 3-Methylhexane

Abstract

Infrared spectra were obtained for 2-methylhexane and 3-methylhexane, and were interpreted with the aid of normal coordinate calculations. It was shown that 2-methylhexane exists in three conformations. Evidence for the presence of three conformations of 3-methylhexane is presented, but a fourth conformer probably exists. Transferred force constant values resulted in an overall average difference between observed and calculated wavenumbers of 4.3 cm^?1, or 0.5%, for seven conformers of these two compounds.     

Experimental Study of Natural Convection from Electrically Heated Vertical Cylinders Immersed in Air

Abstract

An experimental study of laminar steady-state natural convection heat transfer from electrically heated vertical cylinders immersed in air has been undertaken. Three stainless steel (316 SS) test sections of different slenderness ratios were employed. Surface temperature profiles along the vertical cylinders were obtained using miniature thermocouples when the cylinders were heated with different power levels resulting in different total wall heat fluxes. After the mandatory corrections for the radiation heat fluxes were made, three correlation equations relating the local Nusselt number Nu_y with the local modified Rayleigh number Ra^* _y and the position-to-cylinder diameter y/d were developed. The correlation equations are valid for Ra^* _y ≤ 2 × 10¹².     

Probability diffusion in non-Markhovian,non-Gaussian molecular ensembles: A theoretical analysis and computer simulation

A theoretical generalisation of the Fokker/Planck equation for atomic and molecular diffusion is compared with the results of a molecular dynamics simulation of a triatomic molecule ofC _2v symmetry. The molecular dynamics results are non-Markhovian and non-Gaussian in nature, markedly so in the case of the centre of mass linear velocityV. This may be ascertained by simulating the long-time limit of the three dimensional kinetic energy autocorrelation function <V ²(t)V ²(0)>/<V ²(0)V ²(0)>, which falls well below the theoretical Gaussian value of 3/5. By expressing the Mori continued fraction as a multidimensional Markhovian chain of differential equations and expressing this in turn as a non-Gaussian probability-diffusion equation of the Kramers/Moyal type it is possible to account for the simulation results in a qualitative fashion.     

Resonant Ionization Laser Ion Source Project at TRIUMF

Resonant laser excitation and ionisation is one of the most successful tools for the selective production of radioactive ion beams (RIB) at on-line mass separator facilities. TRIUMF plans to augment the current ion sources with a resonant ionisation laser ion source (RILIS), to use the high production yields from the target, as shown by the delivery of 3*10⁴/s ¹¹Li ions from a standard target ion source with surface ionisation. The development and installation of TRIUMF's RILIS (TRILIS) is necessary to provide beams of short lived isotopes that conventional ion sources could not produce in sufficient intensity and purity for nuclear-, and nuclear astrophysics- experiments. A laser system consisting of three tunable titanium–sapphire (TiSa) lasers with frequency doubling and tripling was employed to demonstrate first off-line resonance ionisation of Ga, and is being installed for first on-line test and a run on ⁶²Ga in December 2004.     

On the existence of <Emphasis Type="Bold">1, 3</Emphasis>P <Emphasis Type="Bold">o</Emphasis> resonances in H<Superscript>-</Superscript> between n = 2 and 3 H thresholds

We examine the influence of relativistic and QED effects on the existence of the ^1,3P ^o H^- resonances between n = 2 and 3 hydrogen thresholds, the relativistic and QED corrections and the coupling effects between the high singlet and triplet states are considered as first-order perturbations. We firstly obtain accurate non-relativistic resonant energies and widths of fifteen ¹P ^o resonances, and fifteen ³P ^o resonances. The fifteen ¹P ^o resonances are classified to be ₃ (2, 0) ^- _n ( 4 ? n ? 12) and ₃ (1, 1) ⁺ _n ( 3 ? n ? 8). The fifteen ³P ^o resonances are classified to be ₃ (2, 0) ⁺ _n ( 3 ? n ? 12) and ₃ (1, 1) ^- _n ( 4 ? n ? 8). We found there exist six Feshbach resonances for ₃ (2, 0) ^- _n (¹P ^o ) series, four Feshbach resonances for ₃ (1, 1) ⁺ _n (¹P ^o ) series, seven Feshbach resonances for ₃ (2, 0) ⁺ _n (³P ^o ) series, and three Feshbach resonances for ₃ (1, 1) ^- _n (¹P ^o ) series. Received 22 February 2002 Published online 24 September 2002     

Theoretical design of azaacene-based non-fullerene electron transport material used in inverted perovskite solar cells

