Sub-nanometer distances and cluster shapes in dense hydrogen and in higher levels of hydrogen Rydberg matter by phase-delay spectroscopy

The inter-atomic distances in potassium clusters of Rydberg matter (RM) at excitation levels n _B = 4–8 were recently measured by phase-delay spectroscopy (Holmlid, J Nanopart Res 12: 273, 2010). Excitation levels n _B < 4 with shorter inter-atomic distances exist for hydrogen clusters, and distances down to 140 pm are now measured with this light-scattering method. The clusters studied have maximum dimensions from 0.3 nm up to several tens of nm, often being planar. A weak carbon dioxide laser beam interacts with the clusters in a tunable RM cavity. A strong fringe structure is observed as a function of the end-grating angular position. Delay lengths in the clusters are derived from the fringe structure, corresponding to twice the distance between rows or planes in the clusters. Good agreement with predicted and a few previously measured distances in excitation levels n _B = 1, 2, and 3 is found. Close-packing is the main structure both in planar and 3D clusters. Planar clusters are only observed for n _B = 1 and 3, while 3D clusters are found in excitation levels n _B = 1, 2 and 3. The cluster–cluster distance in stacks of planar clusters for n _B = 2 and 3 is now observed for the first time.     

Precision bond lengths for Rydberg Matter clusters K19 in excitation levels n =4, 5 and 6 from rotational radio-frequency emission spectra

Several long series of up to 40 equally spaced lines are observed in the radio-frequency range 15–90?MHz that are attributed to stimulated emission from the electronically excited condensed matter called Rydberg Matter (RM). These frequencies are more than a factor of 1000 smaller than for most ordinary molecules, and if they did not agree with RM clusters they would indicate extremely large and heavy molecules that are unlikely to exist in the gas phase at room temperature. Theoretical predictions for RM clusters agree within 2% with the observed frequencies. Such clusters are planar, six-fold symmetric oblate rotors. The most prominent series with B?=?0.9292?±?0.0001?MHz (3.067?×?10^?5?cm^?1) agrees accurately with the theoretically predicted B value for the cluster K₁₉ in excitation level n?=?4, thus with a K–K bond length of 2.4074?nm. Two other prominent long series agree accurately with K₁₉ at n?=?5 and 6, with bond lengths of 3.804 and 5.518?nm, respectively. The ratio between the interatomic distance and the electron orbit radius for n?=?4 is found to be 2.8433?±?0.0003, a considerable improvement in precision over the theoretical value of 2.9.     

Structural,energetic, and electronic properties of hydrogenated aluminum arsenide clusters

The chemisorptions of hydrogen on aluminum arsenide clusters are studied with density functional theory (DFT). The on-top site is identified to be the most favorable chemisorptions site for hydrogen. And the Al-top site is the preferred one in the most cases for one hydrogen adsorption in (AlAs) _n (n = 2, 5, 6, 8–15) clusters. Top on the neighboring Al and As atoms ground-state structures are found for two hydrogen adsorption on (AlAs) _n except for (AlAs)₂ cluster. The Al–As bond lengths decrease generally as the size of the cluster increases. And there is a slight increase in the mean Al–As bond lengths after H adsorption on the lowest-energy sites of the most AlAs clusters. In general, the binding energy of H and 2H are both found to decrease with an increase in the cluster size. And the result shows that large binding energies (BE) of a single hydrogen atom on small AlAs clusters and large highest occupied and lowest unoccupied molecular-orbital gaps for (AlAs)H and (AlAs)₃H make these species behaving like magic clusters. Calculations on two hydrogen atoms on (AlAs) _n clusters show large BE for (AlAs) _n H₂ with an odd number of n. The stability of these complexes is further studied from the fragmentation energies. (AlAs)₇H₂ and (AlAs)₉H₂ clusters are again suggested to be the stable clusters. On the other hand both the fragmentation energy and the binding energy for (AlAs)₁₃H are close to the lowest values.     

