Rotational spectrum and structure of Si3

The rotational spectrum of a pure silicon cluster, the Si3 trimer, has been observed for the first time. From the rotational constants of the normal and the 29Si and 30Si isotopic species, a precise geometrical structure has been derived: the trimer is an isosceles triangle with a bond to the apex Si of length 2.177(1) A and an apex angle of 78.10(3) degrees. The substantial inertial defect and fairly large centrifugal distortion suggest that the molecule possesses a shallow bending potential. Si3 is a good candidate for astronomical detection because radio lines of comparably massive silicon molecules (e.g., SiC2, SiC4, and SiS) are readily observed in at least one astronomical source. The rotational spectra of Si6, Si9, and even larger polar silicon clusters may be detectable with the present technique, as well as similar germanium clusters.     

High resolution microwave spectroscopy of the isomeric pair vinylcyanoacetylene and cyanovinylacetylene

The carbon chain molecules vinylcyanoacetylene and cyanovinylacetylene have been investigated between 8 and 41 GHz by Fourier transform microwave spectroscopy of a supersonic molecular beam. Owing to the high spectral resolution of the present technique, significantly more accurate rotational and centrifugal distortion constants have been derived for both molecules. In addition, the dipole moments have been calculated at the B3LYP/cc-pVTZ level of theory. Because these carbon chains are similar in structure and composition to known astronomical molecules and because of their high polarity, both species are good candidates for radioastronomical detection.     

The Correspondence of Isaac Newton,Volume V, 1709–1713, edited by A. Rupert Hall and L. Tilling

This report reviews the recent progress that has been made toward understanding the necessary-for-life chemistry that took place on the prebiotic Earth, and that led to the appearance of the ht living cells. This understanding is based on the simulation, in the laboratory, of conditions analogous to those presumed (on geological and astronomical evidence), to have been present on the primitive Earth. Such research has led to the production of many of the classes of compounds that are key constituents of our contemporary biology. It has also led to the knowledge that abiogenetically produced organic compounds have an intrinsic tendency to assume the forms and the aggregations that are found in living cells. The report concludes with a summary of the exciting new finds of ‘biological’ molecules in interstellar space.     

极性分子的激光冷却及囚禁技术

分子由于其不同于原子的特殊性质,在原子、分子和光物理研究中有其独特的地位.冷分子研究已经开展了二三十年,取得了很多重大的进展.但是以斯塔克减速器为代表的传统冷却方案遇到瓶颈,很难进一步提高分子的相空间密度.将原子中成熟的激光冷却技术拓展到极性分子中是本领域近年来的重大突破,使得冷却和囚禁分子的范围得以大大扩展,分子的相空间密度也得以提高.本文对国内外激光冷却极性分子的最新成果进行综述,并以BaF分子为例介绍激光冷却极性分子的相关理论和技术,包括分子能级结构分析及精密光谱测量,采用缓冲气体冷却进行态制备和预冷却,以及通过冷分子束研究激光与BaF分子间的相互作用.这些为后续开展激光冷却与囚禁实验研究奠定了基础,也为开展其他新的分子冷却实验提供了参考.     

Self-assembled and electrochemically deposited mono/multilayers for molecular electronics applications

For the development of molecular electronics, it is desirable to investigate characteristics of organic molecules with electronic device functionalities. In near future, such molecular devices could be integrated with silicon to prepare hybrid nanoelectronic devices. In this paper, we review work done in our laboratory on study of characteristics of some functional molecules. For these studies molecular mono and multilayers have been deposited on silicon surface by self-assembly and electrochemical deposition techniques. Both commercially available and specially designed and synthesized molecules have been utilized for these investigations. We demonstrate dielectric layers, memory, switching, rectifier and negative differential resistance devices based on molecular mono and multilayers.     

