Reparameterization of Semiempirical Techniques to Remove Anomalous Energy Minima

Semiempirical molecular orbital calculations have been shown to predict double minima potential surfaces which are not confirmed by further experimental or theoretical evidence.¹ These same techniques predict barriers to internal rotation which are not only in large error but may not even follow the experimental trends.² These discrepancies offer a large decrease in self confidence for the application of these techniques to molecular systems where direct experimental evidence is not available, and these are often the circumstances where one wants a theory to be used. Therefore, our research group is in the process of reparameterizing the procedure INDO³ to yield barriers to internal rotation, bond angles, and bond lengths within reliable confidence limits. During this process of determining new parameters we have observed that some sets of parameters will also remove the anomalous energy minima predicted by the original INDO parameters. To illustrate this we consider in this paper the molecule CO₂.     

Polarized single top quark production in eγ collision and anomalous Wtb couplings

We investigate the potential of eγ collisions to probe anomalous Wtb couplings via the polarized single top quark production process e⁺γ→tb̄ν_ē. We find 95% confidence level limits on the anomalous coupling parameters F_2L and F_2R with an integrated luminosity of 500 fb^-1 and , 1 and 1.5 TeV energies. The effects of top quark spin polarization on the anomalous Wtb couplings are discussed. It is shown that polarization leads to a considerable improvement in the sensitivity limits. PACS 14.65.Ha; 13.88.+e     

Bosonic stimulation of cold 1s excitons into a harmonic potential minimum in Cu2O

The density distribution of cold exciton clouds generated into a strain-induced potential well by two-photon excitation in Cu₂O is studied at 2 K. We find that an anomalous spike, which can be interpreted as accumulation of the excitons into the ground state, emerges at the potential minimum. The accumulation can be due to stimulated scattering of cold excitons, mediated by acoustic phonon emission. The possibility of the formation of the thermodynamic Bose-Einstein condensate of paraexcitons is discussed.     

Temperature dependence of the work function of Bi2Sr2CaCu2O8 single crystal cleaved at low temperature

We measured the anomalous change in the work function of Bi₂Sr₂CaCu₂O₈ around a critical temperature (T_c ≈ 85 K). The work function becomes a minimum at T_c; the work function decreases in a normal-conductive state and then increases in a superconductive state as the temperature decreases. An increase in the work function for a transition from a normal-conductive state to a superconductive state at 0 K is about 9 meV. The contribution of the chemical potential and the surface dipole barrier to the work function are discussed.     

Adiabatic and non-adiabatic corrections to properties of the hydrogen molecular cation and its isotopomers: dissociation energies and bond lengths

A study is presented of adiabatic and non-adiabatic corrections to the dissociation energies and bond lengths of H⁺ ₂, D⁺ ₂ and HD⁺ in vibration-rotation levels of their ground electronic states, with particular attention to isotopic scaling. In previous work (MOSS, R. E., 1999, Molec. Phys., 97, 1) on rotationless levels, an anomalous non-adiabatic correction to the bond length was found for v = 20, N = 0 of HD⁺. Other levels close to dissociation are identified that display anomalous non-adiabatic corrections to the dissociation energies and to the bond lengths. The source of these anomalies is discussed.     

Characteristics of Ti0.97Co0.03O2:Sb0.01 dilute magnetic semiconducting thin films deposited at 500 °C by pulsed laser deposition

Epitaxial Ti_0.97Co_0.03O₂:Sb_0.01(TCO:Sb) films were deposited on R-Al₂O₃ (1 1 0 2) substrates at 500 °C in various deposition pressures by pulsed laser deposition. The solubility of cobalt within the films increases with decreasing deposition pressure at a deposition temperature of 500 °C. The TCO:Sb films deposited at 5×10⁻⁶ Torr exhibit a p-type anomalous Hall effect having a hole concentration of 6.1×10²²/cm³ at 300 K. On the other hand, films deposited at 4×10⁻⁴ Torr exhibits an n-type anomalous Hall effect having an electron concentration of about 1.1×10²¹/cm³. p- or n-type DMS characteristics depends on the change of the structure of TCO:Sb films and the solubility of Co is possible by controlling the deposition pressure.     

