以二乙烯硫/砜基为中心的新型电荷转移分子双光子吸收特性

理论研究分子结构与双光子吸收性质之间的关系对于指导实验者设计与合成功能分子材料具有重要意义. 在杂化密度泛函水平上, 利用响应函数方法, 计算了一类以二乙烯硫/砜基为中心的新型电荷转移分子的双光子吸收截面, 并在相同计算水平上, 与联苯乙烯类强双光子吸收分子做了比较; 以新型电荷转移分子为基础, 利用异构效应, 设计出了可以增强双光子吸收强度的分子结构. 研究表明, 在可应用波长范围内, 该系列分子表现出较强的双光子吸收响应, 与相似共轭长度的强双光子吸收分子具有相同量级的双光子吸收截面; 二乙烯硫/砜基在分子中心作为吸电子基团可以形成有效的电荷转移分子; 改变咔唑基的连接方式可以有效提高双光子吸收截面. 该研究为实验合成新型双光子吸收分子材料提供了理论依据.     

Influence of radiation on thin ZnS-Tb films

Changes in thin zinc-sulfide films under the action of the γ-radiation of Co⁶⁰ are studied by investigating electroluminescence spectra of terbium embedded in these films as a luminescent probe. It is shown that changes in the relation of the intensities of bands, a decrease in their halfwidth and the background component, and simplification of the spectrum are observed in a short-wave region of the Tb radiation spectrum that corresponds to⁵D₃→⁷F_j transitions. The same modification of the radiation spectrum is characteristic of ZnS films whose crystalline structure is ordered in the course of thermal annealing at a temperature of 350°C. Based on the analysis of the data obtained it is inferred that irradiating the ZnS films with small radiation doses of 10⁴–10⁵ rad leads to the ordering of their crystalline structure due to the elimination of one of the types of structural defects. Institute of Physics of Semiconductors, National Academy of Sciences of Ukraine, 45, Nauka Ave., Kiev-28, 252650. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 338–341, May–June, 1997.     

Infrared spectra of carbon monoxide-hydrogen sulfide van der Waals complexes in the C-O stretching region

The CO-stretching vibration-rotation spectra of CO-H₂S, CO-D₂S, and CO-HDS complexes have been studied in the 2150 cm⁻¹ region using a supersonic slit-jet expansion and a tunable diode laser spectrometer. The spectra were analyzed with the help of very recent microwave pure rotational studies of the same complexes. Two bands were assigned for each of the symmetric hydrogen sulfide isotopes, corresponding to the two nuclear spin modifications, para and ortho. The band origins were blue shifted, relative to the free CO molecule, by about 3.8 cm⁻¹ for CO-H₂S and 4.3 cm⁻¹ for CO-D₂S. These are considerably smaller shifts than exhibited by the related CO-water complexes, indicating that the intermolecular forces in CO-H₂S are weaker and more isotropic.     

Study on hydrogen sulfide plasma passivation of 790-nm laser diode cavity surface

In order to improve the optical properties of the Ⅲ-Ⅴ laser diodes(LDs) by means of H2S plasma passivation technology,H2S plasma passivation treatment is performed on the GaAs(110) surface.The optimum passivation conditions obtained are 60-W radio frequency(RF)power and 20-min duration.So the laser cavity surfaces axe treated under the optimum passivation conditions.Consequently,compared with unpassivated lasers with only AR/HR-coatings,the catastrophic optical damage (COD) threshold value of the passivated lasers by H2S plasma treatment is increased by 33%,which is almost the same as that of (NH4)2Sx treatment.And the life-test experiment has demonstrated that this passivation method is more stable than(NH4)2Sx solution wet-passivated treatment.     

RCCo_3(CO)_9的电化学和RCCo_3(CO)_9~-的ESR谱研究

本文对三种RCCo_3(CO)_9及相应的自由基进行了电化学和ESR谱研究.电化学研究表明,RCCo_3(CO)_9被还原为自由基的难易与R的性质有关,RCCo_3(CO)_9在室温下可以稳定存在.在对分子轨道对称性分析的基础上对簇合物自由基的ESR谱进行了讨论.确定了超精细偶合常数的符号和未成对电子占据轨道的性质,计算了Co的3d轨道和4s轨道的自旋密度.     

