The onset of coulomb explosions in polyatomic molecules

With the development of high intensity femtosecond lasers, the ionisation and dissociation dynamics of molecules has become an area of considerable interest. Using the technique of femtosecond laser mass spectrometry (FLMS), the molecules carbon disulphide, pyrimidine, toluene, cyclohexanone and benzaldehyde are studied with pulse widths of 50 fs in the near infrared (IR) wavelength region (790 nm). Results are presented and contrasted for laser beam intensities around 10(15) and 10(16) W cm(-2). For the lower intensities, the mass spectra yield dominant singly charged parent ions. Additionally, the appearance of doubly charged parent ions is evident for carbon disulphide, toluene and benzaldehyde with envelopes of doubly charged satellite species existing in these local regions. Carbon disulphide also reveals a small triply charged component. Such atomic-like features are thought to be a strong fingerprint of FLMS at these intensities. However, upon increasing the laser intensity to approximately 10(16) W cm(-2), parent ion dominance decreases and the appearance of multiply charged atomic species occurs, particularly carbon. This phenomenon has been attributed to Coulomb explosions in which the fast absorption of many photons may produce transient highly ionised parent species which can subsequently blow apart. Copyright 1999 John Wiley & Sons, Ltd.     

Cobalt coated substrate for matrix-free analysis of small molecules by laser desorption/ionization mass spectrometry

Small molecule analysis is one of the most challenging issues in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. We have developed a cobalt coated substrate as a target for matrix-free analysis of small molecules in laser desorption/ionization mass spectrometry. Cobalt coating of 60-70 nm thickness has been characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, and laser induced breakdown spectroscopy. This target facilitates hundreds of samples to be spotted and analyzed without mixing any matrices, in a very short time. This can save a lot of time and money and can be a very practical approach for the analysis of small molecules by laser desorption/ionization mass spectrometry.     

Etude experimentale de la structure fine du spectre Raman de rotation de l'oxygene

It has been demonstrated that the output from a discharge pumped KrF laser (249 nm) is capable of ionizing a variety of molecules. The nature and yield of ions generated in this process, which have been identified by time of flight mass spectrometry, exhibit a striking intensity dependence.     

Electromagnetically induced transparency in double quantum dot under intense laser and magnetic fields: from Λ to Ξ configuration

We theoretically investigated the effects of non-resonant intense laser and magnetic fields on the optical properties of asymmetric GaAs/AlGaAs double quantum dot related to the occurrence of electromagnetically induced transparency, using compact density-matrix formalism and effective mass approximation. The chosen structure has the advantage to present x-lambda(Λ)-configuration or y-ladder(Ξ)-configuration for EIT occurrence, depending on lasers polarization, at low values of the non-resonant laser, and to change the configuration from Λ to Ξ at the increase of the x-polarized non-resonant laser intensity. We discussed in detail the influences of the control laser field intensity, non-resonant laser strength and polarization, and magnetic field intensity on the absorption coefficient, refraction index and group index. It is found that: (i) the control laser or the non-resonant laser at the same control laser intensity influences more the system being in x-Ξ-configuration than in x-Λ-configuration and have intermediate effects on y-Ξ-configuration; (ii) the magnetic field has the greatest influence on the system being in x-Λ-configuration and the lowest for y-Ξ-configuration; (iii) the increment of the non-resonant intense laser or magnetic fields induces a red-shift of the transparency windows and sub (super) luminal frequency intervals for the Λ-configuration but a blue-shift for both Ξ-configurations.     

Non-resonant multophoton ionization of cyclopentane and its heterocyclic analogues

We report non-resonant multiphoton ionization time-of-flight mass spectra for cyclopentane, tetrahydrofuran, tetrahydrothiophene and pyrrolidine for 355 nm excitation over a wide range of laser intensities. Unlike the corresponding three-membered ring system, there is little dependence of the fragmentation pathways upon the laser intensity. The results also indicate that the mechanisms for the molecules studied cannot be generalized and are not necessarily related to those of the three-membered rings.     

Intense laser-induced electronic and optical properties in double finite oscillator potential

In the present paper, a theoretically study of the non-resonant laser field effect on the optical response, such as nonlinear optical rectification (NOR), second (SHG) and third harmonic generation (THG) coefficients in double finite oscillator potential (DFO) quantum wells is performed in the framework of the effective mass approximation. The obtained results reveal that, energy states and optical response is significantly affected by the non-resonant intense laser field (ILF) intensity and symmetry of the structure. Also it was found that the laser field is more effective on the optical response in the DFO potential when the asymmetric character of the confinement potential is strong. Thus, the NOR, SHG and THG coefficients with designated values can be obtained by using a properly adjusted ILF intensity and symmetry parameter of confinement potential.     

