Effects of the structural order of canthaxanthin on the Raman scattering cross section in various solvents: A study by Raman spectroscopy and ab initio calculation

In this work,we measure the Raman scattering cross sections(RSCSs) of the carbon-carbon(CC) stretching vibrational modes of canthaxanthin in benzene,acetone,n-heptane,cyclohexane,and m-xylene.It is found that the absolute RSCS of CC stretching mode of canthaxanthin reaches a value of 10 24 cm 2 ·molecule 1 ·sr 1 at 8×10 5 M,which is 6 orders of magnitude larger than general RSCS(10 30 cm 2 ·molecule 1 ·sr 1),and the RSCSs of canthaxanthin in various solvents are very different due to the hydrogen bond.A theoretical interpretation of the magnetic experimental results is given,which is introduced in a qualitative nonlinear model of coherent weakly damped electron-lattice vibration in the structural order of polyene chains.In addition,the optimal structure and the bond length alternation(BLA) parameter of canthaxanthin are calculated using quantum chemistry calculation(at the b3lyp/6-31g(d,p) level of theory).The theoretical calculations are in good agreement with the experimental results.Furthermore,the combination of Raman spectroscopy and the quantum chemistry calculation study would be a quite suitable method of studying the structures and the properties of the π-conjugated systems.     

Theoretical and experimental studies on stability of the C‐ON bond in new ketone functionalized N‐alkoxyamines

Three new ketone functionalized N‐alkoxyamines derived from 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO) were prepared: N‐(1‐phenylpropyloxy)‐2,2,6,6‐tetramethylpiperidin‐4‐one, 1‐phenyl‐1‐(2,2,6,6‐tetramethylpiperidinoxy)propanone, 1‐phenyl‐1‐(4‐oxo‐2,2,6,6‐tetramethylpiperidinoxy)propanone. The rate constants of C‐ON bonds homolysis in the synthesized alkoxyamines were determined over a range of temperatures via nitroxide‐exchange experiments using HPLC to monitor the concentration. The Arrhenius parameters of homolysis for the investigated alkoxyamines were determined (lnA, E_a). Homolytic bond dissociation energies (BDE) of the C‐ON bond in the synthesized compounds were determined from quantum‐mechanical calculations at the B3‐LYP/6‐31G(d) and BMK/6‐311+G(3df,2p) levels. Ketone functionalization of the alkyl fragment of alkoxyamine in β position dramatically increases the rate constant of homolysis (by a factor of ca. 500 at the temperature of 363 K) suggesting that the new ketone functionalized N‐alkoxyamines should be effective as C‐radical precursor and unimolecular initiators in NMRP at lower temperatures than the alkoxyamines applied earlier. The analyses of natural bond, frontal orbitals and spin distribution indicated that the decrease in the strength of C‐ON bonds in ketone fuctionalized alkoxyamines in the alkyl fragment predominantly originates from a substantially smaller HOMO–LUMO gap and more delocalized spin density in leaving alkyl radicals as compared with unfunctionalized alkoxyamines. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermal stability of ultrathin amorphous carbon films synthesized by plasma-enhanced chemical vapor deposition and filtered cathodic vacuum arc

Abstract

Ultrathin hydrogenated amorphous carbon (a-C:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and hydrogen-free amorphous carbon (a-C) films of similar thickness deposited by filtered cathodic vacuum arc (FCVA) were subjected to rapid thermal annealing (RTA). Cross-sectional transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) were used to study the structural stability of the films. While RTA increased the thickness of the intermixing layer and decreased the sp³ content of the a-C:H films, it did not affect the thickness or the sp³ content of the a-C films. The superior structural stability of the FCVA a-C films compared with PECVD a-C:H films, demonstrated by the TEM and EELS results of this study, illustrates the high potential of these films as protective overcoats in applications where rapid heating is critical to the device functionality and performance, such as heat-assisted magnetic recording.     