Chemistry in space

Summary Molecules have been observed in widely disparate astronomical objects, from comets to supernova remnants. Interstellar space appear to be a real chemical laboratory, able to produce a large number of molecules, some of them relatively complex. The abundances show a very high sensitivity to local physical properties and dynamical history. This sensitivity renders molecular observations and astrochemical modelling very flexible tools for investigating the properties and evolution of the interstellar medium. A brief outline of morfology of interstellar medium is given, together with a discussion of the basic chemical processes leading to the molecular formation. Since interstellar-dust particles play a crucial role in the chemical evolution of interstellar medium, physical and chemical properties of dust are reviewed. Finally, by way of an example of modelling exercise, a toy model of the chemical evolution of interstellar gas is presented. Paper presented at the V Cosmic Physics National Conference, S. Miniato, November 27–30, 1990.     

Vibrational spectroscopy of interstellar molecules

In this paper we describe how infrared vibrational spectroscopy has been applied in our laboratory to three areas of interest to interstellar chemistry: the origin of the unidentified interstellar infrared emission bands, the depletion of the iron in the interstellar medium, and the fractionation of isotope-bearing molecules in space. In the first area, infrared absorption spectra of polycyclic aromatic hydrocarbons and their ions trapped in cryogenic rare gas matrices have been analyzed and shown to coincide well with the frequencies and relative intensities of the unidentified infrared emission bands. These bands have been observed from many sources in interstellar space, including reflection and planetary nebulae and H II regions, in parts of the Milky Way, as well as other galaxies. In the second area, a free electron laser, with tunable output in the infrared, has been utilized to record resonant multiphoton photodissociation vibrational spectra of various polycyclic aromatic hydrocarbons complexed with Fe⁺ in a Fourier transform ion cyclotron resonance mass spectrometer. Stable complexes found for Fe⁺ and a number of PAHs suggest that iron could be sequestered in such species and that they could function as carriers of the unidentified infrared emission bands. In the third area, the photo-induced ¹³C-isotopic scrambling in the C₃ carbon cluster has been investigated by matrix isolation infrared spectroscopy. Fractionation is shown to arise from small zero-point energy differences in the C₃ isotopomers. A proposed mechanism of isotopic scrambling involving the formation of cyclic C₃ intermediates may be applicable to other species for which isotopic fractionation has also been observed in the ISM.     

Rovibrational and energetic analysis of the hydroxyethynyl anion (CCOH−)

For the first time, high-level structural and rovibrational data are provided for the hyroxyethynyl anion, CCOH^?. CCOH^? is a promising molecule for interstellar detection even though no new anions have been observed in the interstellar medium for the past half-decade. The large dipole moment of the corresponding neutral radical may be key for its creation as has been hypothesised and supported for other anions known to exist in various astronomical environments. Highly accurate quartic force fields are employed where previous benchmarks have produced spectroscopic constants and anharmonic vibrational frequencies within 20 MHz and 1 cm^?1, respectively, of experiment. This same approach is applied here for CCOH^? and its deuterated isotopologue with the goal of assisting laboratory experiments and/or astronomical observers in the potential detection of this anion.     

On weaker forces than gravity

The limits on hypothetical new interactions with a range accessible to detection by laboratory and geophysical experiments are briefly reviewed, and the limits at larger distances imposed by a rich body of astronomical observations are elaborated on. The systematic deviations correlated with baryon number that have recently been unearthed from the data of Eötvös' classical experiment, can bravely but consistently be interpreted as a new force whose range is narrowly bracketed somewhere in between Mercury's distance to the sun and our distance to the moon. This hypothetical long-range interaction would be five and a half orders of magnitude weaker than gravity. The new force would make like bodies attract, and would therefore not constitute an elegant explanation of why protons have not been seen to decay.     

Sulphur on rutile(1 1 0): A theoretical study

Reactions of elementary sulphur with the rutile (1 1 0) surface are of interest for catalytic desulphurization and have recently been studied experimentally. Here a complete mechanism for the sulphurization of the surface in UHV experiments has been derived from the results of first principles molecular dynamics simulations. It provides the dissociation of S₂ molecules, the reaction of S atoms with oxygen atoms in the surface, the insertion of sulphur atoms into surface vacancies and the formation of SO_x species. Possible elementary steps for these processes are discussed in the paper on the basis of the calculations.     

