Combined nonlinear effects for UV to visible wavelength generation in a photonic crystal fiber

We experimentally study the combined nonlinear effects,including four-wave mixing,stimulated Raman scattering,soliton dynamics,and cross-phase modulation by coupling femtosecond pulses around 850 nm into the normal dispersion region near the zero-dispersion wavelength in the fundamental mode of a homemade silica photonic crystal fiber. The nonlinear optical dynamics at different stages are demonstrated,and the discrete ultraviolet(UV) to visible wavelengths widely separated from the pump wave are generated by the interaction of several nonlinear effects involved. The UV to visible wavelengths can be used as short pulse sources for multiphoton ionization,fluorescence spectroscopy,and biochemical imaging.     

Optical probing and imaging of live cells using SERS labels

During surface‐enhanced Raman scattering (SERS), molecules exhibit a significant increase in their Raman signals when attached, or in very close vicinity, to gold or silver nanostructures. This effect is exploited as the basis of a new class of optical labels. Here we demonstrate robust and sensitive SERS labels as probes for imaging live cells. These hybrid labels consist of gold nanoparticles with Rose Bengal or Crystal Violet attached as reporter molecules. These new labels are stable and nontoxic, do not suffer from photobleaching, and can be excited at any excitation wavelength, even in the near infrared. SERS labels can be detected and imaged through the specific Raman signatures of the reporters. In addition, surface‐enhanced Raman spectroscopy in the local optical fields of the gold nanoparticles also provides sensitive information on the immediate molecular environment of the label in the cell and allows imaging of the native constituents of the cell. This is demonstrated by images based on a characteristic Raman line of the reporter as well as by displaying lipids based on the SERS signal of the C H deformation/bending modes at ∼1470 cm⁻¹. Copyright © 2008 John Wiley & Sons, Ltd.     

Orienting molecules using half-cycle pulses

Using a rigid-rotor model, we study the orientation dynamics of polar diatomic molecules excited by experimentally available half-cycle pulses. The results of the numerical solution of the time-dependent Schr?dinger equation are compared to those of an approximate “sudden-impact” impulsive model neglecting the molecular rotation during the pulse. We show that efficient orientation is achieved during time periods of several picoseconds for LiCl. For short pulses, where the kicked molecule model is valid, orientation turns out to be mainly sensitive to the time-integrated field amplitude and not the shape or rise time of the pulse. Received 16 August 2000 and Received in final form 4 December 2000     

Femtosecond selective optical Kerr-effect spectroscopy: Molecular dynamics study of chloroform

The femtosecond selective spectroscopy of vibrational-rotational dynamics of molecules in a liquid was realized using optical Kerr effect registration under two-pulse nonresonant excitation. The object chosen for the study was the chloroform at room temperature. It was shown that control of the separate molecular motions by creating the constructive or destructive interference of corresponding wave packets allows one to determine directly from the experiment such constants of molecular dynamics as the relaxation times of the coherent vibrations (≈1.5 ps) and those of orientational anisotropy (≈1.2 ps).     

Femtosecond dynamics and coherent control in atoms, molecules and clusters: Theory and experiments

The understanding and control of the dynamics in atoms, molecules and clusters has been a tremendously growing field in the past decade. This has been acknowledged with the 1999 Nobel prize in chemistry awarded to Ahmed Zewail. The present issue collects some of the newest theoretical and experimental results in the field of ultrafast dynamics and coherent control in the gas phase. The papers are grouped into three categories. The first section contains work on the “Coherent Control with Femtosecond Laser Pulses”. Topics like the general theory of quantum control, the control of electron transfer processes, transformation of chiral molecules and coherent population transfer are treated here. The “Femtosecond Dynamics” taking place in molecules and clusters is the topic of the second section. New insight into the nature of atomic motion within molecules and relaxation processes is provided. The last section collects most recent work on the interaction of ultrashort laser pulses with matter. In particular, high harmonic generation, multi-photon ionization and interference effects, as well as the possible orientation of molecules in external fields are discussed. We think that the present compilation demonstrates that the field of ultrashort pulse spectroscopy is of still growing importance and exciting new phenomena have been revealed in the past and will be discovered in the future.     

Broadband coherent anti-Stokes Raman scattering spectroscopy using soliton pulse trains from a photonic crystal fiber

Pulse trains of fundamental soliton pulses with different center wavelengths and delay times from a photonic crystal fiber were generated and used as Stokes optical pulses in coherent anti-Stokes Raman scattering (CARS) spectroscopy. The pulse trains were created by shaping optical pulses with a pulse shaper and their waveforms were measured by a cross-correlation frequency-resolved optical gating method. By the use of pulse trains, the time required for obtaining broadband CARS signals was reduced to be about one third compared with our previous study without using pulse trains. With this setup, broadband CARS signals between 500 and 3100 cm⁻¹ of a single polystyrene bead sample have been measured and the most of the Raman peaks in this frequency range of samples have been observed clearly.     

