Spectroscopy of vibrational modes in metal nanoshells

In this work we study the spectrum of vibrational modes in metal nanoparticles with a dielectric core. Vibrational modes are excited by the rapid heating of the particle lattice that takes place after laser excitation, and can be monitored by means of pump-probe spectroscopy as coherent oscillations of transient optical spectra. In nanoshells, the presence of two metal surfaces results in a substantially different energy spectrum of acoustic vibrations than for solid particles. We calculated the energy spectrum as well as the damping of nanoshell vibrational modes. The oscillator strength of the fundamental breathing mode is larger than that in solid nanoparticles. At the same time, in very thin nanoshells, the fundamental mode is overdamped due to instantaneous energy transfer to the surrounding medium. PACS 78.67.-n; 78.67.Bf; 63.22.+m     

FT‐IR,FT‐Raman,and computational calculations of 4‐chloro‐2‐(3‐chlorophenyl carbamoyl)phenyl acetate

FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(3‐chlorophenylcarbamoyl) phenyl acetate were studied. Vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes and the normal modes are assigned by potential energy distribution (PED) calculations. Simultaneous IR and Raman activation of the CO stretching mode shows the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with the reported values. Analysis of the phenyl ring modes shows that C C stretching mode is equally active as strong bands in both IR and Raman, which can be interpreted as the evidence of intramolecular charge transfer via conjugated ring path and is responsible for hyperpolarizability enhancement leading to nonlinear optical activity. The red‐shift of the NH‐stretching wavenumber in the infrared spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighboring oxygen atom. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface vibrations of oxygen and sulphur in the p(2 × 2) and c(2 × 2) structures on Ni(100)

Vibrational excitations of oxygen and sulphur chemisorbed on Ni(100) in the consecutive p(2 × 2) and c(2 × 2) structures have been investigated by high-resolution electron energy loss spectroscopy (EELS). Vibrational losses due to localized modes are observed at 53 and 39 meV for the p(2 × 2)O and c(2 × 2)O structures respectively and at 46 and 44 meV for the corresponding p(2 × 2)S and c(2 × 2)S structures. The large difference in Vibrational excitation energies for the two oxygen structures as compared to those for sulphur is attributed to differences in the shape of the chemisorption potential well.     

铁电液晶MBOPDOB相变的光散射研究

我们对铁电液晶 MBOPDOB 进行了温度有关的拉曼散射研究。在低频范围记录了三条拉曼谱线(15,49,93cm~(-1))。其中15和49cm~(-1)谱线消失于 C-Sm C相变温度,没有检测到任何频移现象。93cm~(-1)拉曼线产生部分频移,消失于各向同性相,联系着偶极-偶极互作用。高频范围四个振动模(1178和1116cm~(-1),1710和1738cm~(-1))之间能量转移归于由电子转移引起的 C=0键硬化和 C-0健的弱化。同时也讨论了该液晶 Sm C-Sm A 相变的二级连续型特征。     

罗丹明101染料的光谱特性研究

观测了罗丹明101染料在甲醇和酸性甲醇溶液巾的稳态吸收、稳态荧光和时间分辨荧光光谱,得到了吸收与荧光光谱的特征信息以及荧光寿命;通过拉曼光谱、红外光谱和密度泛函理论计算,对罗丹明101染料分子的振动模式进行了指认.研究结果全面系统地表征了罗丹明101染料的光谱特征以及分子结构和振动信息,为罗丹明101染料在染料敏化太阳能电池和生物荧光标记等方面的应用研究提供了依据.     

