Highly Coherent Spectroscopy of Ultracold Atoms and Molecules in Optical Lattices

Cooling and trapping of neutral atoms using laser techniques has enabled extensive progress in precise, coherent spectroscopy. In particular, trapping ultracold atoms in optical lattices in a tight confinement regime allows us to perform high‐resolution spectroscopy unaffected by atomic motion. We report on the recent developments of optical lattice atomic clocks that have led to optical spectroscopy coherent at the one second timescale. The lattice clock techniques also open a promising pathway toward trapped ultracold molecules and the possible precision measurement opportunities such molecules offer.     

Atomic hydrogen concentrations in pulsed microwave discharges used for diamond synthesis

Pulsing of a microwave discharge is a promising new technique to improve the control of the diamond deposition process. A small amount of argon (5% Ar) was added to the usual feed stock (0.5% methane in hydrogen) to act as an actinometer. Plasma emission was observed during the pulse on-times for pulse repetition rates from 50 Hz to 10 kHz by time-resolved optical spectroscopy. Determined relaxation time constants for atomic hydrogen are on the order of 1 ms. Thus, the atomic hydrogen concentrations do not vary very much at a pulse repetition rate of 20 kHz, whereas at 50 Hz the radical concentrations vary between a saturation value and zero. The saturation value of atomic hydrogen increases with increasing peak power, but mean values are generally lower as in the continuous wave mode with the same average power and decrease with decreasing duty cycles and pulse repetition rates. The results are consistent with deposition experiments.     

Cavity-Enhanced Saturation Spectroscopy of Molecules with sub-kHz Accuracy

Saturation spectroscopy is frequently used to obtain sub-Doppler measurement of atomic and molecular transitions. Optical resonant cavities can be used to enhance the effective absorption path length, and the laser power inside the cavity as well to saturate very weak ro-vibrational transitions of molecules. Three different cavity-enhanced methods, cavity enhanced absorption spectroscopy, cavity ring-down spectroscopy, and noise-immune cavity enhanced optical heterodyne molecular spectroscopy (NICE-OHMS), were compared by measuring the Lamb dip of a C₂H₂ line at 1.4 μm using a cavity with a finesse of 120000. The center of the line was determined by different cavity-enhanced methods, each giving a sub-kHz (δv/v≈10^-12) statistical uncertainty. The sensitivity and precision of different methods were analyzed and compared. As demonstrated in this study, the NICE-OHMS method is the most sensitive one, but more investigation on the systematic uncertainty is necessary before its application in metrology studies toward a sub-kHz accuracy.     

Element selective detection of molecular species applying chromatographic techniques and diode laser atomic absorption spectrometry

Tunable diode laser atomic absorption spectroscopy (DLAAS) combined with separation techniques and atomization in plasmas and flames is presented as a powerful method for analysis of molecular species. The analytical figures of merit of the technique are demonstrated by the measurement of Cr(VI) and Mn compounds, as well as molecular species including halogen atoms, hydrogen, carbon and sulfur.     

原子发射光谱分析

本文是《分析试验室》期刊定期评述中“原子发射光谱分析”课题的第一篇评述文章。文中对1987～1990年期间我国原子发射光谱分析(AES)领域所取得的进展作了全面评述。内容包括概述、火焰发射光谱法、电弧发射光谱法、火花发射光谱法、电感耦合等离子体原子发射光谱法、直流等离子体原子发射光谱法、微波等离子体原子发射光谱法、亚稳态能量转移发射光谱法、激光显微发射光谱法、空心阴极灯和Grimm灯发射光谱法等方面。     

Differential sub-Doppler,one-photon,optical absorption spectroscopy of gases,and vapors with lasers

We consider in this work a high resolution, Doppler-free, one-photon, optical absorption differential spectroscopy of a mixture of two different mutually interacting gases or vapors in order to display the effects of this interaction directly in the optical spectra. Those interactions are restricted to binary collisions and they are treated in the so-called impact approximation (hard collisions). Usually, the high resolution, Doppler-free optical spectra are observed when two counterpropagating laser beams pass through the gas cell. One beam is strong enough to saturate the optical transition to several different degrees. The other beam is a weak probe absorbed by the saturated atomic or molecular pair of energy levels (a two-energy level system with angular frequency ω₀). The laser beams are supposed to have different angular frequencies and to be linearly polarized. In order to achieve the Doppler-free differential optical absorption one-photon spectra, a convenient geometrical experimental set up is proposed.     