Analysis of ionic fragments from 308 nm photoablation of polyimide

The ionic products from excimer laser photoablation (=308 nm) of polyimide (Kapton) film have been studied as a function of fluence. Large ion masses up to about 900a.m.u. are easily observed, the mass distribution depending strongly on the fluence. Velocities of the emitted particles lie between 1400 and 10 000 ms^–1, again dependent on the fluence. A mechanism to explain the high velocities is suggested consisting of ionisation of the surface polymer molecules followed by a Coulomb explosion combined with expansion of the high density gas formed by the photoablation.     

High-order harmonic generation from organic molecules in ultra-short pulses

We have studied high-order harmonic generation (HHG) from organic molecules irradiated with near-infrared high intensity laser pulses of 70 fs and 240 fs duration. The molecular systems studied were the aromatics benzene and naphthalene and the alkanes cyclopropane and cyclohexane (cyclic) and n-hexane (linear). Harmonic intensities were measured both as a function of laser intensity (in the range 5×10¹³-5×10¹⁵ W cm^-2) and as a function of ellipticity of the laser field polarisation. The results were compared with those from the xenon atom. For 70 fs pulses, harmonic generation from the organic systems was similar to that of xenon, revealing an atom-like behaviour for molecules when the laser pulse duration is shorter than the fragmentation timescale of the molecule. We note significant differences between molecules with respect to HHG efficiencies and the suppression of HHG in larger species. We discuss these differences in the context of the molecular properties, electronic structure and behaviour of ionisation and fragmentation that result in enhancement of field ionisation in larger systems. Study of the polarisation ellipticity dependence of HHG shows that the harmonic yield in molecules is less sensitive to the polarisation than for atoms (xenon). This is consistent with the expected behaviour given the larger recollision cross-section presented by the core in the molecular system compared to the atom. Our results suggest that study of HHG from molecules exposed to ultra-short pulses is potentially a powerful tool for understanding the electron dynamics of molecules exposed to an intense field. Received 14 September 2000 and Received in final form 6 December 2000     

Possibilities and limitations of high-resolution mass spectrometry in life sciences

We have applied time-of-flight secondary ion mass spectrometry (ToF-SIMS) and laser post-ionization secondary neutral mass spectrometry (laser-SNMS) to examine the immobilization process of PNA and its hybridization capability to unlabeled complementary DNA fragments, to characterize immobilized proteins, and to image intrinsic elements and molecules with subcellular spatial resolution in different types of frozen non-dehydrated biological samples.The possibilities and limitations of ToF-SIMS and laser-SNMS for imaging elements and molecules in biological samples are discussed. Furthermore possibilities for enhancing the detection sensitivity by using polyatomic and cluster primary ions and different laser post-ionization schemes, as well as ways of obtaining 3D molecular images from biological samples are described.The data shows that both ToF-SIMS and laser-SNMS are capable of imaging elements and molecules in complex biological samples and that they are very valuable tools in advancing applications in life sciences. It was found that cluster-ion bombardment is very useful for enhancing the molecular yield, while laser-SNMS resulted in much higher detection sensitivity for elements and specific molecules and is particularly well suited for imaging ultra-trace element concentrations in biological samples.     

Waveguide propagation of laser beams in media with saturating non-linearity

The waveguide propagation of Gaussian laser beams in dielectric media with saturating non-linearity has been investigated analytically, using two profiles for the dependence of the dielectric constant on intensity. An expression for the radius of the uniform wave-guide, corresponding to a given power of the beam, has been obtained and the existence of a minimum radius, corresponding to an optimum power, has been predicted. For high power laser beams, oscillatory waveguides have been obtained; for very high powers the oscillations of the radius of the waveguide are small.Work supported by NOAA, USA.Work supported by CSIR, India.Work supported by NSF, USA; on sabbatical leave from IIT, Delhi.     

Controlling isotopic effects in the resonance ionisation mass spectrometry of krypton

We have investigated and characterised possible sources of variation in measured isotope ratios in the resonance ionisation mass spectrometry of krypton using resonant transitions at 116.48 and 558.04 nm and ionisation at 1064 nm. Variation arises when the spectral width of the hyperfine structure of the odd isotopes is comparable to the laser bandwidth and from the alignment of the first excited state, which depends on the relative polarisations of the laser pulses exciting the resonant transitions.     