空气/甲醇界面和频振动光谱的定量偏振分析

对空气／甲醇液体界面的和频振动光谱进行了定量的理论分析．虽然甲醇的红外和Raman光谱中都具有明显的反对称伸缩振动峰,但该光谱峰在界面和频振动光谱中却从未被观测到．利用已知的甲醇液体的红外和Raman光谱对和频振动光谱的键极化模型进行了修正,从而对此实验现象进行了定量的解释．此修正可以广泛地应用于界面和频振动光谱的研究中．     

Vibrational properties and phase transitions in II-VI materials: lattice dynamics, ab initio studies and inelastic neutron scattering measurements

Inelastic neutron scattering measurements were carried out to determine the phonon density of states of ZnSe and interpreted with lattice dynamical computations (ab initio as well as a potential model). Calculations are also reported for other II-VI compounds, ZnTe and ZnS. Vibrational (phonon spectra and Grüneisen parameters), and thermal (negative thermal expansion and non-Debye specific heat) properties have been calculated and found to be in good agreement with available experimental data. This model has been further employed to study the pressure-induced solid-solid phase transitions exhibited by these compounds and the results have been compared with experimental data. Total energy calculations for zincblende and SC16 phases of ZnSe were carried out employing the pseudopotential approach under the local density approximation (LDA) as well as the generalized gradient approximation (GGA). The density functional perturbation theory is applied to study the vibrational properties of the zincblende and SC16 phases of ZnSe. An investigation of the pressure dependence of the phonon frequencies shows that the existence of the (experimentally undetected) SC16 phase as a thermodynamically stable high pressure phase is impeded due to dynamical instabilities. A detailed investigation of the polarization of phonons of different energies for the various phases of these compounds indicates that in the case of the zincblende phase the low energy modes are librational, while in the rocksalt phase the low energy modes are bending modes. Further, in ZnTe the low energy bending modes display a larger amplitude of bending than that in ZnSe and ZnS.     

A RAIRS study of methoxy and ethoxy on oxidised Cu(100)

The adsorption and reaction of methanol and ethanol on a preoxidised Cu(100) surface was studied with Reflection-Absorption Infra-Red Spectroscopy (RAIRS). Both alcohols reacted with the modified surface well below room temperature, undergoing OH bond scission to form alkoxide species. The alkoxides were stable up to 340–360 K at which stage they desorbed as aldehydes. Vibrational assignments of the observed modes were made with reference to the RAIRS spectra of the alcohols and their deuterium substituted analogues on Cu(100) together with literature values for the gaseous, liquid and solid alcohols. Application of the metal surface selection rule to the alkoxide spectra indicate that in both cases the C---O bond lies perpendicular to the surface. The methoxy species is therefore assigned to an upright C_3v configuration. Oxygen precoverage is found to govern the amount of alkoxide formation which passes through a maximum at a precoverage of about 150 L.     

Vibration-assisted coherent excitation energy transfer in a detuned dimer

The important role of high-energy intramolecular vibrational modes for excitation energy transfer in the detuned photosynthetic systems is studied. Based on a basic dimer model which consists of two two-level systems(pigments)coupled to high-energy vibrational modes, we find that the high-energy intramolecular vibrational modes can enhance the energy transfer with new coherent transfer channels being opened when the phonon energy matches the detuning between the two pigments. As a result, the energy can be effectively transferred into the acceptor. The effective Hamiltonian is obtained to reveal the strong coherent energy exchange among the donor, the acceptor, and the high-energy intramolecular.A semi-classical explanation of the phonon-assisted mechanism is also shown.     

Vibrational mode shapes in Caribbean steelpans. I. Tenor and double second

Vibrational mode shapes have been studied in several tenor (soprano range) and double-second (alto range) steelpans by three well-known makers. Normal modes are determined from operating deflection shapes recorded by means of electronic TV holography. Vibrational modes of the various note areas are designated by the number of radial and circumferential nodal lines. Tuners generally tune one mode an octave above the fundamental and, if possible, a third mode is tuned either a twelfth or two octaves above the fundamental. Note dimensions follow an approximate scaling law L=Kf(213), and the larger note areas can be roughly modeled as rectangular plates with simply supported edges. Modal shapes in the skirt correspond to standing bending waves propagating around the ring.     