(Li3N)n(n=1—5)团簇结构与性质的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(Li₃N)_n(n=1—5)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构. 并对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究. 结果表明,(Li₃N)_n(n=1—5)团簇中N原子的配位数以4,5较多见,Li—Li键长为0.210—0.259nm,Li原子在桥位时Li—N键长为0.185—0.204nm,Li原子在端位时Li—N键长为0.172—0.178nm;团簇中N原子的平均自然电荷为-2.01e,Li原子的平均自然电荷为+0.67e;Li₃N,(Li₃N)₅团簇有相对较高的动力学稳定性. 关键词： 3N)_n(n=1—5)团簇')" href="#">(Li₃N)_n(n=1—5)团簇 密度泛函理论 结构与性质 储氢材料     

Ab initio study of structural, electronic, optical, and vibrational properties of ZnxSy (x?+?y?=?2 to 5) nanoclusters

An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn _x S _y (x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS₂, ZnS₃, and ZnS₄ nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2–3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.     

［Mg(NH2)2］n(n=1—5)团簇的密度泛函理论研究

用密度泛函理论的杂化密度泛函B3LYP方法在6-31G^*基组水平上对［Mg(NH₂)₂］_n(n=1—5)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究.结果表明：团簇易形成链状结构,Mg—N键长为0.190—0.234 nm,N—H键长为0.101—0.103 nm,H—N—H键角为100.2°—107.5°;团簇中M 关键词： 2)₂］_n(n=1—5)团簇')" href="#">［Mg(NH₂)₂］_n(n=1—5)团簇 密度泛函理论 结构与性质 储氢材料     

CO adsorption on neutral iridium clusters

The adsorption of carbon monoxide on neutral iridium clusters in the size range of n = 3 to 21 atoms is investigated with infrared multiple photon dissociation spectroscopy. For each cluster size only a single ν(CO) band is present with frequencies in the range between 1962 cm^-1 (n = 8) and 1985 cm^-1 (n = 18) which can be attributed to an atop binding geometry. This behaviour is compared to the CO binding geometries on clusters of other group 9 and 10 transition metals as well as to that on extended surfaces. The preference of Ir for atop binding is rationalised by relativistic effects on the electronic structure of the later 5d metals.     

(Ca3N2)n(n=1—4)团簇结构与性质的密度泛函理论研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G^*基组水平上对(Ca₃N₂)_n(n=1—4)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了理论分析.结果表明,(Ca₃N₂)_n(n=1—4)团簇最稳定构型中N原子为3—5配位,Ca—N键长为0.231—0.251nm,Ca—Ca键长为0.295—0.358nm;N原子的自然电荷在-1.553e—-2.241e之间,Ca原子的自然电荷在1.035e—1.445e之间,Ca和N原子间相互作用呈现较强的离子性,Ca₃N₂和(Ca₃N₂)₃团簇有相对较高的动力学稳定性. 关键词： 3N₂)_n(n=1—4)团簇')" href="#">(Ca₃N₂)_n(n=1—4)团簇 密度泛函理论 结构与性质     

Generation of CdS clusters using laser ablation: the role of wavelength and fluence

The formation of cationic clusters in the laser ablation of CdS targets has been investigated as a function of wavelength and fluence by mass spectrometric analysis of the plume. Ablation was carried out at the laser wavelengths of 1064, 532, 355, and 266 nm in order to scan the interaction regimes below and above the energy band gap of the material. In all cases, the mass spectra showed stoichiometric Cd _n S _n ⁺ and nonstoichiometric Cd _n S _n−1⁺, Cd _n S _n+1⁺, and Cd _n S _n+2⁺ clusters up to 4900 amu. Cluster size distributions were well represented by a log-normal function, although larger relative abundance for clusters with n=13, 16, 19, 34 was observed (magic numbers). The laser threshold fluence for cluster observation was strongly dependent on wavelength, ranging from around 16 mJ/cm² at 266 nm to more than 300 mJ/cm² at 532 and 1064 nm. According to the behavior of the detected species as a function of fluence, two distinct families were identified: the “light” family containing S₂⁺ and Cd⁺ and the “heavy” clusterized family grouping Cd₂⁺ and Cd _n S _m ⁺. In terms of fluence, it has been determined that the best ratio for clusterization is achieved close to the threshold of appearance of clusters at all wavelengths. At 1064, 532, and 355 nm, the production of “heavy” cations as a function of fluence showed a maximum, indicating the participation of competitive effects, whereas saturation is observed at 266 nm. In terms of relative production, the contribution of the “heavy” family to the total cation signal was significantly lower for 266 nm than for the longer wavelengths. Irradiation at 355 nm in the fluence region of 200 mJ/cm² has been identified as the optimum for the generation of large clusters in CdS.     