A DFT study of CO adsorbed on clean and hydroxylated anatase TiO2 (001) surfaces

The adsorbate–substrate interaction between carbon monoxide and clean and hydroxylated surfaces of anatase (001) was simulated by periodic DFT calculations. For the clean surface, different periodicities were taken into account in order to investigate the influence of lateral effects. The results show that the molecule interacts only with the penta-coordinated titanium ion when high surface coverages are employed, whereas it interacts with both the titanium and the di-coordinated oxygen ions when the smallest surface coverage is considered. Adsorption on the hydroxylated surface, which was carried out for the first time, was studied by considering the largest used periodicity and focusing attention on the influence of both the terminal and bridging OH groups. The resulting data show that, in the case of adsorption on the hydroxylated surface, no additional bond between the surface oxygen and the carbon atom is present. Therefore, in a regime of very low surface coverage, the molecule behaves in a very different way when it interacts with a clean or a hydroxylated surface.     

CuX(X=Al, Ga, In)分子的势能函数与稳定性的密度泛函研究

根据原子分子反应静力学原理导出了CuX(X=Al,Ga,In) 分子基态电子状态及其离解极限,并在B3LYP/LANL2DZ水平上计算了平衡几何、振动频率和解离能.利用Murrell-Sorbie 函数拟合出了解析势能函数,并计算出光谱参数和力常数.计算结果表明该分子体系是稳定存在的,其稳定性排序为 CuAl＞CuGa＞CuIn.     

Growth mode and interface structure of Ag on the HF-treated Si(111):H surface

A growth mode and interface structure analysis has been performed for Ag deposited at a high temperature of 300°C on the HF-treated Si(111):H surface by means of medium-energy ion scattering and elastic recoil detection analysis of hydrogen. The measurements show that Ag grows in the Volmer-Weber mode and that the Ag islands on the surface are epitaxial with respect to the substrate. The preferential azimuthal orientation is A-type only when Ag is deposited slowly. The interface does not reconstruct to the √3 × √3-Ag structure, which is normally observed for Ag deposition above 200°C on the Si(111)7 × 7 surface, but retain bulk-like structure. The presence of hydrogen at the interface is demonstrated after deposition of thick (1100 Å) Ag films. However, the amount of hydrogen at the interface is not a full monolayer. This partial desorption of hydrogen from the interface explains why the Schottky barrier heights of Ag/Si(111):H diodes are close to those of Ag/Si(111)7 × 7 and Ag/Si(111)2 × 1.     

Theoretical study on structures and stability of SiC3S isomers

Various levels of calculations are carried out to explore the potential energy surfaces (PES) of singlet and triplet SiC₃S, a molecule of potential interest in interstellar chemistry. At the DFT/B3LYP/6-311G(d) level, a total of 57 minimum isomers and 92 interconversion transition states are located. The structures of the most relevant isomers and transition states are further optimized at the QCISD/6-311G(d) level followed by CCSD(T)/6-311?+?G(2df) single-point energy calculations. At the QCISD level, the lowest-lying isomer is the chain-like SiCCCS ³ 1 (0.0?kcal/mol) with a great kinetic stability of 54.1?kcal/mol. In addition, ring isomers CC-cCSSi ¹ 9 (19.8?kcal/mol), S-cCCCSi ¹ 12 (30.4?kcal/mol), S-cCCSiC ¹ 18 (9.4?kcal/mol), S-cSiCCC ¹ 21 (34.4?kcal/mol) and cage-like isomer cage-SiSCCC ¹ 23 (51.8?kcal/mol) also possess considerable kinetic stability (more than 10.0?kcal/mol). As a result, these six isomers are predicted to be possible candidates for future experimental and astrophysical detection. The bond natures and possible formation pathways in interstellar space of the SiCCCS are discussed. The predicted structure and spectroscopic properties for it are expected to be informative for the identification of SiC₃S and even larger SiC _n S species either in laboratory or in space.     