Vibrationally inelastic scattering of high- n Rydberg H atoms from N2 and O2

The vibrationally inelastic scattering of Rydberg H atoms (n = 30-50) from N2 and O2 at E(coll) = 1.84 eV was studied as a function of laboratory deflection angle. On average, 4 times more vibrational excitation was observed in collisions with O2 than with N2. Vibrational excitation of O2 results largely from collisions in which an electron is briefly transferred from O2 to the proton core, while the Rydberg electron remains a spectator. This provides further evidence that the free electron model applies to low energy collisions involving the ionic core leading to substantial momentum transfer.     

Correlation Between Energy Transfer Rate and Atomization Energy of Some Trinitro Aromatic Explosive Molecules

运用密度泛函理论的b3p86/6-31G (d,p)方法计算三硝基芳香族分子苦味酸、TBN、TNT、TATNB、2,4,6-三硝基-间甲酚、2,4,6-三硝基-苯甲醛、2,4,6-三硝基-苯甲醛肟和2,4,6-三硝基-o-三苯酚的红外振动频率以及它们的原子化能. 计算并讨论了这些炸药分子的能量迁移率与原子化能的相关性,发现能量迁移率与原子化能有较好的线性相关性. 在具有十分相近结构和相近分子量的炸药分子之间,这种相关性要更好一些.     

Generation of quadrature-squeezed light during the propagation of a light wave in a birefringent fiber

It is shown that generation of quadrature-squeezed states of a vector electromagnetic field in which quantum fluctuations in one of the quadrature components are smaller than in the coherent state can occur in cubically nonlinear media (birefringent fibers) with efficient energy transfer between the polarization modes of the field. It is shown that for certain distributions of the initial total power between modes, light with suppressed quantum fluctuations in both polarization modes of the vector field is formed at the fiber exit. The optimal conditions for obtaining quadrature-squeezed light are determined. New analytical expressions are obtained for the degree of squeezing in the two polarization modes in the case when there is no energy transfer between the polarization components of the field propagating in the fiber (eigenmodes of two-wave mixing).     

Vibrational dynamics of nitromethane mixed with IR780 dye studied by coherent anti‐stokes Raman spectroscopy

Vibrational coupling between different kinds of molecules in liquid mixture is studied by multiplex coherent anti‐Stokes Raman spectroscopy (CARS). To identify vibrational coherence, fs‐probe with high time resolution and narrowband‐probe with high spectral resolution are adopted in CARS experiments. Using liquid nitromethane (NM) mixed with organic dye IR780 perchlorate as the sample, we can clearly observe the interference between different vibrational modes. The intermolecular vibrational interaction between NM and IR780 molecules results in the vibrational coherence transfer (VCT) in the form of a change of phase correlation. Compared with symmetric bending vibration of NO₂, coherence transfer is found to be easier to take place between C―N bond of NM and vibrations of IR780, which indicates the selectivity of intermolecular vibrational interaction. The selectivity is deduced to be related to the coordination between intramolecular and collective motion of molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

Investigation of energy transfer in terbium doped Y (2)SiO(5) phosphor particles

The kinetics of luminescence of sol-gel synthesized terbium doped Y (2)SiO(5) (YSO) phosphor particles is investigated in detail with reference to Tb concentration in the 0.001%-10% range. By increasing the dopant concentration, the luminescence profile changes from a blue to a green peaked emission spectrum because of the energy transfer among centers. The inter-center energy transfer mechanism is well accounted for by the Inokuti-Hirayama (IH) kinetic model which is based on a statistical average of inter-center distance dependent decay modes of the donor luminescence. The distribution of the decay modes is implemented from the F?rster-Dexter resonance theory of energy transfer by assuming a rate constant for the energy transfer by multipolar interactions between donors and acceptors. However, the experimental results recorded in the low concentration limit show the presence of green emission contributions in the luminescence spectrum which cannot be related to the Tb concentration; for this reason an additional internal energy transfer mechanism, occurring among levels of the same center, is proposed to account for the recorded emission properties. Thus, a new and more exhaustive model which includes both the internal and external energy transfer processes is considered; the proposed model allows a better explanation of the spectroscopic features of Tb related centers in YSO crystals and discloses the critical concentration and the quantum yields of the different energy transfer mechanisms.     