表面等离子体共振传感技术应用于小分子检测

人体内的生物小分子对维持生命体健康具有重要影响,此类分子参与生命体的血液循环及免疫系统,因此检测生命体中生物小分子对研究小分子在生命体中的生理功能有着重要的意义.傅里叶变换-表面等离子体共振(Fourier transform-surface plasmon resonance,FT-SPR)光谱技术具有操作简便、灵敏...     

Investigation of atomic and molecular clustering in a pulsed gas-dynamic jet with a pyroelectric detector

The clustering of atoms and molecules in a pulsed gas-dynamic jet has been investigated by the method of time-of-flight measurements performed with an uncooled pyroelectric detector (PED). The method is based on measuring the amplitude of the pyroelectric signal induced on the detector by a molecular (atomic) beam and the particle velocity in the beam as a function of the gas pressure above the nozzle. In addition, the number of molecules (atoms) emerging from the nozzle in a pulse has been measured. We describe the method and present the results of our studies on the clustering of He, Xe, CH₄, CO₂, and other gases. The peculiarities of the detection of molecular and cluster beams with PED are considered. We show that the described method allows the clustering threshold as a function of the gas pressure above the nozzle to be determined. We have established the threshold pressures at which particle clustering in the jet begins. Optimal conditions for the generation of intense cluster beams have been found.     

On the nonequivalency of Si-O bonds in silicon dioxide

Abinitio and INDO investigations of both the electronic structure and potential surfaces of various SiO₂ molecular conformations and (SiO₂)_n (n = 2, 3, 4) molecular complexes have been carried out. The possibility of the formation of spatial structures resulting from the interaction of separate SiO₂ molecules has been shown, the structures formed being similar to those existing in condensed forms of silicon dioxide. Starting from the concept of the formation of crystalline silicon dioxide structure and other silicates by consistent joining of separate SiO₂ molecules, the explanation of the non-equivalent nature of the Si-O bonds in these compounds has been given. Two different mechanisms of switching these non-equivalent Si-O in silicates and the corresponding rearrangements of their structures and silification are also discussed.     

Very Low Frequency Far-Infrared Spectra of Mixtures of Dioxan with the Halogens and Related Molecules

Abstract

There has been considerable interest recently in the study of the submillimetre (or very far-infrared) absorption shown by both polar^1–4 and non-polar molecules.^2,5–8 Such absorption, in the ～5–100 cm^?1 region, for non-polar molecules is thought^2,6 to be caused by fluctuating dipoles associated with classical quadrupole-induced dipole interactions (in general multipole-induced dipole interactions). These effects are said to be “collision-induced” and can be thought of as being due to “collision” complexes in the liquid phase. For polar molecules the absorption is now thought^1–4 to be due to libration of the dipole in a “cage” of surrounding molecules (either molecules of the same species or of solvent). This so-called Poley-Hill model^9,10 is not inconsistent with the idea^1,2 of a residual rotation of the molecular dipole in the liquid phase. This similarity is underlined by the fact that some simple polar molecules^11,12 have a liquid phase Poley-Hill absorption the general shape and position of which follow quite closely that of the pressure broadened, gas phase spectrum. Our interest in the far-infrared region stems from our studies on halogen complexes with various n and bπ donors.^13,14 The pyridine-I₂ system (in cyclohexane) for example shows two bands in the far in frared not present in either component. The band at -183 cm is thought to be the stretching mode of the iodine, perturbed in the complex. The band at ～96 cm to the v(1-I) band, has so far been interpreted molecular″ stretching modebetween donor and acceptor, v(D-A).     

Defocusing effects in astronomical speckle interferometry

Theoretical transfer functions for astronomical speckle interferometry, through a defocused telescope, have been computed assuming a log-normal complex amplitude for the incoming wavefront. They are found in reasonable agreement with recently published observations. The theory also applies to the effect of astigmatism.     