A simple and accurate approach for calculating the vibration spectra of molecules on surfaces: Comparisons to high resolution electron energy loss data for ethylene on silicon

Peak assignment is a complex but important task for analyzing the vibration spectra of surface-bound molecules. Here we describe a simple approach for calculating infrared and Raman spectra for surface-bound molecules using a cluster model approach with quantum capping potentials (QCPs). The utility of the approach is demonstrated by comparisons to the measured high resolution electron energy loss spectra for ethylene on clean silicon. By capping the silicon cluster with QCPs we computed spectra that agree very well with the HREEL spectrum, allowing us to easily assign the experimental peaks. QCPs are similar to effective core potentials, can be used with any ab initio technique and most computational chemistry packages, and their use requires no special expertise.     

利用传感器距离和能耗约束的无线传感器网络路由优化

针对大多数现有的无线传感器网络设计方法通常仅找到给定图的最短路径而导致只能优化单个用户性能的问题,提出了一种寻找节点之间的最短路径和最低能耗的路由优化模型,该模型约束WSNs的特定资源,考虑多种约束条件：多周期、最短距离和低能耗。本文按照混合整数线性规划,使用11.0 ILOG CPLEX优化引擎的ILOG OPL开发工具5.5进行编码和求解本文的优化模型。实验结果表明,相比一般可行网络,本文模型的节点的总距离和能耗均有明显降低,此外,在三个不同周期和约束条件数下,每组实验花费的时间均少于10s,完全满足资源有限的无线网络应用要求。     

用能量自洽法研究部分卤化钙分子CaX (X=Br, Cl, F)的解析势能函数

采用研究解析势能函数的能量自洽法Energy Consistent Method (ECM), 研究了部分卤化钙分子CaX (X=Br, Cl, F) 的C2S+、A2和B2S+态等基态和低激发态的解析势能曲线。并与曾经常使用的Morse 势、Huxley-Murrell-Sorbie (HMS)势和基于实验的Rydberg- Klein-Rees (RKR) 数据进行了比较。结果表明,这些 ECM 势能不仅能与RKR 数据符合得很好,而且还能得到实验方法难以得到、常用的Morse 势和HMS 势函数可能会产生较大误差、但在许多研究中又非常重要的渐近区和离解区的势能数据,得到了物理性质优秀的全程解析势能。     

Adsorption of organic molecules by photochemical reaction on Cl:Si(1 1 1) and H:Si(1 1 1) evaluated by HREELS

The covalent attachment of alkyl groups to silicon surfaces, via carbon-silicon bond formation, has been attempted using gas-surface reactions starting from Cl-terminated Si(1 1 1) or H:Si(1 1 1) under ultraviolet light irradiation. The formation of Cl-terminated Si(1 1 1) and its resulting stability were examined prior to deposition of organic molecules. High-resolution electron energy loss spectroscopy (HREELS) was utilized for detecting surface-bound adsorbates. The detection of photo-deposited organic species on Cl:Si(1 1 1) from gas-phase CH₄ or CH₂CH₂ was not significant. On H:Si(1 1 1), it was evident that after the photoreaction with gas-phase C₂H₅Cl, C₂H₅ groups were chemically bonded to the surface Si atoms through single covalent bonds. The C₂H₅ groups were thermally stable at temperatures below 600 K. Alkyl monolayers prepared on silicon surfaces by dry process will lead to a new prospective technology of nanoscale fabrication and biochemical applications.     

CuPc molecules adsorbed on Au(1 1 0)-(1 × 2): growth morphology and evolution of valence band states

We present the growth morphology, the long-range ordering, and the evolution of the valence band electronic states of ultrathin films of copper phthalocyanine (CuPc) deposited on the Au(1 1 0)-(1 × 2) reconstructed surface, as a function of the organic molecule coverage. The low energy electron diffraction patterns present a (5 × 3) reconstruction from the early adsorption stages. High-resolution UV photoelectron spectroscopy data show the disappearance of the Au surface states related to the (1 × 2) reconstruction, and the presence of new electronic features related to the molecule-substrate interaction and to the CuPc molecular states. The CuPc highest occupied molecular orbital gradually emerges in the valence band, while the interface electronic states are quenched, upon increasing the coverage.     