CNDO studies of Y-Ba-Cu-O superconductors I. Comparative study of CuO n polyhedra

Electronic structure of CuO _n ^q clusters (n=2, 4, 5) is calculated in experimental geometries of YBa₂Cu₃O₆ and YBa₂Cu₃O₇ for various formal oxidation states of Cu modelled by total cluster charges,q, both by non-relativistic and by quasi-relativistic CNDO and INDO methods. The results for standard Cu (d¹⁰s¹p⁰) as well as for nonstandard Cu (d⁹s²p⁰) reference configurations are compared from the point of view of the Cu oxidation state. Cu (III) oxidation state seems to be improbable.     

1π→1π* Ultraviolet Absorption Bands and Electronic Charge Transfers in Singlet Excited States of Sulfur Aromatic Heterocycles

Abstract

Indoline‐2‐thione (BC), benzimidazole‐2‐thione (BN), benzoxazole‐2‐thione (BO), and benzothiazole‐2‐thione (BS) define an interesting series of aromatic compounds containing a NCS synthonic unit in a heterocyclic ring of five centers, substituted by atomic centers of the type C, N, O, or S, where the main electronic absorption bands are localized in the spectral range of ultraviolet A or B.

The first two singlet electronic transitions of this series, ¹S₀→¹S₁(n,π*) and ¹S₀ → ¹S₂(π,π*), determine the main spectroscopic characteristic of these compounds in order to be used as potential photochemical actinometers of solar ultraviolet radiation. Furthermore, the second electronic transition, localized in the 270–360 nm ultraviolet spectral range, presents a hipsochromic spectral shift as function of the electronic nature of the heteroatomic centers in the heterocyclic ring.

In order to determine a spectroscopic assignment of the main absorption bands in aqueous solution and analyze the effect of the substituent on the electronic charge distributions in the ground and the first two singlet excited electronic states, we have used a semiempirical molecular orbital calculation in the INDO/S‐CIS approach. On the other hand, we have carried out a molecular orbital calculation in the AM1 framework, in order to determine the energetic stability of the thiones with respect to the thiol compounds.     

双荷电双原子分子的新解析势能函数

提出了能更好反映双荷电双原子分子势能曲线特点的新解析势能函数，并推导出了相应的二、三、四阶力常数计算公式；作为新函数的应用实例，给出了BH2+, He22+ 和HF2+等分子离子的解析势能函数，力常数和光谱数据。     

Calculation of electronic spectra of porphin and its derivatives by a modified INDO/S method

Quantum-chemical calculations of excited electronic states of porphin (H₂P) and Mg-porphin (MgP) have been carried out in the framework of the INDO/S method with varying off-diagonal matrix elements of the one-electron Hamiltonian {ie027-01} and electron-electron interaction integrals {ie027-02} as functions of the internuclear distance. It has been found that a simultaneous increase in the π-type overlap factor for {ie027-03} and decrease in the {ie027-04} integrals, as compared with {ie027-05} calculated by the Nishimoto-Mataga formula, make it possible to reproduce the positions of the Q-and B-transitions in the experimental absorption spectrum with a precision of ∼300 cm⁻¹. In this case, the N_x-transition intensity of the H₂P molecule is halved, which means that only two B-transitions should be related to the Soret band as in the four-orbital model. Using the proposed parameterization (INDO/Sm), electronic spectra have been calculated for a number of porphyrin compounds including chlorine, bacteriochlorin, tetrabenzoporphin, and tetraazaporphin. The results obtained agree with the experimental data to an accuracy of 300–700 cm⁻¹ whereas the accuracy of the standard INDO/S calculation is no better than 3000 cm⁻¹. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 28–35, January–February, 2008.     