光子芯片中类比引力的研究

探索和理解引力场弯曲时空的本质一直是人类孜孜不倦追求的目标。尤其最近天文学上两大事件：激光干涉引力波天文台探测到引力波信号以及事件视界望远镜拍到黑洞的影子,进一步激发人类对古老而神秘引力的兴趣。尽管人类在探测引力现象的天文实验技术上取得了巨大的进步,但是对于有些引力现象的研究仍然面临着挑战,特别是与引力有关的量子效应。另一方面,类比引力系统为人类研究引力效应提供了一个新的实验平台,它可以在实验室环境下研究目前天文观测仍面临挑战的引力现象,例如黑洞附近引力场的量子效应。文章将介绍以光子芯片作为一种类比引力的实验体系而实现的引力场弯曲时空的模拟与研究。     

嵌入多孔硅中的C60分子的发光行为

1990年团簇C60分子分离的成功[1],立即引起了科学界的极大重视,有关C60分子的超导电性、光谱特性以及电子能级结构的研究报道与日俱增,由于单个C60分子是直径为7.1Å的球形分子,因而在某种程度上对于由C60分子聚集而成的具有几个纳米尺寸的CBO微晶的体系应该也具有类似于半导体超微粒低维量子限域的物理特性.     

七种新的SiC六方多型体

本文提出了用X射线劳埃法鉴定SiC六方多型体类型的方法。在详细地研究了xH类型与基本类型6H,15R和4H的倒易阵点间相互配置关系的基础上,推导出了这些具体关系,这种关系对于xH—6H来说仅有十二种,对于xH—15R仅有三十种,对于xH—4H仅有八种。上述的点间关系表和推求xH类型单位晶胞密堆积层数的公式同样可以普遍适用于以其他X射线照相法鉴定SiC六方多型体类型的工作中。用本文所提出的方法研究了许多实验室升华法制备的SiC单晶体以及部分工业SiC晶体。发现了七种六方SiC新多型体141H,80H,58H,55H,15H,9H和7H。新类型的定间羣为C_3v¹(C3m),六方晶胞c轴参数分别为:355.26?,201.57?,146.14?,138.58?,37.794?,22.676?和17.637?。     

Acrylic acid (CH2CHCOOH): the rotational spectrum in the millimetre range up to 397 GHz

In order to facilitate its detection in astronomical observations, the measurement of the rotational spectrum of acrylic acid has been extended to 397 GHz using a free space cell at room temperature. 295 new lines were assigned to the s-cis conformer and 286 new lines to the s-trans conformer of acrylic acid. Using the determined experimental parameters, the predictions of the rotational transition frequencies up to 900 GHz and their intensities were obtained at temperatures of 100 and 200 K and at room temperature. Based on these predictions, a search of the most intense transitions of acrylic acid in star-forming regions was performed using published data from the HERSCHEL Science Archive. No lines were found but the possibility of observing rotational transitions of acrylic acid in astronomical objects is discussed.     

Adsorption of hydrogen and hydrocarbon molecules on SiC(001)

Adsorption of hydrogen and hydrocarbon molecules on semiconductor surfaces plays a key role in surface science and technology. Most studies have employed silicon (Si) as a substrate because of its paramount technological importance and scientific interest. However, other semiconductor substrates are gaining an increasing interest as well. Silicon carbide (SiC), which is a material with very special properties allowing developments of novel devices and applications, offers particularly fascinating new degrees of freedom for exceptional adsorption behaviour. For example, a very unusual hydrogen-induced metallization of a SiC(001) surface has been reported and hydrogen molecules show very different adsorption behaviour on different SiC(001) reconstructions although the latter exhibit very similar surface dimers. In marked contrast to the Si(001) surface, the adsorption of hydrocarbon molecules on SiC(001) can yield structurally well-defined adlayers in favourable cases which may have large potential for organic functionalization. We review and discuss theoretical ab initio results on conceivable adsorption scenarios of atomic and molecular hydrogen as well as acetylene, ethylene, butadiene, benzene and cyclohexadiene on various reconstructions of the SiC(001) surface. The main emphasize is on a detailed understanding of these adsorption systems and on identifying the physical origin of the particular adsorption behaviour. The results will be discussed in the light of related adsorption events on the Si(001) surface and in comparison with available experimental data.