Analysis on the laser beam pointing instability induced fringe shift and contrast dilution from different interferometers used for writing fiber Bragg grating

This paper presents an analysis on the effect of laser beam pointing instability on the fringe shift and hence the contrast dilution of superposed fringes from two beam interferometers. The interferometers analyzed are those commonly used in writing fiber Bragg grating (FBG) such as phase mask, bi-prism and phase mask based Talbot/Holographic type. The beam pointing instability is incorporated as slight change in the angle between two interfering beams. The relative immunity of different interferometers to laser beam pointing is discussed vs location of FBG writing plane from the beam splitter. The effect of the beam pointing was minimum in proximity FBG writing by phase mask. The effect, in terms of fringes contrast dilution, was worst in case of large length interferometers e.g. phase mask based-Talbot interferometer. For intermediate length prism interferometers, the effect was moderate. For a given length interferometer, the fringe shift was directly proportional to beam pointing angle and inversely proportional to fringe separation. Theoretical analysis is verified experimentally by studying the fringe instability of interference pattern formed by a bi-prism of angle 2^o with the copper vapour laser (CVL, λ = 510 nm) beams of different beam pointing instabilities.     

The effect of sub-band gap photon illumination on the properties of GaN layers grown on Si(111) by MBE

Nanostructured GaN layers are fabricated by laser-induced etching processes based on heterostructure of n-type GaN/AlN/Si grown on n-type Si(111) substrate. The effect of varying laser power density on the morphology of GaN nanostructure layer is observed. The formation of pores over the structure varies in size and shape. The etched samples exhibit dramatic increase in photoluminescence intensity compared to the as-grown samples. The Raman spectra also display strong band at 522 cm⁻¹ for the Si(111) substrate and a small band at 301 cm⁻¹ because of the acoustic phonons of Si. Two Raman active optical phonons are assigned h-GaN at 139 and 568 cm⁻¹ due to E2 (low) and E2 (high), respectively. Surface morphology and structural properties of nanostructures are characterized using scanning electron microscopy and X-ray diffraction. Photoluminance measurement is also taken at room temperature by using He–Cd laser (λ = 325 nm). Raman scattering is investigated using Ar⁺ Laser (λ = 514 nm).     

(HMgN3)n(n=1–5)团簇结构与性质的密度泛函理论研究

利用密度泛函理论在B3LYP/6-311G^*水平上对叠氮化合物(HMgN₃)_n(n=1–5)团簇各种可能构型进行了几何优化,预测了各团簇的最稳定结构. 并对最稳定结构的成键特性、电荷分布、振动特性及稳定性进行理论研究. 结果表明:HMgN₃团簇最稳定结构为直线型;(HMgN₃)_n(n=2,5)团簇最稳定结构为叠氮基中N原子和金属原子相连构成Mg–N–Mg结构;(HMgN₃)_n(n=3,4)团簇最稳定结构为叠氮基与Mg原子相互链接形成的环状结构. 团簇最稳定结构中金属Mg原子均显示正电性,H原子均显示负电性,叠氮基中间的N原子显示正电性、两端的N原子显示负电性,且与Mg原子直接作用的N原子负电性更强. Mg–N键和Mg–H键为典型的离子键,叠氮基内N原子之间是共价键. 团簇最稳定结构的红外光谱分为三部分,其最强振动峰均位于2258–2347 cm^-1,振动模式为叠氮基中N–N键的反对称伸缩振动. 叠氮基在团簇和晶体中结构不变,始终以直线型存在. 稳定性分析显示,(HMgN₃)₃团簇相对于其他团簇更为稳定. 关键词： 3)_n(n=1–5)团簇')" href="#">(HMgN₃)_n(n=1–5)团簇 叠氮基 密度泛函理论 结构与性质     