基于荧光分析技术的大鼠肠灌流液中H_2S含量测定

荧光素汞在碱性条件下具有很强的荧光,H2S能与荧光素汞结合,使其荧光猝灭,据此建立了一种荧光法测定大鼠肠灌流液中H2S含量的方法。在0.1mol·L-1 NaOH溶液中,以Na2S作为H2S供体,荧光素汞浓度为5.0×10-5 mol·L-1,Na2S浓度为1.0×10-5 mol·L-1时,以498nm为激发波长,在522nm处测定此二元体系的荧光强度。结果表明,在4.0×10-7~2.0×10-6 mol·L-1范围内,H2S浓度与荧光强度的下降程度呈良好的负相关性,r=0.998 0,精密度实验RSD=4.59%(n=7),检出限3.5×10-8 mol·L-1,样品中H2S含量分别为1.01×10-6和1.15×10-6 mol·L-1,加标回收率为95.8%~101.0%。该方法操作简单,灵敏度高,稳定性好,可准确测定肠灌流液中H2S含量,为内源性H2S的测定提供了依据。     

Interaction of H2S with α-Fe2O3(0 0 0 1) surface

The atomic-scale structural changes in an α-Fe₂O₃ (hematite) (0 0 0 1) surface induced by sulfidation and subsequent oxidation processes were studied by X-ray photoemission spectroscopy, LEED, and X-ray standing wave (XSW) measurements. Annealing the α-Fe₂O₃(0 0 0 1) with a H₂S partial pressure of 1 × 10⁻⁷ Torr produced iron sulfides on the surface as the sulfur atoms reacted with the substrate Fe ions. The oxidation state of the substrate Fe changed from 3+ to 2+ as a result of the sulfidation. The XSW measured distance of the sulfur atomic-layer from the unrelaxed substrate oxygen layer was 3.16 Å. The sulfide phase consisted of three surface domains identified by LEED. Formation of the two-dimensional FeS₂ phase with structural parameters consistent with an outermost layer of (1 1 1) pyrite has been proposed. Atomic oxygen exposure oxidized the surface sulfide to a sulfate () and regenerated the α-Fe₂O₃(0 0 0 1) substrate, which was indicated by a (1 × 1) LEED pattern and the re-oxidization of Fe to 3+.     

Morphological and chemical study of the initial growth of CdS thin films deposited using an ammonia-free chemical process

We study the initial growth stages of CdS thin films deposited by an ammonia-free chemical bath deposition process. This ammonia-free process is more environmentally benign because it reduces potential ammonia release to the environment due to its high volatility. Instead of ammonia, sodium citrate was used as the complexing agent. We used atomic force microscopy (AFM), Rutherford backscattering (RBS) and X-ray photoelectron spectroscopy (XPS) to investigate the morphological and chemical modifications at the substrate surface during the first initial stages of the CdS deposition process. Additionally, X-ray diffraction (XRD) and optical transmission spectroscopy measurements were carried out to compliment the study. XPS results show that the first nucleation centers are composed by Cd(OH)₂ which agglomerate in patterns of bands, as demonstrated by AFM results. It is also observed that the conversion to CdS (by anionic exchange) of the first nucleus begins before the substrate surface is completely covered by a homogenous film.     

Scanning probe microscopy studies of PbS surfaces oxidized in air and etched in aqueous acid solutions

Natural n-type PbS single crystals have been studied using AFM, STM and STS after long-term oxidation in air at ambient temperatures and extensive etching in aqueous acid solutions, in contrast to previous work devoted to initial corrosion of fresh surfaces. The exposure of PbS to atmosphere at high relative humidity for several days yields widespread loose oxidation products; the process is much slower at low humidity. Surface morphologies diverge after the treatment in 1 M perchloric and hydrochloric acid solutions at room temperature and become widely different at elevated temperatures, displaying commonly etch pits up to several micrometers in size and depth along with rather uniformly distributed 20-100 nm protrusions of PbS phase. The changes both in topography and semiconducting properties of PbS found by tunneling spectroscopy have been explained in terms of the non-uniform distribution of donor- and acceptor-type defects D⁺/D⁻ in the metal depleted surface layer, which are generated by chemical reactions and, in turn, determine the rates of the PbS corrosion. In particular, the D⁻ centers exhibit a self-catalyzing effect on the non-oxidative local dissolution of PbS in HCl media, resulting in the deep etch pits.     

Optical properties of cadmium sulfide nanocrystal film prepared by electrochemical synthesis at liquid-liquid interface

Dendritic nanocrystalline CdS film was deposited at liquid-liquid interface of surfactants and an electrolyte containing 4 mmol L⁻¹ cadmium chloride (CdCl₂) and 16 mmol L⁻¹ thioacetamide (CH₃CSNH₂) with an initial pH value of 5 at 15 °C by electrochemical synthesis. The nanofilm was characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), ultraviolet visible (UV-vis) absorption spectroscopy and fluorescence spectroscopy. The surface morphology and particle size of the nanofilm were investigated by AFM, SEM and TEM, and the crystalline size was 30-50 nm. The thickness of the nanofilm calculated by optical absorption spectrum was 80 nm. The microstructure and composition of the nanofilm was investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), showing its polycrystalline structure consisting of CdS and Cd. Optical properties of the nanofilm were investigated systematically by UV-vis absorption and fluorescence spectroscopy. A λ_onset blue shift compared with bulk CdS was observed in the absorption spectra. Fluorescence spectra of the nanofilm indicated that the CdS nanofilm emitted blue and green light. The nanocomposites film electrode will bring about anodic photocurrent during illumination, showing that the transfer of cavities produces photocurrent.