Electronic states of neutral and ionized tetrahydrofuran studied by VUV spectroscopy and ab initio calculations

The electronic spectroscopy of isolated tetrahydrofuran (THF) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 5.8–10.6 eV with absolute cross-section measurements derived. In addition, an electron energy loss spectrum was recorded at 100 eV and 10° over the 5–11.4 eV range. The He(I) photoelectron spectrum was also collected to quantify ionisation energies in the 9–16.1 eV spectral region. These experiments are supported by the first high-level ab initio calculations performed on the excited states of the neutral molecule and on the ground state of the positive ion. The excellent agreement between the theoretical results and the measurements allows us to solve several discrepancies concerning the electronic state spectroscopy of THF. The present work reconsiders the question of the lowest energy conformers of the molecule and its population distribution at room temperature. Electronic supplementary material  Supplementary Online Material     

Hole interactions with molecular vibrations on DNA

We report on a study of the interactions between holes and molecular vibrations on dry DNA using photoinduced infrared absorption spectroscopy. Laser photoexcited holes are found to have a room-temperature lifetime in excess of tau > 1 ms, clearly indicating the presence of localization. However, from a quantitative model analysis of the frequency shifts of vibrational modes caused by the holes, we find the hole-vibrational coupling constant to be relatively small, lambda approximately 0.2. This interaction leads to a change in the conformational energy of DeltaE0 approximately 0.015 eV, which is too small to cause self-trapping at room temperature. We conclude that, at least in the dry (A) form, DNA is best understood in terms of a double chain of coupled quantum dots arising from the pseudorandom chain sequence of base pairs, in which Anderson localization prevents the formation of a metallic state.     

Angle Integrated Photoemission Study of SmO0.85F0.15FeAs

The electronic structure of the new superconductor SmO_1-xF_xFeAs (x=0.15) is studied by angle-integrated photoemission spectroscopy. Our data show a sharp feature very close to the Fermi energy, and a relative flat distribution of the density of states between 0.5eV and 3eV binding energy, which agrees well with the band structure calculations considering an antiferromagnetic ground state. No noticeable gap opening is observed at 12K below thesuperconducting transition temperature, indicating the existence of large ungapped regions in the Brillouin zone.     

Abnormal temperature dependence of photoluminescence from self-assembled InAs quantum dots covered by an InAlAs/InGaAs combination layer

In this report we have investigated the temperature dependence of photoluminescence (PL) from self-assembled InAs quantum dots (QDs) covered by an InAlAs/InGaAs combination layer. The ground state experiences an abnormal variation of PL linewidth from 15 K up to room temperature. Meanwhile, the PL integrated intensity ratio of the first excited state to the ground state for InAs QDs unexpectedly decreases with increasing temperature, which we attribute to the phonon bottleneck effect. We believe that these experimental results are closely related to the partially coupled quantum dots system and the large energy separation between the ground and the first excited states.     

Adsorption of carbon monoxide on the molybdenum (100) surface

The interaction of CO with Mo(100) has been studied by means of thermal desorption spectrometry, work function measurements and electron stimulated desorption, in conjunction with LEED and AES. Results have been obtained for adsorption at room temperature and at temperatures down to 200 K. The study confirms previous results, showing that the β-states formed at room temperature are atomic. The thermal desorption data for the β-states are analyzed to give directly the desorption activation energy as a function of coverage. This energy is found to vary smoothly from an initial value of 3.7 to a final value of 2.9 eV molecule, indicating an average repulsive interaction between a pair of adjacent adatoms of 0.2 eV. The data at low temperature indicate that a molecular state, virgin-CO, is produced in competition with β-CO and probably one other state, from a common precursor. The step leading to virgin-CO has both a low activation energy and a low pre-exponential factor, suggesting that a reorientation of the molecule is required.     

PbWO4闪烁晶体的发光动力学模型

在对PbWO₄闪烁晶体的光谱特性、发光衰减及其温度依赖以及热释光的研究基础上,并结合理论计算,提出了PbWO₄晶体发光的动力学模型,给出了PbWO₄晶体的基本能带结构及激子发光中心能态、陷阱能级在能隙中的位置。用此模型可以完整说明PbWO₄的发光过程,特别是导致室温下发光效率低的原因。最后还对其主发射成分蓝、绿发光中心的起源作了简要讨论。     

Thermal behavior of the roughened Cu(110) surface

The roughened Cu(110) surface was prepared by annealing the clean surface at various temperatures ranging from 700 to ∼1000 K. A significant drop in intensity of reflection anisotropy spectroscopy (RAS) peak at 2.1 eV photon energy as a function of increasing sample temperature was found for annealing above the roughening transition at 900 K. The observed change of 2.1 eV peak in RAS spectra is because of the surface state Fermi level shift due to temperature change. The RAS result is in good agreement with an unoccupied surface state energy using inverse photoemission spectroscopy (IPES). New IPES results indicate that the unoccupied surface state intensity decreases with increasing annealing temperature. It was also found that the unoccupied surface state was shifted. IPES results provide that the contributions of the surface state to surface optical properties at 2.1 eV are relevant for the RAS technique.     