Controllable nanostructure and optical properties of ZrO2 thin films by glancing angle deposition

In this paper, nanostructured ZrO₂ films were prepared by electron beam evaporation with the glancing angle deposition (GLAD) technique. Columnar films with voids in between formed owing to the self-shadowing effect and the limited diffusion of deposited atoms. The microstructure evolves from slanted columnar structure to helical and pillar structures as the substrate rotational speed increases. The diameter of the columns is in the range of 30–50 nm. A higher rotational speed favors a larger nodule size and a greater surface roughness. Due to the porous structure, the refractive index n of GLAD ZrO₂ films varies from 1.75 to 1.80, lower than that of bulk material. A maximum value of birefringence (Δn=0.03) is obtained in a slanted columnar structure, and the relationship between birefringence and microstructure orientation is discussed. Our results demonstrate that glancing angle deposition is a feasible approach for designing the nanostructure and optical properties of thin films.     

The Rydberg matter laser: excitation, delays and mode effects in the laser cavity medium

Temporal and temperature effects are studied in Rydberg matter (RM) formed from K atoms and N₂ molecules as the active medium in a cavity. The function of this setup as a laser was recently described. Temperature-variation studies show that the photons re-exciting the RM clusters usually have a longer wavelength than the photons emitted in the stimulated emission process in the cavity. The deficit is probably covered by background photons. Very long time constants observed after emitter temperature changes indicate that long-wavelength photon energy is accumulated in the RM clusters. Long-wavelength modes are located farther from the RM emitter. The modal structure can be TEM₀₁ or TEM₀₀, as observed clearly by the spatial structure in rapid pulsing experiments. The in-cavity chopped beam signal is delayed by approximately 50 μs. The initial growth rate of the signal during chopping is temperature dependent. Tailing is also observed by chopping, but rapid pulsing of the beam with a spinning mirror does not show any delay of the start of the lasing. The conclusion is that delays exist in the stimulated emission process. The broad intense band appearing at 11 000 nm is shown to be formed partly by light in the range 3500–5000 nm, probably by standing wave interaction at the grating surface (grating bands).     

CNDO studies of Y-Ba-Cu-O superconductors V. Co/Cu substitution

Electronic properties of [Co _n Cu_3–n O₁₂]^–17 and [Ba₈Co _n Cu_3–n O₁₂]^–1 model clusters (n=0–3) are investigated using CNDO molecular orbital method. Our results well reproduce the trends of experimental data on Cu-O bond lengths and supposed negative charge transfer from central Cu(1)O chains to lateral Cu(2)O₂ planes with increasing Co content.     

Electronic structure and infrared spectrum of a WnC0＇± （n= 1-6） cluster

W_nC^0,± (n=1-6) clusters are investigated by using the density functional theory (DFT) at the B3LYP/LANL2DZ level. We find that the neutral, anionic and cationic ground state structures are similar within the same size, and constituted by substituting a C atom for one W atom in the structures of W_n+1 clusters. The natural bond orbital (NBO) charge analyses indicate that the direction of electron transfer is from the W atom to the 2p orbital of the C atom. In addition, the calculated infrared spectra of the W_nC^0,± (n=2-6) clusters manifest that the vibrational frequencies of neutral, anionic and cationic clusters are similar in a range of 80 cm^-1-864 cm^-1. The high frequency, strong peak modes are found to be an almost stretched deformation of the carbide atom. Finally, the polarizabilities of W_nC^0,± (n=1-6) clusters are also discussed.     