Chemically modified semiconductor surfaces: 1,4-phenylenediamine on Si(100)

The formation of inorganic/organic hybrid systems in ultra-high-vacuum (UHV) is studied for the adsorption of 1,4-phenylenediamine (PDA) and aniline on Si(100)(2 × 1) single crystal surfaces. X-ray photoemission spectra (XPS) of PDA and aniline adsorbed on silicon are interpreted in terms of an adsorbate configuration involving two covalent bonds between one amino group per molecule and the dangling bonds of the clean silicon surface. Vibrational high resolution electron energy loss spectroscopy (HREELS) allows us to identify the remaining amino groups in the PDA-adsorbate. Ultraviolet photoemission spectroscopy (UPS) and electron energy loss (EELS) data in the valence band range indicate that the aromatic ring stays intact after the chemisorption of PDA. Changes in work function and energetic shifts of the electronic transitions characterize the charge transfer between adsorbate and substrate. The experimental results are finally discussed in the framework of semi-empirical cluster calculations using MNDO-PM3.     

分子自组装膜表面滴膜共存冷凝传热的研究

本文以不同处理工艺制备十八烷基硫醇自组装膜,研究制备的表面上蒸气冷凝传热过程.结果表明不同的成膜温度,可以实现膜表面上水蒸气冷凝形态从膜状到滴状的过渡.并研究了该表面上滴膜共存状态下的冷凝传热特性,表明过渡状冷凝传热随固液自由能差渐进变化的实质是冷凝形态的渐进变化,表面上冷凝液运动形态的不同也将导致传热性能的改变,并对自组装膜表面上的冷凝传热系数可能随操作时间的增加而回升的现象进行了分析.     

Numerical ensemble study of the approach to equilibrium of an anharmonic chain

The equation of motion of a 17-particle chain with anharmonic nearest neighbour forces have been numerically integrated for 101 different initial conditions. The 101 stored histories constitute a constant energy ensemble. The time dependence of the coarse grained mode Boltzmann H functions indicates that the ensemble evolves reversibly from an initial non-equilibrium state to a final equilibrium state characterized by a minimum in each mode H function. There is no equipartition of energy among the modes.     

Experimental investigations on energy-transfer characteristics and performance of some laser dye mixtures

Energy transfer from both Coumarin 120 (C120) and p-Bis(o-methylstyryl)-benzene (Bis-MSB), energy donors, to coumarin 7(C7) (acceptor) individually has been studied by steady-state emission measurements in methanol. The dye laser characteristics of the above-mentioned dyes have also been studied with respect to the energy transfer mechanism in the same solvent using a pulsed nitrogen laser as a pumping source. The large values of the critical transfer distances, R₀, indicate that the dominant mechanism responsible for energy transfer is due to long-range dipole–dipole interaction between the excited donor and ground state acceptor molecule. Both photophysical and photochemical stability of the donors has been examined under the effect of N₂ laser pumping.     

激发态H2(X1∑+g,v=1,J=1)之间的碰撞能量合并

受激拉曼激发H2(0,1)基态的Q支得到H2(1,1)能级.在室温条件下,利用反斯托克斯拉曼散射(CARS)探测技术测量了碰撞能量合并(EP)过程H2(1,1)+H2(1,1)→H2(2,J)+H2(0,J″)及H2(1,1)与H2(1,J)转动能级间的碰撞转移速率系数.扫描CARS谱表明在H2(1,1)能级的碰撞能量...