Integrated target-ion source unit for on-line production of radioactive short-lived isotopes

A new version of integrated target-ion source unit (ionising target) has been developed for the on-line production of radioactive single-charged ions. The target is able to withstand temperatures up to 2500 ^°C and acts also as an ion source of the surface and laser ionisation. Off-line and on-line experiments with the ionising target, housing tantalum foils as a target material, have been carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility. The off-line surface ionisation efficiency measured for stable atoms of Li, Rb and Cs was correspondingly 6% , 40% and 55% at the target temperature of 2000 ^°C and 3-10% for atoms of rare-earth elements Sm, Eu, Tm and Yb at a temperature of 2200 ^°C. The off-line measured values of the ionisation efficiency for stable Gd and Eu atoms by the laser beam ionisation inside the target were 1% and 7%, respectively. The radioactive beam intensities of neutron-deficient rare-earth nuclides from Eu to Lu produced by the integrated target-ion source unit have been measured at a temperature of 2500 ^°C. The results of the integrated target-ion source unit use for on-line laser resonance ionisation spectroscopy study of neutron-deficient Gd isotopes have been also presented.     

Photoionization mass-spectrometry of benzene and benzaldehyde molecules with an excimer KrF laser

A laser photoionization time-of-flight mass-spectrometer has been developed and used to investigate the photoionization and photofragmentation of benzene and benzaldehyde molecules by an excimer KrF laser radiation at the wavelength of 249 nm in the intensity range from 5·10⁴ to 5·10⁹ W/cm². It has been found that at low laser intensity ions formed by two-step photoionization are most abundant in mass spectra. By increasing laser intensity an extensive fragmentation of molecules, up to C⁺ ions, was observed. The maximum ionization yield of benzaldehyde comes to 0.1% of the number of molecules in the photoionization volume and, according to calculations, to 10% for benzene molecules, when the radiation intensity is 5·10⁹ W/cm².     

原子光谱/元素质谱在生命分析中的应用进展

原子光谱/元素质谱是元素分析的强有力手段,其在生命分析领域的应用也越来越广泛。在单细胞元素分析方面,相关研究工作主要关注元素在单细胞中的分布和形态变化;在元素标记策略分析领域,利用原子光谱（atomic spectrometry, AS）和电感耦合等离子体质谱（inductively coupled plasma mass spectrometry, ICP-MS）实现对小分子、核酸、蛋白质等目标分析物的高灵敏检测是研究热点;在金属药物分析领域,ICP-MS为研究金属药物在生物体中的摄入、分布、代谢和排泄等过程提供了便利,也为进一步阐明药物作用机理以及金属药物的设计和改进提供了数据支持;在生物元素成像领域,ICP-MS与激光剥蚀技术（laser ablation, LA）联用,可以对生物样品进行原位分析和微区分析,结合有机质谱实现元素相关生物过程的分子机制研究;与相关分离方法联用,原子光谱和元素质谱还可以对生物组织中元素进行形态分析,研究其在相关过程中的生物转化过程。本文从单细胞元素分析、元素标签标记策略、金属药物转运与代谢以及生物组织中元素分布分析等方面,评述了原子光谱和ICP-MS在生命分析中的应用实例,并对该领域的发展前景进行了展望。     

Measuring technique for thermal ionisation mass spectrometry of human tracer kinetic study with stable cerium isotopes

Thermal ionisation mass spectrometry (TIMS) method has been developed for the simultaneous detection of different cerium isotopes in biological samples (i.e., blood and urine) at very low concentrations. The work has been done in the frame of a biokinetic study, where different stable cerium isotopes have been administered orally and intravenously as tracers to the human body. In order to develop an appropriate detection method for the tracers in the biological samples, an optimum sample preparation technique has been set and adapted to the specific requirements of the analysis technique used, i.e., TIMS. For sample evaporation and ionisation, the double tantalum filament technique showed the best results. The ions produced were simultaneously collected on a secondary electron multiplier so that the isotopic ratios of the cerium isotopes in the biological samples could be measured. The technique has been optimised for the determination of cerium down to 1?ng loaded on the evaporation filament corresponding to cerium concentrations of down to 1?ng?ml(-1) in the blood or urine samples. It has been shown that the technique is reliable in application and enables studies on cerium metabolism and biokinetics in humans without employing radioactive tracers.     