Spectroscopic applications of femtosecond optical frequency combs

Over the past twelve years, notable advances have occurred in a diverse range of scientific areas following the development of femtosecond optical frequency combs. Compared to a conventional laser source, the distinguishing feature of a femtosecond comb is that it provides a broadband source with well-defined phase coherence across the optical spectrum. This makes it a unique tool for spectroscopic applications, simultaneously providing high spectral resolution and broad spectral coverage. This tutorial review provides an introduction to femtosecond optical frequency combs, covering their principles of operation and examples of how they can be applied to spectroscopy. In this way it aims to demonstrate their potential as a versatile spectroscopic tool that could play a very significant role in future advances in the chemical sciences.     

Defining and measuring optical frequencies: the optical clock opportunity--and more (Nobel lecture).

Four long-running currents in laser technology met and merged in 1999-2000. Two of these were the quest toward a stable repetitive sequence of ever-shorter optical pulses and, on the other hand, the quest for the most time-stable, unvarying optical frequency possible. The marriage of ultrafast- and ultrastable lasers was brokered mainly by two international teams and became exciting when a special "designer" microstructure optical fiber was shown to be nonlinear enough to produce "white light" from the femtosecond laser pulses, such that the output spectrum embraced a full optical octave. Then, for the first time, one could realize an optical frequency interval equal to the comb's lowest frequency, and count out this interval as a multiple of the repetition rate of the femtosecond pulse laser. This "gear-box" connection between the radiofrequency standard and any/all optical frequency standards came just as sensitivity-enhancing ideas were maturing. The four-way union empowered an explosion of accurate frequency measurement results in the standards field and prepared the way for refined tests of some of our cherished physical principles, such as the time-stability of some of the basic numbers in physics (e.g. the "fine-structure" constant, the speed of light, certain atomic mass ratios), and the equivalence of time-keeping by clocks based on different physics. The stable laser technology also allows time-synchronization between two independent femtosecond lasers so exact they can be made to appear as if the source were a single laser. By improving pump-probe experiments, one important application will be in bond-specific spatial scanning of biological samples. This next decade in optical physics should be a blast!     

Laser sources for precision spectroscopy on atomic strontium

We present a new laser setup designed for high-precision spectroscopy on laser cooled atomic strontium. The system, which is entirely based on semiconductor laser sources, delivers 200 mW at 461 nm for cooling and trapping atomic strontium from a thermal source, 4 mW at 497 nm for optical pumping from the metastable P23 state, 12 mW at 689 nm on linewidth less than 1 kHz for second-stage cooling of the atomic sample down to the recoil limit, 1.2 W at 922 nm for optical trapping close to the "magic wavelength" for the 0-1 intercombination line at 689 nm. The 689 nm laser was already employed to perform a frequency measurement of the 0-1 intercombination line with a relative accuracy of 2.3 x 10(-11), and the ensemble of laser sources allowed the loading in a conservative dipole trap of multi-isotopes strontium mixtures. The simple and compact setup developed represents one of the first steps towards the realization of a transportable optical standards referenced to atomic strontium.     