Three-nucleon calculations without the explicit use of two-body potentials

Using as two-nucleon interaction input the ³S₁-³D₁ and ¹S₀ partial waves, the Faddeev equations are solved for the three-nucleon bound state. The ³S₁³D₁T-matrix is calculated from the Reid potential. Avoiding the usual potential fit, the ¹S₀T-matrix is directly continued off-shell and is constructed consistent with the ¹S₀ phase shift of elastic two-nucleon scattering. The off-shell part of the ¹S₀T-matrix is parametrized and with this parametrization the dependence of the three-nucleon bound-state properties is studied. As a result it is found that the binding energy varies only between 6.2 MeV and 6.8 MeV, while the minimum in the charge form factor for electron scattering from ³He lies between 12.9 fm^?2 and 18.7 fm^?2. The larger (smaller) ³He binding energy is accompanied by a ³He charge form factor whose minimum is at larger (smaller) momentum transfers.     

Mössbauer Study of Ferrite-garnets as Matrixes for Disposal of Highly Radioactive Waste Products

Mössbauer study of synthesized ferrite-garnet samples containing Zr, Th, Ce and Gd of the following composition: 1C – Ca_{2, 5} Ce_{0, 5} Zr₂ Fe₃ O₁₂, 2C – Ca_{1, 5} GdCe_{0, 5} ZrFeFe₃ O₁₂, 1T – Ca_{2, 5} Th_{0, 5}Zr₂ Fe₃ O₁₂ and 2T – Ca_{1, 5} GdTh_{0, 5} ZrFeFe₃ O₁₂ are carried out. As a result of ⁵⁷Fe Mössbauer study it is found that iron atoms in all investigated samples of garnets are in a trivalent state. The analysis of experimental Mössbauer spectra definitely specifies a various structural state of iron atoms in two investigated groups of samples: 1T, 1C and 2T, 2C. X-ray study have shown that 1T and 1C garnet samples crystallize in tetragonal space group I4₁/acd, but 2T and 2C samples crystallize in cubic space group Ia3d.     

The Skyrme model with a U*(1) gauged Wess‐Zumino term in a noncommutative spacetime

The Skyrme model is generalized for a noncommutative spacetime with the Weyl‐operators of SU(2) matrices and the corresponding star‐product. The unitary condition and the topological current can be extended to star‐exponential matrices. The Wess‐Zumino term which breaks unphysical symmetries of the Skyrme action is gauged with the U_*(1) group to allow for electromagnetic processes in a noncommutative spacetime. Apart from corrections to the anomalous decay γ→π⁰π⁺π^– in commuting spacetime, the additional anomalous process γ→π⁰π⁰π⁰ is found in the U_*(1) gauged Wess‐Zumino action for a noncommutative spacetime.     

The short distance behaviour of the anomalous magnetic moment of the electron

The effective anomalous magnetic moment of the electron vanishes at short distances because the electrodynamic form factor F₂(q²) vanishes for |q²| → ∞. The effective potential due to the interaction between the anomalous magnetic moment and the Coulomb field of a nucleus only diverges logarithmically at short distances, and not, as might naively be expected, quadratically. There are no other bound states of an electron in a Coulomb field than the well-known atomic states. In particular, there is no room for high mass resonances emulating the ψ as suggested by Barut and Kraus.     

Scintillation and anomalous emission in elpasolite Cs2LiLuCl6:Ce

The luminescence and scintillation properties of Cs₂LiLuCl₆:0.5%Ce³⁺ are presented. Special attention is devoted to a 9.4 ns fast emission at 275 nm that can only be excited via the highest cubic field 5d_e state of Ce. Contrary to Cs₃LuCl₆ and Cs₂LiYCl₆, where the same type of fast emission was observed, the emission in Cs₂LiLuCl₆ is still observed at room temperature. Assuming that the 5d_e state is located inside the host conduction band (CB), we propose that the emission originates from a mixed state at or just below the bottom of the CB and ends at the 4f ground state of Ce³⁺. To proof this model we studied the thermal quenching of the anomalous luminescence and performed X-ray photoelectron spectroscopy. A model for a temperature-activated energy transfer from the anomalous state to the lowest 5d_t excited state of Ce³⁺ explains most of the results. Besides the 275 nm emission, the material shows 5d_t-4f Ce³⁺ emission at 370 and 406 nm and 2 ns fast core-valence luminescence when excited with 16-22 eV photons. The scintillation properties of Cs₂LiLuCl₆:Ce are briefly discussed.     

