Surface acoustic phonon modes of Ge nanocrystals embedded in SiO2

Ge nanocrystals (NCs) embedded in SiO₂ are synthesized by ion implantation, and the surface vibrational modes of the Ge NCs are investigated using the low-frequency Raman scattering (LFRS) technique. LFRS studies show distinct low-frequency Raman modes in the range 6.5-21.2 cm⁻¹ for the Ge NCs depending on the implant dose and annealing temperature. These low-frequency Raman modes are attributed to the confined surface acoustic phonon modes of Ge NCs with (0,0) spheroidal mode and (0,3) torsional modes. Our results are in excellent agreement with the recent theoretical predictions of surface vibrational modes in Ge NCs.     

Anharmonicity in polyatomic molecules: The problem of phase coincidence and applications to the CH-stretching overtone spectrum of benzene

A previous analysis of the first six members of the CH-stretching overtone spectrum of benzene in terms of local oscillators is reexamined (1). The importance of the choice of relative phases in the transformation from normal modes to local modes is elucidated. The theory is recast in a form more consistent with the limitations indicated by this analysis. The frequencies of all eight members of the CH-stretching overtone spectrum of benzene are calculated on this basis and excellent agreement with experiment is obtained.     

Raman spectroscopy on single- and multi-walled nanotubes under high pressure

The pressure dependence of the high-energy Raman modes in single- and multi-walled carbon nanotubes was measured in the range 0–10 GPa. We found the pressure coefficient to be linear in both materials but 25% smaller in MWNT. Given that the curvature effects on vibrational properties of the rolled-up graphene sheets are small, we can explain this difference simply with elasticity theory. Received: 17 May 1999 / Accepted 18 May 1999 / Published online: 4 August 1999     

Optical investigation of CdS quantum dots in Langmuir–Blodgett films

Structures with CdS quantum dots produced by the Langmuir–Blodgett (LB) technique were investigated by Raman, IR, and UV spectroscopies. The confinement effect of longitudinal optical (LO) phonons in CdS quantum dots was investigated by Raman spectroscopy. Surface vibrational modes of CdS quantum dots were observed in IR spectra. It was shown experimentally that the frequency of the surface vibrational modes depends on the properties of the surrounding media. An average size of CdS quantum dots of about 3–6.4 nm was obtained from the analysis of UV measurements. Received: 1 February 1999 / Accepted: 1 April 1999 / Published online: 19 May 1999     

Picosecond pulse generation in a benzene raman generator amplifier system

Picosecond ruby laser pulses generate simultaneously Stokes pulses of the 992 cm^–1 ring breathing mode and of the 3063 cm^–1 CH-stretching mode of benzene in a Raman generator cell by stimulated Raman scattering under self-focusing conditions. The Raman generator light is spectrally filtered, collimated, and amplified in three Raman amplifier cells pumped by ruby laser pulses. Both first Stokes lines have been selectively amplified to short, low divergence, intense light pulses.     

Coherent excitation of molecular vibrational modes by high-power ultrashort infrared laser pulses

Coherent dynamics of multiphoton excitation of molecular vibrational modes by subpicosecond IR laser pulses differs greatly from that of picosecond pulse excitation. The resonance response of a molecule is primarily determined by the power broadening rather than the laser carrier frequency. Selective excitation of high vibrational levels is possible with the use of subpicosecond pulses.     

Near-infrared coherent anti-Stokes Raman scattering microscopy using supercontinuum generated from a photonic crystal fiber

Coherent supercontinuum generated from a photonic crystal fiber is applied to near-infrared coherent anti-Stokes Raman scattering (NIR-CARS) microscopy. A clear CARS image of polystyrene beads has been successfully obtained at a wavenumber difference resonant with the CH-stretching vibrational mode. PACS 87.64.Je; 39.30.+w; 87.64.Vv     

Vibrational properties of single-wall BC3 nanotubes

The phonon dispersions of single-wall BC₃ nanotubes with any chirality are calculated within a symmetry-based force constant model of the lattice dynamics. Based on the non-symmorphic symmetry group of the BC₃ tubes, the symmetries and number of the Raman- and infrared-active modes at Γ point of the one-dimensional Brillouin zone are given. The neighbor atom-atomic interaction force constants are recalculated by fitting them to the experimental phonon energy-dispersion curves of honeycomb BC₃ sheet. The frequencies of the optically active modes are presented as the function of diameters and chiralities for BC₃ tubes. The obtained phonon density-of-states spectra, phonon dispersion relations, and vibrational patterns of the zone-center phonons are presented and discussed in detail. The calculated frequencies of infrared-active modes are compared with the experimental values reported in the literature. The results provide comprehensive information about the vibrational properties of the BC₃ tubes and shed light on the interpretation of Raman scattering and infrared spectroscopies.     