氢终止金刚石表面的形成机理

为考察金刚石形成氢终止表面的反应机制,采用微波氢等离子体处理以及电阻丝氢气气氛加热处理进行对比研究.利用光发射谱(OES)和漫反射傅里叶变换红外光谱(DRIFTS)分别表征了微波氢等离子体中的活性基团和金刚石表面氢终止浓度.结果表明,微波氢等离子体环境下,随着衬底温度、等离子体密度和能量的增加,温度至700 ℃ (800 W/3 kPa)时,等离子体中出现了明显的CH基团;相应地,金刚石表面氢终止浓度随温度、等离子体密度和能量的增加而增加.采用氢气气氛下电阻丝加热的方法同样形成了氢终止金刚石表面,表明微波等离子体处理金刚石表面形成氢终止主要源于由温度控制的表面化学反应,而非等离子体的物理刻蚀作用.氧终止金刚石表面形成氢终止的机制是表面C=O键在高于500 ℃时分解为CO,相应的悬挂键由氢原子或氢分子占据.     

Comparison of double-pulse and single-pulse laser-induced breakdown spectroscopy techniques in the analysis of powdered samples of silicate raw materials for the brick-and-tile industry

Single- and double-pulse laser-induced breakdown spectroscopy techniques applied to the analysis of pressed pellets of silicate raw materials were compared in terms of precision, sensitivity and limits of detection. Two Nd:YAG lasers (1064 and 532 mm) in an orthogonal configuration with a reheating arrangement have been employed. The main factors influencing system performance were optimized, i.e. laser pulse energies and interpulse separation. The behaviour of plasma temperature was studied over a period of time and calibration curves for Mg were constructed for both the single and double-pulse setup. When comparing the single- and double-pulse techniques, limits of detection of Si and Mg for the double-pulse technique were found to be 10 times lower.     

The Hydrogen Bond and Beyond: Perspectives for Rotational Investigations of Non-Covalent Interactions

In the last decade, experiment and theory have expanded our vision of non-covalent interactions (NCIs), shifting the focus from the conventional hydrogen bond to new bridging interactions involving a variety of weak donor/acceptor partners. Whereas most experimental data originate from condensed phases, the introduction of broadband (chirped-pulse) microwave fast-passage techniques has revolutionized the field of rotational spectroscopy, offering unexplored avenues for high-resolution studies in the gas phase. We present an outlook of hot topics for rotational investigations on isolated intermolecular clusters generated in supersonic jet expansions. Rotational spectra offer very detailed structural data, easily discriminating the isomeric or isotopic composition and effectively cancelling any solvent, crystal, or matrix bias. The direct comparison with quantum mechanical predictions provides insight into the origin of the inter- and intramolecular interactions with much greater precision than any other spectroscopic technique, simultaneously serving as test-bed for fine-tuning of theoretical methods. We present recent examples of rotational investigations around three topics: oligomer formation, chiral recognition, and identification of halogen, chalcogen, pnicogen, or tetrel bonds. The selected examples illustrate the benefits of rotational spectroscopy for the structural and energetic assessment of inter-/intramolecular interactions, which may help to move from fundamental research to applications in supramolecular chemistry and crystal engineering.     

Atomic oxygen detection using two-photon degenerate four wave mixing

We report a new application of Forward Degenerate Four Wave Mixing to the two-photon transition 2p → 3p of atomic oxygen. This spectroscopy has been used to detect oxygen atoms produced in a microwave discharge. The possibility to determine number densities over a range of microwave plasma parameters is investigated. In contrast to conventional linear techniques, quantitative data are relatively easy to obtain even for environments with high background luminosity, limited optical access and inhomogeneous quenching.     