Coadsorption of water and CO molecules on Ru(0 0 1) at high CO coverages: comparisons with a Ru(0 0 1) electrode surface

The coadsorption of carbon monoxide (CO) and water molecules on a Ru(0 0 1) surface has been studied by infrared spectroscopy, LEED and STM. At high CO coverage phases, a 2×2-(2CO+D₂O) structure was observed on both UHV and electrode surfaces. Electrode potential dependent structures from CO and water adlayers on an electrode surface were reproduced on a UHV surface by controlling molecular orientations of the first layer and second over-layer water molecules. At lower CO coverages, a CO band center showed coverage dependent shift down to 1444 cm⁻¹ due to an electron transfer from a lone pair of a water molecule to CO 2π^*.     

Electron and lattice structure of ultra thin Ag films on Si(1 1 1) and Si(0 0 1)

We studied the low temperature (T ? 130 K) growth of Ag on Si(0 0 1) and Si(1 1 1) flat surfaces prepared by Si homo epitaxy with the aim to achieve thin metallic films. The band structure and morphology of the Ag overlayers have been investigated by means of XPS, UPS, LEED, STM and STS. Surprisingly a (√3 × √3)R30° LEED structure for Ag films has been observed after deposition of 2-6 ML Ag onto a Si(1 1 1)(√3 × √3)R30°Ag surface at low temperatures. XPS investigations showed that these films are solid, and UPS measurements indicate that they are metallic. However, after closer STM studies we found that these films consists of sharp Ag islands and (√3 × √3)R30°Ag flat terraces in between. On Si(0 0 1) the low-temperature deposition yields an epitaxial growth of Ag on clean Si(0 0 1)-2 × 1 with a twinned Ag(1 1 1) structure at coverage’s as low as 10 ML. Furthermore the conductivity of few monolayer Ag films on Si(1 0 0) surfaces has been studied as a function of temperature (40-300 K).     

Calculated polar substituent effects on the stability of 3‐substituted(X) bicyclo[1.1.1]pent‐1‐yl cations and 4‐substituted(X) bicyclo[2.2.1]hept‐1‐yl cations: a DFT study

The effects of substituents on the stability of 3‐substituted(X) bicyclo[1.1.1]pent‐1‐yl cations (3) and 4‐substituted(X) bicyclo[2.2.1]hept‐1‐yl cations (4), for a set of substituents (X = H, NO₂, CN, NC, CF₃, CHO, COOH , F, Cl, HO, NH₂, CH₃, SiH₃, Si(CH₃)₃, Li, O^?, and NH₃⁺) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6‐311 + G(2d,p) and B3LYP/6‐31 + G (d) levels of theory, respectively. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 3/4 and polar field/group electronegativity substituent constants (σ_F and σ_χ, respectively). The analysis reveals that the ΔE values for both systems are best described by a combination of both substituent constants. The result highlights the importance of the σ_χ dependency of charge delocalization in these systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Calculated polar substituent effects on the stability of 4‐substituted(X) ‐ cub‐1‐yl and ‐bicyclo[2.2.2]oct‐1‐yl cations: a DFT study

The effects of substituents on the stability of 4‐substituted(X) cub‐1‐yl cations ( 2 ), as well as the benchmark 4‐substituted(X) bicyclo[2.2.2]oct‐1‐yl cation systems ( 7 ), for a set of substituents (X = H, NO₂, CN, NC, CF₃, COOH , F, Cl, HO, NH₂, CH₃, SiH₃, Si(CH₃)₃, Li, O^?, and NH) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6‐311 + G(2d,p) level of theory. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 2 / 7 and polar field/group electronegativity substituent constants (σ_F and σ_χ, respectively). The analysis reveals that the ΔE values of both systems are best described by a combination of both substituent constants. This highlights the distinction between through‐space and through‐bond electronic influences characterized by σ_F and σ_χ, respectively. Copyright © 2010 John Wiley & Sons, Ltd.