Adsorption of HCl and HBr on Si(111): AES,ELS, and EID studies

The combined techniques in situ of Auger electron spectroscopy, electron energy loss spectroscopy, electron impact desorption, and work-function change measurement have been applied to the study of the adsorption of HCl and HBr on thermally cleaned Si(111) surfaces. Major results are summarized as follows: (1) HCl shows a fast adsorption to the saturation coverage of $\text{θ}{}_{\mathrm{s}}\text{? 0.3}$ (estimated using the continuum approximation) by the exposure of about 1 L at room temperature. (2) The average sticking probabilities for HCl and HBr are ～0.7. (3) Two adsorbed states of HCl or HBr at room temperature are discriminated. For HCl, the first state is characterized by the emission of ～1.2 eV ions and the electronic transition at 8.4 eV, which is subsequently converted to the second state characterized by the emission of ～3.2 eV ions and the electronic transitions at 7.0 and 8.4 eV. Heating the sample at ～800 K causes the desorption of hydrogen and the appearance of the Cl-related peaks at 6.0, 7.0, and 9.0 eV in the loss spectra. For HBr, the first and the second states are characterizied by the emission of ～1.2 and ～3.2 eV ions, respectively. The electronic transition is observed at 7.8 eV in both states. (4) It is proposed that HCl and HBr are adsorbed as molecules initially, which are subsequently dissociated into atoms spontaneously at room temperature.     

Electronic structure,optical dielectric constant and born effective charge of EuAlO3

EuAlO₃ (EAO) is synthesized by the sol–gel process. The Rietveld refinement of the X-ray diffraction data shows that the material has orthorhombic structure with Pbnm space group. The density functional theory calculations are initiated with the experimental lattice parameters. The full potential linearized augmented plane wave method and projector augmented wave method are used to investigate the ground state properties of EAO. An indirect band gap of 1.8 eV is observed with the valence band maximum at the Γ point and the conduction band minimum at the R point. The X-ray photoemission spectroscopy (XPS) spectra of EAO are obtained in the energy window of 0–1000 eV. Using the electronic density of states, the valence band (VB) spectrum of EAO is generated and compared with the observed VB-XPS spectrum. The optical dielectric constant and the refractive index of the material are calculated for the photon energy radiation. The optical properties show a considerable anisotropy in the material. The Born effective charge of various elements and the dielectric tensor of EAO have been calculated.     

Theoretical search for half-metallic material: Y MnS3

Half-metallic material, perovskite sulfide Y MnS₃, is theoretically discovered. Our calculated results show that the ground state is the ferromagnetic state with a high estimated Curie temperature of about 869 K, and the ground-state structure exhibits Pm3m space group with no Jahn–Teller distortion. The ferromagnet behaves as half-metal with an energy gap of 1.30 eV at the Fermi level in the down-spin band. Additionally, Mn ions are in the high-spin state with the chemical valence state of Mn³⁺.     

7LiH分子基态及若干激发态的平衡几何及垂直激发能的从头算

使用“对称性匹配簇-组态相互作用方法”(SAC/SAC-CI),在多种基组下计算了7LiH分子X1Σ 、A1Σ 、B1Π及b3Π态的平衡几何,并将由“几何优化”得到的相应各态的平衡几何与“单点能扫描”得到的结果进行了比较。比较的结果表明,由“几何优化”得到的相应各态的平衡几何,与“单点能扫描”得到的结果存在着差异。分析的结果表明,在完全活性空间中,由“SAC/SAC-CI”方法进行“单点能扫描”得到的结果,比“几何优化”得到的结果更加合理。首次报告了使用6-311G(3df,3pd)基组进行“单点等扫描”得到的相应各态的平衡几何。其值分别是:基态(X1Σ )为0.1588 nm、单重态的第一激发态(A1Σ )为0.2487 nm、单重态的第二激发态(B1Π)为0.2434 nm、三重态的第二激发态(b3Π)为0.1958 nm。这一计算结果与实验值非常接近。还研究了从基态到上述相应各态的垂直激发能,在基态的平衡位置处,其值分别为(A1Σ ←X1Σ )3.613 eV(、B1Π←X1Σ )4.612 eV和(b3Π←X1Σ )4.233 eV。与其它理论计算结果进行比较后得出,本文的计算结果非常接近于使用很复杂的计算方法获得的结果。     