Raman Spectroscopy of Biological Tissues

Abstract

We previously published a comprehensive review paper reviewing the Raman spectroscopy of biological molecules. This research area has expanded rapidly, which warranted an update to the existing review paper by adding the recently reported studies in literature. This article reviews some of the recent advances of Raman spectroscopy in relation to biomedical applications starting from natural tissues to cancer biology. Raman spectroscopy, an optical molecular detective, is a vibrational spectroscopic technique that has potential not only in cancer diagnosis but also in understanding progression of the disease. This article summarizes some of the most widely observed peak frequencies and their assignments. The aim of this review is to develop a database of molecular fingerprints, which will facilitate researchers in identifying the chemical structure of the biological tissues including most of the significant peaks reported both in the normal and cancerous tissues. It has covered a variety of Raman approaches and its quantitative and qualitative biochemical information. In addition, it covers the use of Raman spectroscopy to analyse a variety of different malignancies including breast, brain, cervical, gastrointestinal, lung, oral, and skin cancer. Multivariate analysis approaches used in these studies have also been covered.     

Control of femtosecond filamentation by field-free revivals of molecular alignment

We show that the filamentation dynamics of a femtosecond laser probe pulse can be readily controlled by properly matching it to the quantum revivals of pre-aligned molecules prepared through impulsive rotational Raman excitation with an advancing ultrashort pump pulse. Several features of the filamentation process including supercontinuum generation, the length of the plasma channel generated in the wake of the filament, the associated secondary radiations and the multiple filamentation pattern are all easily modified by tuning the cross phase modulation induced by the field-free revivals of molecular alignment, through the delay between the pump and the probe pulses. We show that molecular alignment can also be used to generate conical waves with extremely short intensity spike called shocked X-waves and to further tune the frequency of a few-cycle laser pulse in the wake of a self-guided intense filament.     

Probing single molecules and molecular aggregates: Raman spectroscopic advances

Development of Raman spectroscopy, profiting from surface‐enhanced Raman scattering and tip‐enhanced Raman scattering techniques, has inspired extensive research interest for trace analysis and dynamic measurements up to single‐molecule level. For another, Raman spectroscopy has also been recognized of significance in solving some important issues relating to molecule aggregates in chemistry and biology, owing to the capability of non‐destructive detection and high‐resolution fingerprints by which molecules and their aggregates can be identified. Herein, we summarize the recent progress of Raman spectroscopy in probing single molecules and molecular aggregates and block out a future prospective of Raman spectroscopy applied in cluster science. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigation of the glow and contracted discharge plasmas in nitrogen by coherent anti-Stokes Raman spectroscopy,optical interferometry,and numerical simulation

The translational temperature in the plasma of glow and contracted discharges is measured using the methods of coherent anti-Stokes Raman spectroscopy and optical interferometry. The current density in the discharge is determined by measuring the electron concentration with optical interferometry and emission spectroscopy. The distribution of nitrogen molecules over vibrational and rotational levels in the ground state, the electron energy distribution, and the time dependence of the gas temperature are numerically found based on a model including the homogeneous Boltzmann equation and balance equations for the concentrations of charged and excited particles and for the gas temperature. The dynamics of transition to the quasi-steady-state distribution of nitrogen molecules over vibrational levels is studied.     

Surface-enhanced raman scattering and nonlinear optics applied to electrochemistry

The most recently developed diagnostic technique in metal-electrolyte and metal-gas interfaces adapts spontaneous Raman scattering and nonlinear optical generation, techniques normally applied to bulk media, to surface science investigation. For certain metallic surfaces, an enormous increase exists in the Raman (as much as 10⁶ to 10⁸ times) and nonlinear optical signals resulting from submonolayer coverage of molecular adsorbates at the interface. Spontaneous Raman scattering and nonlinear optical scattering are well developed in both theory and practice for the analysis of molecular structure and concentration in bulk media. Instrumentation to generate and detect these inelastically scattered signals is readily available and is adequate for adaption to surface science. However, the mechanism (or mechanisms) giving rise to such a large enhancement at the interfaces is still being actively researched and remains controversial. Theoretical and experimental investigations related to the underlying physics of this enhancement and the application of such surface enhancement as a vibrational probe for adsorbates on the metal surface have been labeled “surface-enhanced Raman scattering” (SERS) and “surface-enhanced nonlinear optics”. Soon after the recognition that molecules adsorbed onto metal electrodes under certain conditions exhibit an anomalously large Raman scattering efficiency,^1–3 it became evident that such a phenomenon makes possible an in situ diagnostic probe for detailed and unique vibrational signatures of adsorbates in the ambient phase (electrolyte and atmospheric gas surroundings). Optical spectroscopy in the visible range has a much higher energy resolution (e.g., 0. I cm-I) than is presently available in electron energy loss spectroscopy (EELS), as well as the capability to measure much lower frequency modes (e.g., as low as 5 cm^?1) than is possible in infrared spectroscopy. Perhaps the most significant attribute of SERS and surface-enhanced nonlinear optical scattering is that the surrounding media in front of the interface (e.g., several meters of gas and several centimeters of liquid) do not introduce optical loss or overwhelmingly large signals. The recognition that SERS is capable of performing vibrational spectroscopy with this resolution, frequency range, and in such dense surroundings has therefore brought an explosion of activity to the field since 1977.     