Carbon chains and rings in the laboratory and in space

Seventy-seven reactive organic molecules of astrophysical interest have been identified in a supersonic molecular beam, 73 in the radio band by Fourier-transform microwave spectroscopy, four in the optical by laser cavity ringdown spectroscopy. Most are linear carbon chains, but six consist of carbon chains attached to the compact, highly polar C3 ring, and two are rhomboidal cyclic configurations of SiC3. The laboratory astrophysics of the radio molecules is complete for the time being, in the sense that essentially all the rotational transitions of current interest to radio astronomy (including hyperfine structure when present) can now be calculated to a small fraction of 1 km s(-1) in equivalent radial velocity; six of the radio molecules have already been detected in space on the basis of the present data. The FTM spectrometer employed in this work is far from fundamental limits of sensitivity, so many more molecules can probably be found by refinements of present techniques. The density of reactive molecules in our supersonic beam is generally high by the standards of laser spectroscopy, and many of the radio molecules probably have detectable optical transitions which we are attempting to find, largely motivated by the long-standing problem of the diffuse interstellar bands. Our most interesting result to date is the detection of a fairly strong molecular band at 443 nm in a benzene discharge, in exact coincidence with the strongest and best known interstellar band. Isotopic shifts measured with partially and totally deuterated benzene suggest that the carrier of the laboratory band is a hydrocarbon molecule with the elemental formula CnH5, with n most likely in the range 3-6.     

The autofluorescence of plastic materials and chips measured under laser irradiation

Plastic materials have the potential to substitute for glass substrates used in microfluidic and microTAS systems adding flexibility in materials' choices. Optical quality plastic materials with a low autofluorescence are crucial for optimal detection by fluorescence and laser induced fluorescence techniques. This paper summarizes a series of optical investigations on commercially available plastic chip materials (PMMA, COC, PC, PDMS) and chips made from those materials. Intrinsic optical constants of plastic materials-refractive index for bulk materials-determined by spectroscopic ellipsometry and transmission spectroscopy in the visible range are presented. The laser-induced autofluorescence of materials and chips was assessed at four laser wavelengths, namely, 403, 488, 532 and 633 nm. Considerable bleaching of the autofluorescence was observed under continuous laser illumination. Overall, the longer wavelength laser excitation sources yielded less autofluorescence. PDMS exhibited the least autofluorescence and was comparable to BoroFloat glass. In all cases, chips exhibited slightly higher autofluorescence than the raw plastic materials from which they had been made.     

High frequency excitation of vapours produced by hollow cathode sputtering

Using a hollow cathode discharge for producing a suitable atomic vapour, the spectral lines of elements were excited by a high frequency discharge of 2450 MHz. These lamps were used as primary light sources for atomic absorption spectroscopy and were compared with conventional hollow cathode lamps. Higher intensity of radiation as well as higher sensitivity was obtained with the high frequency discharge. The interaction of the microwave field with the hollow cathode discharge limits the ultimate intensity. The stability of radiation from these sources is good. Measurements of line halfwidths indicate gas temperatures of approximately 500°K for both the high frequency and conventional hollow cathode discharges.     

Tungsten devices in analytical atomic spectrometry

Tungsten devices have been employed in analytical atomic spectrometry for approximately 30 years. Most of these atomizers can be electrically heated up to 3000 °C at very high heating rates, with a simple power supply. Usually, a tungsten device is employed in one of two modes: as an electrothermal atomizer with which the sample vapor is probed directly, or as an electrothermal vaporizer, which produces a sample aerosol that is then carried to a separate atomizer for analysis. Tungsten devices may take various physical shapes: tubes, cups, boats, ribbons, wires, filaments, coils and loops. Most of these orientations have been applied to many analytical techniques, such as atomic absorption spectrometry, atomic emission spectrometry, atomic fluorescence spectrometry, laser excited atomic fluorescence spectrometry, metastable transfer emission spectroscopy, inductively coupled plasma optical emission spectrometry, inductively coupled plasma mass spectrometry and microwave plasma atomic spectrometry. The analytical figures of merit and the practical applications reported for these techniques are reviewed. Atomization mechanisms reported for tungsten atomizers are also briefly summarized. In addition, less common applications of tungsten devices are discussed, including analyte preconcentration by adsorption or electrodeposition and electrothermal separation of analytes prior to analysis. Tungsten atomization devices continue to provide simple, versatile alternatives for analytical atomic spectrometry.     