Variational study of the ground state energy of theE−b 1,b 2 Jahn-Teller system

In this paper a variational method for the ground state energy approximation of theE−b ₁,b ₂ Jahn-Teller system is presented. This method is based on the choice of a suitable variational ground state wave function. This trial wave function — a correlated squeezed state — is used to account for the correlation and anharmonicity of the interaction between the two vibrational modes; the anharmonicity of both modes is taken into account by the squeeze effects of these modes. The ground state of mode 1 in this trial wave function is considered as a linear combination of the two displaced harmonic oscillators. The ground state energies for the linearE - e Jahn-Teller system calculated by this method are not only in good agreement with the exact diagonalization results, but they are also better than those from the previous analytical studies. Another conclusion which results from the presented model is the following one: the squeezing effect of mode 1 for the linearE - e Jahn-Teller system is substantially smaller, in contrast with the results which are presented in the previous analytical studies.     

吡虫啉的太赫兹(THz)光谱研究

由超短激光脉冲产生的脉冲波是具有较宽频带的电磁辐射,属于远红外波段,该波段电磁波与物质的相互作用是个崭新的研究领域。文章利用太赫兹时域光谱技术测量了室温下吡虫啉在0.2～2.0 THz范围内的吸收谱和折射率谱。结果表明吡虫啉在此波段有明显的特征吸收峰且吸收系数随频率的增加而增大,折射率也随频率的增加而有所增大,其平均折射率为1.65。实验研究的同时,运用半经验理论计算了吡虫啉分子的结构及其在太赫兹波段的振动频率,并根据计算结果对实验数据进行了解析。计算结果与实验光谱吻合得很好,实验光谱的特征吸收峰是由分子的集体振动及扭转形成, 不同的吸收峰位对应分子不同的振转模式。实验和理论研究的对比表明：分子的远红外吸收特征对于分子的结构和空间排列非常敏感,THz-TDS是研究生物分子集体振动模式和构象结构的好方法。     

Femtosecond dynamics of primary processes in visual pigment rhodopsin

The dynamics of the coherent photoisomerization of the 11-cis-retinal in bovine rhodopsin is studied by femtosecond time-resolved laser absorption spectroscopy with a resolution of 30 fs. Rhodopsin is excited with 500-, 535-, and 560-nm femtosecond pulses to produce different initial Franck-Condon states with different vibrational energies of the molecule in its electronically excited state. The time evolution of the photoinduced differential absorption spectra of rhodopsin is measured upon excitation with a femtosecond pulse in a spectral range from 400 to 720 nm. Oscillations in the time-resolved absorption of the rhodopsin photoproducts, such as photorhodopsin with a vibrationally excited all-trans-retinal and in its initial-state rhodopsin with a vibrationally excited 11-cis-retinal, are examined. It is demonstrated that these oscillations reflect the dynamics of coherent vibrational wavepackets. The Fourier transform of these oscillatory components yields frequencies, amplitudes, and initial phases of various vibrational modes involved in the motion the wavepackets in both photoproducts. The main vibrational modes manifest themselves at frequencies of 62 and 160 cm^?1 for photorhodopsin and 44 and 142 cm^?1 for initial-state rhodopsin. It is shown that these vibrational modes are directly involved in the coherent reaction under the study, with their amplitudes in the power spectrum produced by the Fourier transform of the kinetic curves being dependent on the wavelength of rhodopsin excitation.     

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes of C₆₀ in the quasi-1D polymeric RbC₆₀, across the low temperature transition at ∼50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC₆₀ are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system.     

Highly localized vibronic wavepackets in large reactive molecules

The ultrafast dynamics of the internal conversion of S₁ azulene and the excited-state intramolecular proton transfer in 2-(2^′-hydroxyphenyl)benzothiazole (HBT) were investigated by pump–probe spectroscopy with tunable pulses as short as 20 fs. In both cases we find very pronounced oscillatory contributions to the transients, which are due to vibrational wavepacket motion in the excited state. The damping times are on the order of 1 ps even for these large reactive molecules in solution at room temperature. For azulene only 2 out of 48 vibrational modes participate and in HBT only 4 out of 69. This high degree of localization of the wavepacket seems to be a general feature, and supports hopes that even for systems of chemical interest coherent control might be possible. Received: 24 January 2000 / Published online: 24 July 2000     

Localized vibrational modes in a quasi-one-dimensional lattice with a macrodefect

The vibrational spectrum of a quasi-one-dimensional lattice with a crack-like macrodefect is studied. The localized vibrational modes of two types are found to exist in a system: (i) low-frequency vibrational modes localized inside the defect; (ii) high-frequency vibrational modes localized outside the defect. The elastic relaxation length is estimated for localized modes of both types.     