ABSTRACT

Inverted perovskite solar cells (PSCs) have attracted much attention due to their low-temperature and solution-based process. Electron transport layers are important components in inverted PSCs. Non-fullerene n-type organic small molecules seem to be more attractive as electron transport layers, because their structures are easy to be synthesised and modified. In this paper, density functional theory and semi-classical Marcus electron transfer theory were used to explore the electron transport properties in three azaacene derivatives, including one experimentally reported molecule, 1,4,9,16-tetrakis((triisopropylsilyl)ethynyl)quinoxalino[2^?,3^?:4^″,5^″]cyclopenta[1^″,2^″,3^″:5^′,6^′]acenaphtho[1^′,2^′:5,6]pyrazino[2,3-b]phenazine (1), and two theoretically designed molecules (2 and 3). Compound 2 is formed by substituting i-Pr groups in compound 1 with H atoms, which is designed to evaluate the effect of i-Pr groups on the electron transport properties. Compound 3 is designed by adding one more benzopyrazine group to the conjugation structure of compound 1. It shows that i-Pr group can increase HOMO and LUMO energy levels and improve solubility in organic solvent and hydrophobicity. Enlarging conjugation can not only decrease LUMO energy level and electron reorganisation energy, but also can increase solubility and electron mobility. So our designed compound 3 is expected to be a potential electron transport material in inverted PSCs.     

Structure determination, valence, and superexchange in the dimerized low temperature phase of α ′ - NaV 2 O 5

We report results of a new analysis for the low-temperature structure of α ^′ -NaV₂O₅ from synchrotron X-ray diffraction experiments. We confirm the existence of two inequivalent ladder structures in each vanadium layer. Based on our structural data we perform a bond-valence calculation for the vanadium sites in the low temperature state. Due to an asymmetric charge ordering we obtain only two different vanadium valences despite the three inequivalent sites. This explains the ⁵¹V-NMR observation of only two resonant peaks in the charge ordered phase. By use of a Slater-Koster method to obtain hopping matrix elements and cluster calculations we obtain effective vanadium-vanadium hoppings which compare well to LDA results. Using these in a cluster calculation we obtain a superexchange of 0.047 eV between electrons on neighbouring rungs of the same ladder for the undistorted phase. For the distorted phase we find a significant alternation in the shifts of the oxygen atoms along the legs of one of the two ladder types which leads to a significant exchange dimerisation δ _J ≈ 0.25. Received 24 November 2000     

The Schiff Base Probe With J-aggregation Induced Emission for Selective Detection of Cu2+

Here, three Schiff bases 3a-c, differing by the substitutions (–H, –Cl, and –N(CH₃)₂) on the phenyl ring, have been designed and synthesized via the reaction of ortho-aminophenol with benzaldehyde, 2,4-dichlorobenzaldehyde and para-dimethylamine benzaldehyde in 1:1 molar ratio with favourable yields of 89–92%, respectively. Their structural characterizations were studied by FT-IR, NMR, MALDI-MS and elemental analysis. The fluorescence behaviours of compounds 3a and 3b exhibited a severe aggregation caused quenching (ACQ) effect in EtOH/water system. On the contrary, compound 3c had an obvious J-aggregation induced emission (AIE) feature in EtOH/water mixture (v/v?=?1:1), and exhibited excellent sensitivity and anti-interference towards Cu²⁺ with the limit of detection (LOD) of 1.35?×?10^–8 M. Job’s plot analysis and MS spectroscopic study revealed the 2:1 complexation of probe 3c and Cu²⁺. In addition, probe 3c was successfully applied to the determination of Cu²⁺ in real aqueous samples.

     

Properties of doubly excited states of H- and He associated with the manifolds from N = 6 up to N = 25

This paper discusses theory and results on ¹P⁰ doubly excited states (DES) in He and in H^- of very high excitation, up to the N = 25 manifold. Our calculations employed full configuration interaction (CI) with large hydrogenic basis sets and produced correlated wavefunctions for the four lowest roots at each hydrogenic manifold by excluding open channels and the small contribution of series belonging to lower thresholds. The suitability of the hydrogenic basis sets for such calculations is justified, apart from their practicality, by the fact that, by computing from them natural orbitals, the results were shown to be the same with those of earlier multiconfigurational Hartree-Fock (MCHF) calculations on low-lying DES. In total, 160 states were computed, most of them for the first time. Their energy spectrum should be of use to possible future photoabsorption experiments. For certain low-lying DES up to N = 13, for which previous reliable results are available, comparison of the calculated energies shows good agreement. The correlated wavefunctions contain systematically chosen single and double excitations from each hydrogenic manifold of interest. From their analysis, we determined the “goodness" of different quantum numbers and the geometry (average angles and radii) as a function of excitation. For the Sinano lu-Herrick ( K , T ) classification scheme, whose basis is a restricted CI with hydrogenic functions and which has thus far been tested only on low-lying DES, we established that, whereas T remains a good index as energy increases, K does not. Consequently, a more flexible than K quantum number is needed in order to account for most of the additional correlation. This number, represented by F = N - K - 1, where N and K are not good numbers anymore, produces consistently a much higher degree of purity than the ( K , T ) scheme does, especially as N increases and as the relative significance of various virtual excitations due to electron correlation increases. Among the four states of each manifold, in all cases in H^- and in most cases in He, the three are of the intrashell type and one is of the intershell type with ( F , T ) = (0, 0). The lowest intrashell states and the lowest intershell states exhibit a wide angle geometry tending to 180 ^° as N ↦∞. Received 10 September 2001 and Received in final form 12 November 2001     