Sub‐picosecond Raman spectrometer for time‐resolved studies of structural dynamics in heme proteins

We describe a pump–probe Raman spectrometer based on a femtosecond Ti:sapphire laser, an optical parametric generator and two optical parametric amplifiers for time‐resolved studies, with emphasis on the structural dynamics in heme proteins. The system provides a 100‐fs pump pulse tunable in the range 500–600 nm and a transform‐limited sub‐picosecond probe pulse tunable in the range 390–450 nm. The spectrometer has spectral (25 cm⁻¹) and temporal (∼0.7 ps) resolutions which constitute an effective compromise for identifying transient heme protein species and for following their structural evolution by spontaneous Raman scattering in the time range 0.5 ps to 2 ns. This apparatus was applied to time‐resolved studies of a broad range of heme proteins, monitoring the primary dynamics of photoinduced heme coordination state and structural changes, its interaction with protein side‐chains and diatomic gaseous ligands, as well as heme vibrational cooling. The treatment of transient Raman spectra is described in detail, and the advantages and shortcomings of spontaneous resonance Raman spectroscopy for ultrafast heme proteins studies are discussed. We demonstrate the efficiency of the constructed spectrometer by measuring Raman spectra in the sub‐picosecond and picosecond time ranges for the oxygen‐storage heme protein myoglobin and for the oxygen‐sensor heme protein FixLH in interaction with the diatomic gaseous ligands CO, NO, and O₂. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman amplification and optical short pulse generation in a waveguide with periodic gain

In this paper a new configuration of amplification is proposed for Raman amplification. In this new configuration a spatial periodic Raman gain is used to amplify a CW Raman seed that generates a short optical pulse taking into account the SPM, XPM, walk-off and pulse depletion. The amplification process is accomplished by using an intense pump pulse where its energy is transferred through SRS effect. A CW weak seed is used to represent the signal to be amplified and for pump is used a Gaussian pulse. We discuss the advantages to this configuration. First, this scheme means that the Raman-gain coefficient assumes a periodic characteristic and like a modulation process, it gives possibility to control the energy transfer from the pump to Raman seed. Second, the efficient use of the parameters of the periodic Raman coefficient function, like amplitude and frequency of the modulation, can result in a more efficient control of the signal amplification. This new configuration provides some very interesting features in the Raman amplification process when compared to the standard procedure. A complete discussion of this configuration is presented.     

In-situ optical spectroscopy and electronic properties of pyrrole sub-monolayers on Ga-rich GaAs(001)

We report on the characterization of sub-monolayers of pyrrole adsorbed on Ga-rich GaAs(001) surfaces. The interfaces were characterized by scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS) and reflectance anisotropy spectroscopy (RAS) in a spectral range between 1.5 and 8 eV. The adsorption of pyrrole on Ga-rich GaAs(001) modifies the RAS spectrum of the clean GaAs surface significantly at the surface transitions at 2.2 and 3.5 eV indicating a chemisorption of the molecules. By the help of transients at these surface transitions during the adsorption process, we were able to prepare different molecular coverages from a sub-monolayer up to a complete molecular layer. The different coverages of pyrrole were imaged by STM and electronically characterized by STS. The measurements reveal that the adsorbed molecules electronically insulate the surface and indicate the formation of new interface states around −3.5 and +4.2 eV. The RAS measurements in the UV region show new anisotropies in the spectral range of the optical transitions of the adsorbed pyrrole molecules. Our measurements demonstrate the potential of optical and electronic spectroscopy methods for the characterization of atomically thin molecular layers on semiconductor surfaces allowing a direct access to the properties of single adsorbed molecules.     