Optical Frequency Comb-Based Cavity-Enhanced Fourier-Transform Spectroscopy: Application to Collisional Line-Shape Study

Direct-comb spectroscopy techniques uses optical frequency combs (OFCs) as spectroscopic light source. They deliver high sensitivity, high frequency resolution and precision in a broad spectral range. Due to these features, the field has burgeoned in recent years. In this work we constructed an OFC-based cavity-enhanced Fourier-transform spectrometer in the near-infrared region and used it for a line-shape study of rovibrational transitions of CO perturbed by Ar. The highly sensitive measurements spanned the wavenumber range from 6270 cm\begin{document}$^{-1}$\end{document} to 6410 cm\begin{document}$^{-1}$\end{document}, which covered both P and R branch of the second overtone band of CO. The spectrometer delivers high-resolution surpassing the Fourier-transform resolution limit determined by interferogram length, successfully removing ringing and broadening effects caused by instrumental line shape function. The instrumental-line-shape-free method and high signal-to-noise ratio in the measurement allowed us to observe collisional effects beyond those described by the Voigt profile. We retrieved collisional line-shape parameters by fitting the speed-dependent Voigt profile and found good agreement with the values given by precise cavity ring-down spectroscopy measurements that used a continuous-wave laser referenced to a stabilized OFC. The results demonstrate that OFC-based cavity-enhanced Fourier-transform spectroscopy is a strong tool for accurate line-shape studies that will be crucial for future spectral databases.     

Growth, structural, vibrational, optical, laser and dielectric aspects of L-alanine alaninium nitrate single crystal

Bulk single crystals of l-alanine alaninium nitrate [abbreviated as LAAN], an intriguing material for frequency conversion has been grown from its aqueous solution by both slow solvent evaporation and by slow cooling techniques. The optimized pH value to grow good quality LAAN single crystal was found to be 2.5. The grown crystals were subjected to single crystal X-ray diffraction studies to determine the unit cell dimensions and morphology. Vibrational frequencies of the grown crystals by Fourier transform infrared spectroscopic technique were investigated. Also, the presence of hydrogen and carbon atoms in the grown sample was confirmed using proton and carbon NMR analyses. The dielectric constant and dielectric loss measurements of the as grown crystal at different temperatures and frequencies of the applied field are measured and reported. LAAN has good optical transmission in the entire visible region with cutoff wavelength within the UV region confirms its suitability for device fabrications. The existence of second harmonic generation signals was observed using Nd:YAG laser with fundamental wavelength of 1064 nm. Its Laser Damage Threshold (LDT) was measured and also tested by using a Q-switched Nd:YAG laser and the value of LDT of LAAN is 17.76GW/cm2 respectively, is found to be better than certain organic and semiorganic materials.     

Ultra-sensitive high-precision spectroscopy of a fast molecular ion beam

Direct spectroscopy of a fast molecular ion beam offers many advantages over competing techniques, including the generality of the approach to any molecular ion, the complete elimination of spectral confusion due to neutral molecules, and the mass identification of individual spectral lines. The major challenge is the intrinsic weakness of absorption or dispersion signals resulting from the relatively low number density of ions in the beam. Direct spectroscopy of an ion beam was pioneered by Saykally and co-workers in the late 1980s, but has not been attempted since that time. Here, we present the design and construction of an ion beam spectrometer with several improvements over the Saykally design. The ion beam and its characterization have been improved by adopting recent advances in electrostatic optics, along with a time-of-flight mass spectrometer that can be used simultaneously with optical spectroscopy. As a proof of concept, a noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) setup with a noise equivalent absorption of ~2 × 10(-11) cm(-1) Hz(-1/2) has been used to observe several transitions of the Meinel 1-0 band of N(2) (+) with linewidths of ~120 MHz. An optical frequency comb has been used for absolute frequency calibration of transition frequencies to within ~8 MHz. This work represents the first direct spectroscopy of an electronic transition in an ion beam, and also represents a major step toward the development of routine infrared spectroscopy of rotationally cooled molecular ions.