Luminescence characteristics of ultraviolet upconversion from Er 3 + :YAG crystal by Ar + laser (488 nm) excitation

Ultraviolet and violet upconversion signals at 271 nm, 317 nm, 381 nm and 407 nm were observed when an erbium-doped YAG crystal was pumped by an Ar⁺ laser (488 nm). The dependence of intensity of luminescence emitting from the ⁴S _3/2 state and the ²P _3/2 state on pump power (I) was experimentally investigated. Changes from I¹ down to I ^1/2 for the ⁴S _3/2 state and from I² down to I¹ for the ²P _3/2 state were observed. The upconversion mechanism was discussed by means of the rate equations. It appears that energy-transfer upconversion (ETU) is a dominant process for the Er³⁺:YAG crystal used in our experiment. Received 20 March 2001 and Received in final form 11 July 2001     

Influence of Co(III) Polypyridyl Complexes on Luminescence Behavior,DNA Binding,Photocleavage, Antimicrobial Activity and Molecular Docking Studies

A new ligand FIPB?=?5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)furan-2-yl-2-boronic acid, having three cobalt(III) polypyridyl complexes [Co(phen)₂(FIPB)]³⁺(1) {FIPB?=?5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)furan-2-yl-2-boronic acid}, (phen?=?1,10-Phenanthroline), [Co(bpy)₂(FIPB)]³⁺(2) (bpy?=?2,2’bipyridyl), [Co(dmb)₂(FIPB)]³⁺(3) (dmb?=?4, 4′-dimethyl 2, 2′-bipyridine) have been synthesized and characterized by elemental analysis, ES-MS,¹H-NMR, ¹³C-NMR, UV-Vis and FTIR. Their DNA binding behavior has been explored by various spectroscopic titrations and viscosity measurements, which indicated that all the complexes bind to calf thymus DNA by means of intercalation with different binding strengths. The binding properties of these all three complexes towards calf-thymus DNA (CT-DNA) have been investigated by UV-visible, emission spectroscopy and viscosity measurements.The experimental results suggested that three Co(III) complexes can intercalate into DNA base pairs,but with different binding affinities. Photo induced DNA cleavage studies have been performed and results indicate that three complexes efficiently cleave the pBR322-DNA in different forms. The three synthesized compounds were tested for antimicrobial activity by using Staphylococcus aureus and Bacillus subtilis organisms, these results indicated that complex 1 was more activity compared to other two complexes against both tested microbial strains. The in vitro cytotoxicity of these complexes was evaluatedby MTT assay, and complex 1 shows higher cytotoxicity than complex 2 and 3 on HeLa cells.

     

Fluorescence Study of the Relaxation Process in Excited Hetarylthiazole Cations

The absorption and fluorescence spectra of five cations protonated at the quinolyl nitrogen atom (IH⁺–VH⁺) and one ethylated (IEt⁺) cation were investigated. For these compounds (except VH⁺) both an anomalously large fluorescence Stokes shift (up to 238 nm) and a large short-wavelength fluorescence shift (up to 145 nm) at decreasing temperatures (down to 77 K) were observed. This is not the case for unprotonated molecules. The ground-state conjugation between quinolyl and another molecular fragment was found for II, IH⁺, IIH⁺, and IEt⁺. The relaxation process of excited cations is medium viscosity and temperature dependent. The experimental results are explained in terms of excited-state structural relaxation.     

69,71Ga NMR studies of a superconducting Ga 84 cluster compound

We present ^69,71Ga-NMR experiments on microcrystalline samples of the recently discovered supramolecular compound Ga ₈₄ [ N ( SiMe ₃ ) ₂ ] ₂₀ Li ₆ Br ₂ ( thf ) ₂₀ ^. 2 toluene, which is composed of ligand-coordinated Ga₈₄ metal clusters, packed together in a fully ordered crystalline matrix. The compound is highly conducting and even shows superconductivity below T _c ~ 7.2 K. Our preliminary results between 10-300 K show a metallic-like behavior: the nuclear spin-lattice relaxation rate T ₁ ^-1 follows the Korringa law ⁶⁹ ( T ₁ T ) ^-1 = 0.36 s ^-1 K ^-1 , but with a relaxation rate approximately three times smaller than in bulk -Ga metal. No quantum-size effects are observed, the Korringa law being followed down to 10 K, whereas the quantum-gaps for individual clusters should amount to ~ 10 ³ K. These results therefore suggest a transport process based on intermolecular charge transfer, similar as in alkali-doped fullerenes and silicon-clathrates.