Photoelectronic and electrical properties of Tl2InGaS4 layered crystals

Tl₂InGaS₄ layered crystals are studied through the dark electrical conductivity, space charge limited current and illumination- and temperature-dependent photoconductivity measurements in the temperature regions of 220-350 K, 300-400 K and 200-350 K, respectively. The space charge limited current measurements revealed the existence of a single discrete trapping level located at 0.44 eV. The dark electrical conductivity showed the existence of two energy levels of 0.32 eV and 0.60 eV being dominant above and below 300 K, respectively. The photoconductivity measurements reflected the existence of two other energy levels located at 0.28 eV and 0.19 eV at high and low temperatures, respectively. The photocurrent is observed to increase with increasing temperature up to a maximum temperature of 330 K. The illumination dependence of photoconductivity is found to exhibit supralinear recombination in all the studied temperature ranges. The change in recombination mechanism is attributed to exchange in the behavior of sensitizing and recombination centers.     

Luminescence and structure of ZnO-ZnS thin films prepared by oxidation of ZnS films in air and water vapor

Effect of water vapor quantity at oxidation of undoped ZnS films on structural and luminescent properties of the obtained films was investigated. The films were deposited onto glass substrates by electron beam evaporation. ZnO-ZnS layers were prepared by thermal oxidization of ZnS films at 600 °C in dry or wet atmospheres. The films were characterized by X-ray diffraction, atomic force microscopy and photoluminescence spectroscopy. As-deposited ZnS films were sphalerite crystal structure. The “dry annealing” led to the ZnS phase transition from sphalerite to wurtzite structure and from ZnS to ZnO for a small fraction of the film. After the “wet annealing” the amount of ZnO phase with wurtzite structure growing along the 〈0 0 0 2〉 direction varied from 25% to 95% in dependence on the water vapor quantity. Photoluminescent spectrum at room temperature exhibits green emission with maximum at 2.4 eV. A strong influence of the water vapor on shape and intensity of the emission was observed. Photoluminescent spectra at 22 K consisted of two bands—high-energy band at 2.1-2.4 eV and low energy band at 1.7-1.8 eV. Location and intensity ratio depended on the preparation conditions.     

Thermally stimulated current and high temperature resistivity measurements of 4H semi-insulating silicon carbide

High purity semi-insulating 4H SiC single crystals have potential applications for room temperature radiation detectors because of the wide band gap and radiation hardness. To control carrier lifetime, a key parameter for high performance radiation detectors, it is important to understand the nature of the deep traps in this material. For this purpose, we have successfully applied thermally stimulated current (TSC) and high temperature resistivity measurements to investigate deep level centers in semi-insulating 4H SiC samples grown by physical vapor transport. High temperature resistivity measurements showed that the resistivity at elevated temperatures is controlled by the deep level with an activation energy of 1.56 eV. The dominant traps revealed by TSC measurements were at 1.1-1.2 eV. The deep trap levels in 4H-SiC samples, the impurity and point defect nature of TSC traps peaked at ∼106 K (0.23 eV), ∼126 K (0.32 eV), ∼370 K (0.95 eV), ∼456 K (1.1-1.2 eV) are discussed.     

Shape dependent electronic structure and exciton dynamics in small In(Ga)As quantum dots

We present a study of the primary optical transitions and recombination dynamics in InGaAs self-assembled quantum nanostructures with different shape. Starting from the same quantum dot seeding layer, and depending on the overgrowth conditions, these new nanostructures can be tailored in shape and are characterized by heights lower than 2 nm and base lengths around 100 nm. The geometrical shape strongly influences the electronic and optical properties of these nanostructuctures. We measure for them ground state optical transitions in the range 1.25–1.35 eV and varying energy splitting between their excited states. The temperature dependence of the exciton recombination dynamics is reported focusing on the intermediate temperature regime (before thermal escape begins to be important). In this range, an important increase of the effective photoluminescence decay time is observed and attributed to the state filling and exciton thermalization between excited and ground states. A rate equation model is also developed reproducing quite well the observed exciton dynamics.     