The double minimum potential in the spectrum of HCOF

Rotational analyses conducted together with theoretical calculations of the relative intensities for vibronic transitions involving an excited state with a double minimum potential have led to confirmation of the previously established vibrational analysis and to a full characterization of the double-minimum potential function. The origin band at 37 490 cm^?1 has been shown to consist of the two transitions 6₀⁰ (true origin) and 6₀¹ separated by only 0.5 cm^?1 and with rotational structures corresponding to type C, allowed, and hybrid type AB, Herzberg-Teller induced, bands respectively.     

托卡马克的反常电子输运定标律

本文假设导致托卡马克反常电子输运的主要机制为由温度梯度所驱动的重整化电子磁漂移波。通过求解动力学过程自洽地导出了反常电子输运系数的定标律:D^(T)=(c/ω_pe)²{((v_e/qR)²/2π+(v_{c/2)²)^1/2-vc/2}。它在数值上与现有实验给出的AIcator定标律符合。在无碰撞(vc→0)情况下与Ohkawa定标津一致。同时分析了该定标律与Alcator定标律的偏离,并由此讨论了强磁场欧姆加热托卡马克达到热核点火的可能性。 关键词：}     

Analysis of elastic and inelastic α-12C data (Eα = 1.37 GeV) with a multiple diffraction model

High-energy inelastic α-¹²C distributions are analyzed with an eikonalized DWIA. Using an elastic phase function parametrized to fit the elastic α-¹²C distribution and further inelastic form factors from electron scattering data, we obtained reasonable agreement for the 2⁺ and 0⁺ distributions. We observe and discuss the anomalous absence of a predicted diffraction minimum in the 3^? distribution as is also the case for the 1 GeV p-¹²C data.     

Co-silicide layers studied by Mössbauer spectroscopy and Rutherford backscattering spectroscopy

Co-silicides were prepared with several techniques, such as annealing of evaporated Co-layers on a Si-substrate (silicide surface layers) and annealing of Co-implanted Si (buried silicide layers). By adding some⁵⁷Co to the stable⁵⁹Co, the formation of the various Co-silicides could clearly be followed as a function of annealing temperature by means of Mössbauer spectroscopy. In the case of surface silicide layers, Co₂Si, CoSi and CoSi₂ were formed subsequently. In the case of buried layers however, CoSi₂ was the only crystalline phase that could be observed. In both cases, the CoSi₂ spectra showed an anomalous side resonance. Moreover, it was found that when⁵⁷Fe was implanted (instead of⁵⁷Co), a drastic increase in the intensity of this side resonance could be detected by CEMS.     

Phenyl substituted Mg porphyrazines: The effect of annulation of a chalcogen-containing heterocycle on the spectral-luminescent properties

We have performed complex experimental and theoretical investigations of the spectral-luminescent properties and electronic structure of new phthalocyanine analogs, Mg octaphenylporphyrazine and its derivatives with an annulated thiadiazole or selenadiazole ring instead of two phenyl groups. Fluorescence characteristics have been determined at 293 and 77 K: emission, excitation, and fluorescence polarization spectra; fluorescence quantum yield ?? _F , and lifetime ?? _F . Annulation of a five-membered chalcogen-containing heterocycle leads to splitting of the long-wavelength absorption band Q(0-0) and to the bathochromic shift of its longest wavelength component Q _x (0-0), which increase upon passage from S to Se. At the same time, the fluorescence quantum yield ?? _F and lifetime ?? _F decrease, which is related to the intramolecular heavy-atom effect. The geometric structure of the ground state of the Mg porphyrazine molecules has been determined based on the density functional theory (DFT), and excited electronic states have been calculated with modified parametrization of the INDO/S method, INDO/Sm. Semiquantitatively, the calculated level positions of the lowest Q states and spectral shifts of Mg octaphenylporphyrazine and S-derivative agree with experimental data. For the range of the Soret band, calculated transition energies and their intensity distributions substantially depend on the dihedral angle ?? between a phenyl ring and porphyrazine macrocycle. We show that, based on calculations at the angle ?? = 60°, bands in the observed absorption spectra can be assigned with an accuracy of ??2000 cm^?1.