Structural,electronic and magnetic properties of Au<Subscript>n</Subscript>Pt (n = 1−12) clusters in comparison with corresponding pure Au<Subscript>n+1</Subscript> (n = 1−12) clusters

An all-electron scalar relativistic calculation on Au _n Pt (n = 1−12) clusters has been performed by using density functional theory with the generalized gradient approximation at PW91 level. Our results reveal that all the lowest energy geometries of Au _n Pt  (n = 1−12) clusters may be generated by substituting Pt atom for one gold atom of the Au _n+1 cluster at the highest coordinated site. Compared with corresponding pure Au _n+1 cluster, the lowest energy geometries of Au _n Pt clusters are distorted slightly and still keep the planar structures due to the strong scalar relativistic effect in small gold cluster. The Au-Pt bonds are stronger and most Au-Au bonds far from Pt atom are weaker than the corresponding Au-Au bonds in pure Au _n+1 cluster. By substituting Pt atom for one gold atom of Au _n+1 cluster at the highest coordinated site, the relatively stable and inactive odd-numbered Au _n+1 cluster becomes the relatively unstable and reactive odd-numbered Au _n Pt cluster, and the relatively unstable and reactive even-numbered Au _n+1 cluster becomes the relatively stable and inactive even-numbered Au _n Pt  cluster chemically and electronically. All the Au _n Pt clusters prefer low spin multiplicity. The even-numbered Au _n Pt clusters are found to exhibit zero magnetic moment and the odd-numbered Au _n Pt clusters are found to possess magnetic moment with the value of 1 μ _B. The odd-even alterations of magnetic moments and electronic configurations for Au _n Pt clusters are very obvious and may be simply understood in terms of the electron pairing effect.     

The discovery of nanometer fringes in laser self-mixing interference

We demonstrate the influences of optical feedback from an external mirror with high reflectivity in a He-Ne laser on self-mixing interference fringes and laser polarization states. When the external mirror is tilted to a certain level, the stable and uniform nanometer resolution fringes are generated. The fringe density is 40 times than that of the conventional self-mixing interference or two beam interference, and has still potential to be improved. Each self-mixing interference fringe corresponds to λ/80 displacement of the external mirror, i.e. 7.91 nm displacement of the external mirror. Moreover, when the movement direction of the external mirror is changed, the polarization flipping between two eigenstates will happen. The potential applications of the results are also discussed.     

超二代微光像增强器Na2KSb(Cs)多碱光电阴极荧光谱研究

利用785 nm波长激光作为激发源,测量了超二代微光像增强器Na2KSb(Cs)多碱光电阴极的荧光谱.试验中发现该荧光谱不是一条光滑的高斯型曲线,而是一条在高斯型荧光谱上叠加了一定频率间隔小锯齿峰的曲线.经实验验证和理论分析证明该荧光谱上的小锯齿峰是一种干涉条纹,与超二代微光像增强器的结构有关.干涉条纹之间的间距与相邻两干涉峰波长的乘积成正比,与超二代微光像增强器的近贴聚焦距离成反比.干涉条纹调制度大小与Na2KSb(Cs)多碱光电阴极的厚度成反比.通过测量超二代微光像增强器Na2KSb(Cs)多碱光电阴极荧光谱上两相邻干涉条纹的间距和调制度,就可以测量或比较出不同超二代微光像增强器Na2KSb(Cs)多碱光电阴极的膜厚、近贴聚焦距离.研究结果对提高超二代微光像增强器阴极灵敏度和分辨力提供了一个有效的分析手段.     

Interaction of gold and silver cluster cations with CH<Subscript>3</Subscript>Br: thermal and photoinduced reaction pathways

The reactions of free, size selected Au _n ⁺ (n = 1–3, 5, 7) and Ag₃ ⁺ clusters with CH₃Br as well as the photodissociation of the resulting complexes at 266 nm were studied in a radio frequency ion trap under multiple collision conditions. CH₃Br was found to interact more strongly with the gold clusters than with the silver clusters. All investigated metal clusters exhibited characteristic size dependent adsorbate coverages. Furthermore, the successive loss of methyl radicals was identified as a major thermal reaction channel of the adsorbed CH₃Br molecules. Photodissociation experiments were performed with the product complexes of the trimer clusters and revealed the strongly preferred light-induced fragmentation of Au₃Br₃ ⁺ and Ag₃Br₃ ⁺, respectively, over any other thermal reaction products. However, whereas in the case of the gold cluster complexes the bare Au₃ ⁺ was exclusively re-formed through laser irradiation, considerable photoinduced metal cluster fragmentation occurred in the case of Ag₃Br₃ ⁺.