Tuning of group delay with stimulated Raman scattering-induced dispersion in gas-filled optical fiber

We report the first demonstration of group delay tuning with stimulated Raman scattering-induced dispersion in a hydrogen-filled hollow-core optical fiber. A pump laser induces a sharp refractive index change near the S_0(0)Raman transition of hydrogen molecules, enabling the control of the group velocity of signal pulses around the Stokes wavelength. Experiments with an 80-m-long hollow-core fiber filled with 2.5 bar hydrogen achieved continuous tuning of the pulse delay up to 1.42 ns by varying the Raman amplification from 0 to 10 dB. The tunable pulse delay is realized by changing the pump power as well as the hydrogen pressure. This work provides a new technique for controlling the pulse propagation in optical fibers with high flexibility.     

Can Raman spectroscopy detect cumulenic structures of linear carbon chains?

The molecular and vibrational structures of cumulenic carbon chains are investigated by density functional theory calculations and compared with that of hydrogen‐capped polyynes. The small value of bond length alternation (BLA) along the CC bonds sequence obtained by geometry optimization of uncapped C_n chains and vinyl‐capped carbon chains confirms their cumulenic structure. It is demonstrated that for finite length chains the structural parameters are determined by end effects as far as the Peierls distortion, expected for very long molecules, does not occur. The Raman spectra of such molecules are calculated to verify the possibility of identifying markers of cumulenic chains by means of vibrational spectroscopy. As expected, the longitudinal mode consisting of the BLA oscillation, which is responsible for the strongest Raman transition of polyynes, becomes very weak for cumulenes; this behaviour is rationalized in terms of local polarizability derivatives. However, other longitudinal modes can be observed in the Raman spectra of C_n chains. The wavenumber behaviour and the optical activity of these modes are interpreted on the basis of the phonon dispersion branch of an ideally infinite cumulenic polymer. Raman intensities computed for chains of different lengths allow to conclude that cumulenic molecules could be detected and identified by means of Raman spectroscopy. Copyright © 2009 John Wiley & Sons, Ltd.     

Optimization of an AO Q-switched solid-state Raman laser

An extension of the rate equation models for solid-state Raman laser is proposed and investigated with accounting for the dynamics of an acousto-optically (AO) Q-switch modulator and the effects of thermal lens provided by the pump beam. The improved model is aimed at outlining optimization strategies for wonderful laser performance with short pulse width and high peak power. A comparison between traditional intra-cavity and new couple-cavity configurations is made. The simulation results indicate that it is possible to realize an efficient sub-nanosecond coupled-cavity Raman laser by optimizing several important parameters.     

Conformational dynamics of photoexcited conjugated molecules

Time-dependent photoexcitation and optical spectroscopy of pi-conjugated molecules is described using a new method for the simulation of excited state molecular dynamics in extended molecular systems with sizes up to hundreds of atoms. Applications are made to poly(p-phenylene vinylene) oligomers. Our analysis shows self-trapping of excitations on about six repeat units in the course of photoexcitation relaxation, identifies specific slow (torsion) and fast (bond-stretch) nuclear motions strongly coupled to the electronic degrees of freedom, and predicts spectroscopic signatures of molecular conformations.     

可循环使用表面增强拉曼散射基底研究进展

表面增强拉曼散射(SERS)技术克服了拉曼光谱灵敏度低的缺点,可以获得常规拉曼光谱不易得到的分子结构信息,成为分子甚至单一分子痕量检测的一个重要手段,在生命科学、分析化学等领域得到了广泛的应用。SERS基底是SERS检测中的核心部件,只有少量特殊处理的贵金属才具有较强SERS效应,同时这些传统SERS基底一般都是一次性使用,这给实际使用造成资源的浪费。在简要介绍SERS光谱发展的基础上,重点介绍了近期在可循环SERS基底的制备和应用作一述评,并对可循环SERS基底的研究和发展做了展望。     

Laser cooling of molecules via single spontaneous emission

A general scheme for reducing the center-of-mass entropy is proposed. It is based on the repetition of a cycle, composed of three concepts: velocity selection, deceleration and irreversible accumulation. Well-known laser techniques are used to represent these concepts: Raman π-pulse for velocity selection, STIRAP for deceleration, and a single spontaneous emission for irreversible accumulation. No closed pumping cycle nor repeated spontaneous emissions are required, so the scheme is applicable to cool a molecular gas. The quantum dynamics are analytically modelled using the density matrix. It is shown that during the coherent processes the gas is translationally cooled. The internal states serve as an entropy sink, in addition to spontaneous emission. This scheme provides new possibilities to translationally laser-cool molecules for high precision molecular spectroscopy and interferometry. Received 25 June 2002 / Received in final form 28 September 2002 Published online 12 November 2002 RID="a" ID="a"e-mail: ooi@spock.physik.uni-konstanz.de RID="b" ID="b"e-mail: Peter.Marzlin@uni-konstanz.de RID="c" ID="c"e-mail: Juergen.Audretsch@uni-konstanz.de