Spectroscopy precision, optical

Pesticide concentration can be readily measured with NIR spectroscopy and optical imaging technology. However the accuracy and precision could be impa-oved. There is a need to develop rapid optical techniques for pesticide determination which could be used in the future for agro-food safety assurance. The optical technique could be one of the most useful tools along with the advancement of spectral instrument for determination of p>esticide residue. 

This paper reports a sensitive optical interferometric technique dual frequency modulation (DFM) for measuring and stabilizing a laser frequency by comparison, in a single step, to a radio frequency (rf) standard. Conversely, a low-noise rf source can be stabilized by a laser frequency reference. A prototype has demonstrated a resolution of 2 parts in 10 , but devices currently under development should have a resolution of 10 and an absolute accuracy of 10" . The method may be competitive with the optical frequency synthesis chain in accuracy and its simplicity suggests its convenient use in metrology, high-precision optical spectroscopy, and gravity wave detection. 

The ability to make optical measurements on individual molecules and submicroscopic aggregates, one at a time, is a valuable new tool in several areas of molecular science. By eliminating inlromogeneous broadening it allows pure spectroscopy to be perfonned witli unprecedented precision in certain condensed phase systems. As an analytical method it pennits tire rapid detection of certain analytes witli unmatched sensitivity. Finally, it is revolutionizing our... 

Spectroscopic methods for the deterrnination of impurities in niobium include the older arc and spark emission procedures (53) along with newer inductively coupled plasma source optical emission methods (54). Some work has been done using inductively coupled mass spectroscopy to determine impurities in niobium (55,56). X-ray fluorescence analysis, a widely used method for niobium analysis, is used for routine work by niobium concentrates producers (57,58). Paying careful attention to matrix effects, precision and accuracy of x-ray fluorescence analyses are at least equal to those of the gravimetric and ion-exchange methods. 

The first theoretical attempts in the field of time-resolved X-ray diffraction were entirely empirical. More precise theoretical work appeared only in the late 1990s and is due to Wilson et al. [13-16]. However, this theoretical work still remained preliminary. A really satisfactory approach must be statistical. In fact, macroscopic transport coefficients like diffusion constant or chemical rate constant break down at ultrashort time scales. Even the notion of a molecule becomes ambiguous at which interatomic distance can the atoms A and B of a molecule A-B be considered to be free Another element of consideration is that the electric field of the laser pump is strong, and that its interaction with matter is nonlinear. What is needed is thus a statistical theory reminiscent of those from time-resolved optical spectroscopy. A theory of this sort was elaborated by Bratos and co-workers and was published over the last few years [17-19]. 

Zare and coworkers (2009) have recently discussed a continuous flow ring down spectroscopy system integrating chromatographic separation, a catalytic combuster, and an isotopic 13C/12C optical analyzer which conveniently yields 813C values at a precision nearing that for IRMS. A modification yields 8D and 815N values. 

At infrared wavelengths extinction by the MgO particles of Fig. 11.2, including those with radius 1 jam, which can be made by grinding, is dominated by absorption. This is why the KBr pellet technique is commonly used for infrared absorption spectroscopy of powders. A small amount of the sample dispersed in KBr powder is pressed into a pellet, the transmission spectrum of which is readily obtained. Because extinction is dominated by absorption, this transmission spectrum should follow the undulations of the intrinsic absorption spectrum—but not always. Comparison of Figs. 10.1 and 11.2 reveals an interesting discrepancy calculated peak extinction occurs at 0.075 eV, whereas absorption in bulk MgO peaks at the transverse optic mode frequency, which is about 0.05 eV. This is a large discrepancy in light of the precision of modern infrared spectroscopy and could cause serious error if the extinction peak were assumed to lie at the position of a bulk absorption band. This is the first instance we have encountered where the properties of small particles deviate appreciably from those of the bulk solid. It is the result of surface mode excitation, which is such a dominant effect in small particles of some solids that we have devoted Chapter 12 to its fuller discussion. 

An easy calibration strategy is possible in ICP-MS (in analogy to optical emission spectroscopy with an inductively coupled plasma source, ICP-OES) because aqueous standard solutions with well known analyte concentrations can be measured in a short time with good precision. Normally, internal standardization is applied in this calibration procedure, where an internal standard element of the same concentration is added to the standard solutions, the samples and the blank solution. The analytical procedure can then be optimized using the internal standard element. The internal standard element is commonly applied in ICP-MS and LA-ICP-MS to account for plasma instabilities, changes in sample transport, short and long term drifts of separation fields of the mass analyzer and other aspects which would lead to errors during mass spectrometric measurements. 

In flame spectroscopy, the residence time of analyte in the optical path is < 1 s as it rises through the flame. A graphite furnace confines the atomized sample in the optical path for several seconds, thereby affording higher sensitivity. Whereas 1—2 mL is the minimum volume of solution necessary for flame analysis, as little as 1 pL is adequate for a furnace. Precision is rarely better than 5-10% with manual sample injection, but automated injection improves reproducibility to —1%. 

Most of the high precision spectroscopy of He Rydberg states has been done by microwave resonance, which is probably the best way of obtaining the zero field energies. Wing et a/.8-12 used a 30-1000pA/cm2 electron beam to bombard He gas at 10-5-10-2 Torr. As electron bombardment favors the production of low states, it is possible to detect A transitions driven by microwaves. The microwave power was square wave modulated at 40 Hz, and the optical emission from a specific Rydberg state was monitored. When microwave transitions occurred to or... 

The dynamics of the interfacial electron-transfer between Dye 2 and TiOz were examined precisely by laser-induced ultrafast transient absorption spectroscopy. Durrant et al.38) employed subpicosecond transient absorption spectroscopy to study the rate of electron injection following optical excitation of Dye 2 adsorbed onto the surface of nanocrystalline Ti02 films. Detailed analysis indicates that the injection is at least biphasic, with ca. 50% occurring in <150 fsec (instrument response limited) and 50% in 1.2 0.2 psec. 

Since the mid-1960s, a variety of analytical chemistry techniques have been used to characterize obsidian sources and artifacts for provenance research (4, 32-36). The most common of these methods include optical emission spectroscopy (OES), atomic absorption spectroscopy (AAS), particle-induced X-ray emission spectroscopy (PIXE), inductively coupled plasma-mass spectrometry (ICP-MS), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray fluorescence spectroscopy (XRF), and neutron activation analysis (NAA). When selecting a method of analysis for obsidian, one must consider accuracy, precision, cost, promptness of results, existence of comparative data, and availability. Most of the above-mentioned techniques are capable of determining a number of elements, but some of the methods are more labor-intensive, more destructive, and less precise than others. The two methods with the longest and most successful histoty of success for obsidian provenance research are XRF and NAA. 

Photoluminescence spectroscopy is a well-established technique and a very powerful analytical method, which has proven its advantages in chemical sensing. Due to its high sensitivity and reliability it can provide fast and precise information about recognition by variations in the optical signal. Additionally, progress in materials technology as well as advances in microelectronics and computer science have... 

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