Infrared luminescence from spark-processed silicon

The infrared (IR) photoluminescence (PL) emission of spark-processed silicon (sp-Si) was investigated. A broad and strong room temperature PL peak in the 945 nm (1.31 eV) spectral range was observed when sp-Si was excited with an argon laser. This peak is different from the PL commonly reported for anodically etched porous silicon and other silicon-based materials. The PL intensity increases substantially after annealing sp-Si between 350 and 500 °C in air after which it decreases again. The PL wavelength is observed to peak at 1010 nm by annealing sp-Si near 450 °C. It was further found that the most efficient PL occurs for a Si/O ratio of 0.3, for a small spark gap of about 1 mm, and for spark-processing times in the 15-60 min range.A model for the IR PL is proposed which mirrors that for visible PL. Specifically, it is proposed that the electrons which have been pumped by the laser from the ground state into a broad quasi-absorption band (or closely spaced absorption lines between 1.7 and 2.3 eV) revert back to lower IR levels at 1.31 eV by a non-radiative transition from where they revert radiatively to the ground state by emitting the observed 945 nm light.     

Interstitial iron and iron-acceptor pairs in silicon

Deep levels in iron-dopedp-type silicon are investigated by means of Deep Level Transient Spectroscopy (DLTS) and the Hall effect. Pairs of Fe with the acceptors B, Al, and Ga are observed at 0.1, 0.19, and 0.24 eV above the valence band edgeE _v. For interstitial iron, (Fe _i ), a level energy ofE _v+0.39+-0.02 eV is obtained with DLTS after correction with a measured temperature dependence of the capture cross section. The Hall effect yieldsE _v+0.37 eV for Fe_i. The annealing behavior of levels related to Fe is investigated up to 160 °C. Iron participates in at least four different types of impurity states: Fe _i , Fe-acceptor pairs, precipitations (formed above 120 °C) and an additional electrically inactive state, which is formed at room temperature.     

Theoretical Study on Inner Shell Electron Impact Excitation of Lithium

Cross sections for electron impact excitation of lithium from the ground state 1s^22s to the excited states 1s2s^2, 1s2p^2, 1s2snp （n = 2-5）, 1s2sns （n = 3 5）, 1s2pns （n = 3-5）, and 1s2pnp （n = 3-5） are calculated by using a full relativistic distorted wave method. The latest experimental electron energy loss spectra for inner-shell electron excitations of lithium at a given incident electron energy of 2500 eV [Chin. Phys. Lett. 25 （2008）3649] have been reproduced by the present theoretical investigation excellently. At the same time, the structures of electron energy loss spectra of lithium at low incident electron energy are also predicted theoretically, it is found that the electron energy loss spectra in the energy region of 55-57eV show two-peak structures.     

Structure of clusters of pentacene molecules and their polarizabilities

We calculate and compare the ground state structures of one, two and three pentacene molecule clusters, using B3LYP and B97-D density functionals, and polarizabilities in the ground state structure to examine the extent of anisotropy for applications in electronic device fabrication. B3LYP and B97-D functionals perform sufficiently well for a single pentacene molecule, but for two and three molecule clusters, the inclusion of dispersive interactions through B97-D becomes necessary. For two and three molecule clusters the energy landscape near ground state is flat in molecular coordinates, implying multiple related structures may be accessible at room temperature. Further, for the ground state structures, the polarizability along the long axis of the molecule is larger than the other two directions. This may make it possible to explain the beneficial effect of applying an electric field during processing of pentacene films in electronic devices, as observed experimentally; specifically, in this context, the structural and polarizability data presented could allow for development of models for nucleation and growth of pentacene films.     

脉冲放电脱硫反应器中高能电子密度分布的光谱研究

脉冲流光放电产生的大于等于11.2 eV的高能电子能将处于基态的氮分子激发到N₂(C3Π_u)态,测试脉冲流光放电时的N₂(C3Π_u→B3Πg)发射光谱相对强度可以得出脉冲流光放电产生的高能电子的密度。实验在室温常压下研究了空气中线-板式脉冲流光放电脱硫反应器内高能电子密度分布情况,并研究了脉冲电压、反应器的线线间距对反应器内高能电子密度分布的影响。实验结果表明,反应器内的高能电子主要集中在放电线附近高电场区内,随着离放电线的距离增大,高能电子密度减小;脉冲电压对高能电子密度有很大影响,随着电压的升高,高能电子密度基本呈线性增大;线板间距固定,线线间距为线板间距的0.6～1倍时,反应器内高能电子密度分布较为均匀。