Surface shear horizontal waves associated with a periodic array of wires deposited on a substrate

The vibrational and electronic spectra of a semi-infinite crystal with a planar surface are modified by the presence of surface inhomogeneities or roughness such as ridges or grooves, quantum wires or tips. We develop a Green's function formalism to investigate the localized and resonant acoustic modes of shear horizontal polarization associated with the surface of a substrate supporting a single and a periodic array of wires. Each material is assumed to be an isotropic elastic medium. The calculation can be applied to an arbitrary choice of the shape and elastic parameters of the wires. The surface modes are obtained as well-defined peaks of the densities of states (DOS). In this paper, we calculate the variation of the density of states associated with the adsorption of a single wire, and the dispersion curves of the surface modes for a periodic array of wires on the flat surface of a substrate. We discuss their behaviors as a function of the elastic parameters and the relationship between resonant modes of the single wire and dispersion curves of the surface modes for a periodic structure. Received 6 December 2000     

Intramolecular vibrational modes of polychlorodibenzo-p-dioxines of the D 2h symmetry

The infrared and Raman spectra of the octachlorodibenzo-p-dioxine molecule are measured and all normal vibrational modes of the molecule are calculated. Each vibrational mode was assigned to the vibrations of certain functional groups of atoms in the molecule, taking into account the local symmetry characteristics of the vibration mode. A correlation of vibrational modes by their shape was established in a series of molecules: dibenzo-p-dioxine, 2,3,7,8-tetrachlorodibenzo-p-dioxine, and OCDX. The influence of substituents on vibrational frequencies was also examined.     

Moving nonlinear localized vibrational modes for a one-dimensional homogenous lattice with quartic anharmonicity

Moving nonlinear localized vibrational modes (i.e. discrete breathers) for the one-dimensional homogenous lattice with quartic anharmonicity are obtained analytically by means of a semidiscrete approximation plus an integration. In addition to the pulse-envelope type of moving modes which have been found previously both analytically and numerically, we find that a kink-envelope type of moving mode which has not been reported before can also exist for such a lattice system. The two types of modes in both right- and left-moving form can occur with different carrier wavevectors and frequencies in separate parts of the plane. Numerical simulations are performed and their results are in good agreement with the analytical predictions. Received 13 October 1999 and Received in final form 15 May 2000     

Dependence of photoemission efficiency on the pulsed laser cleaning of Tungsten photocathodes, part 1: Experimental

3+ :YAG laser with 5^th harmonic generator, generating 16 ps duration pulses at 213 nm, with energies up to 0.5 mJ. Experimental results concerning the action of laser pulses, as well as the effects of residual pressure on the cleanliness of the photocathodes surface are presented and discussed. Influence of laser pulses and residual pressure on the work function of the metal are also investigated. Received: 15 April 1996/Accepted: 5 November 1996     

Control of de-excitation to selected vibrational levels in the ground state of NaH molecule using two broadband ultrashort pulses

We show that the de-excitation to different vibrational levels of the ground state in NaH molecule can be controlled by using two delayed ultrashort pulses (4 fs Gaussian). A vibrational wave packet generated on the excited A¹Σ⁺ state by the first pulse is de-excited back to the ground state by a second pulse after a time delay. The cross-section for de-excitation of the wave packet to different vibrational levels of the ground electronic state can be controlled by controlling the delay time between the two pulses as well as by choosing a pulse duration much shorter than the vibrational period of the molecule, such that the de-excited wave packet remains localized in the Franck–Condon region of a particular vibrational level of the ground state. Hence, the de-excitation to a particular vibrational level can be enhanced by suppressing that in others. In spite of the large bandwidth of the pulse which includes nine vibrational levels of the upper state and five vibrational levels of the ground state, one can selectively de-excite the molecule to any one or two vibrational levels of the ground state by carefully choosing the delay time between the pulses and the pulse duration. We are designing the wave packet in the ground state by two short pulses and selectively distributing the population in one or two levels at various values of the delay time. In light molecules having small vibrational period, this selectivity in de-excitation to one or two vibrational levels in the ground state can be achieved only by using ultrashort (4 fs) pulses in the presence of which the localization of the wave packet in the Franck–Condon region of the vibrational levels are particularly possible. It has been shown that the de-excitation cross-section to a particular vibrational level oscillates with delay between the pulses which can be realized as a time-dependent quantum gate.     

Sum-frequency spectroscopy of physisorbed and chemisorbed molecules at liquid and solid surfaces using band-width-limited picosecond pulses

We studied the vibrational Sum-Frequency (SF) spectra of long chain fatty alcohols and amines physisorbed at liquid/air interfaces and of OctadecylTrichlorSilan (OTS) chemisorbed on glass/air interfaces in situ, i. e., in normal laboratory environment. The intense, band-width-limited IR pulses generated by our laser system are tunable from 2600 to 4000 cm^–1 with a constant pulse duration of 3 ps and a band width of 5 cm^–1 (FWHM) over the entire tuning range, thus covering the CH-, NH-, and OH-stretching regions.Using suitable polarization geometries, information on the molecular orientation is obtained from the amplitudes of the symmetric and degenerate methyl-stretching modes. Opposite phase of adjacent vibrational modes can lead to destructive interference in the SF signal, as analyzed theoretically. This interference effect is observed experimentally for the first time, due to the superior spectral resolution and signal-to-noise ratio of our spectra.