准分子激光取样与电感耦合等离子体质谱和光谱联用分析仪器研究进展

将准分子激光剥蚀取样后的产物经由电感耦合等离子质谱与光谱分析,从而获得被激光剥蚀样品的元素与同位素含量信息,是迄今为止适应于表面原位微区分析最为重要的分析科学技术手段之一。基于准分子激光剥蚀取样技术分别与电感耦合等离子体质谱或发射光谱技术联用的分析手段, 已经被广泛应用于地质学、材料学、环境科学,甚至生命科学领域的原位微区分析研究当中, 并且分别体现了各自技术的优势：固体材料表面的原位微区激光剥蚀取样技术既可以获取被分析材料的原位微区信息（满足了需要空间高分辨的微区元素与同位素信息提取的需求）,又避免了样品预处理带来的可能污染问题,同时,脉冲宽度为纳秒或飞秒的深紫外准分子激光具有极高的能量密度,用于剥蚀固体材料表面取样产生的热效应较低,引起的化学元素和同位素分馏效应不明显,其剥蚀取样的产物（气溶胶）可以更为接近代表原被剥蚀固体材料表面的化学元素和同位素组成;电感耦合等离子质谱分析和光谱分析技术已被证明可以高质量地提供被分析样品的元素与同位素信息,激光剥蚀取样技术与电感耦合等离子体质谱分析技术联用已经为固体材料表面的原位微区元素和同位素分析,带来了大量可信的科学分析数据,近年来将质谱分析手段与光谱分析手段联用于等离子体分析,并应用于元素和同位素化学分析,利用质谱分析与光谱分析方法各自的优点,优势互补,旨在提高电感耦合等离子质谱和光谱技术的元素和同位素分析精度,有望成为了一种新的分析科学方案。从应用于原位微区微量元素与同位素化学分析的需求出发,介绍了基于准分子激光剥蚀取样技术和电感耦合等离子体质谱与光谱分析技术同步联用的分析技术方案,并对于研发相关分析仪器的进展进行了概括与展望。     

$Ab~initio$ and experimental study of the K-shell spectra of s-triazine

The carbon and nitrogen K-shell spectra of gaseous s-triazine have been studied using inner-shell electron energy loss spectroscopy (ISEELS) method. Ab initio Configuration Interaction calculations have been carried out in order to assign the observed bands. As in many similar molecules, both spectra are dominated by an intense π^* peak, followed by lower intensity features. At the C1s edge, the calculations show that some previous assignments made using an underestimated core ionisation energy of about 2.5 eV have to be revisited. At the nitrogen edge, the calculations predict a high intensity π^* doubly excited state lying below the ionisation threshold, which could be responsible for one the most intense observable bands at 405.32 eV.     

TRIUMF resonant ionization laser ion source

The range of isotopes available at the TRIUMF Isotope Separator Accelerator (ISAC) facility has been greatly enhanced by adding a Resonance Ionization Laser Ion Source (RILIS). A large wavelength range is accessible with the fundamental, second and third harmonic generation of titanium-sapphire laser light. In addition a dedicated laser is available for non-resonant laser ionization. The first on-line beam ⁶²Ga was delivered in Dec. 2004. In general RILIS improves the intensity, purity and emittance of ion beams. ⁶²Ga and ²⁶Al and Be beams have been delivered so far on-line. This work was financed by TRIUMF which is federally funded via a contribution agreement through the National Research Council of Canada.     

Laser beam patterns of an optical cavity formed by two twisted cylindrical mirrors

Propagation of an elliptical Gaussian beam in a multiple-pass optical cell formed by two twisted cylindrical mirrors has been described by means of complex curvature tensors. Using the ABCD tensor approach various light patterns were computed for the use in tunable laser absorption spectroscopy with a multiple-pass optical cell. Light patterns with high beam-spot density can be also defined for a cavity formed by two twisted cylindrical high-reflectivity mirrors. In order to achieve higher cavity output intensity, a high-reflectivity cylindrical mirror cavity with at least one mirror that has a central transparent spot for laser beam injection has been described for applications in non-resonant cavity enhanced absorption spectroscopy. The author was with TDL Sensors Ltd., when the experimental part of this work was performed.     

Silicon nitride nanoparticles for surface-assisted laser desorption/ionization of small molecules

Conventional matrix-assisted laser desorption/ionization mass spectrometry is limited to analyses of higher molecular weight compounds due to high background noise generated by the matrix in the lower mass region. Surface-assisted laser desorption/ionization (SALDI) mass spectrometry is an alternative solution to this problem. Nanoparticles, structured silicon surfaces and carbon allotropes are commonly used as SALDI surfaces. Here, for the first time, we demonstrate the application of silicon nitride nanoparticles as a suitable medium for laser desorption/ionization of small drug molecules.