Search NASA⌕ Search

SEARCH · Search NASA

Results for “Frequency modulation spectroscopy”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Cooper, David E.↗

Computational expressions for signals in frequency-modulation spectroscopy

In this study, general expressions for the signals in frequency-modulation spectroscopy (FMS) appear in the literature but are often reduced to simple analytical equations following the assumption of a weak modulation index. This is little help to the experimentalist who wants to predict signals for modulation depths of the order of unity or greater, where strong FMS signals reside. Here, we develop general formulas for FMS signals in the case of an absorber with a Voigt line shape and then link these expressions to an example and existing numerical code for the line shape. The resulting computational recipe is easy to implement and exercised here to show where the larger FMS signals are found over the coordinates of modulation index and modulation frequency. One can also estimate from provided curves the in-phase FMS signal over a wide range of modulation parameters at either the Lorentzian-broadening or Doppler-broadening limit, or anywhere in between by interpolation.

74 ATOMIC AND MOLECULAR PHYSICS↗

Multiplexing of frequency-modulation spectroscopy by spread-spectrum codes, demonstrated in continuous-wave LIDAR

Frequency-modulation spectroscopy (FMS) is generally suited to code-division multiplexing, and we demonstrate that capacity in a form of continuous-wave LIDAR, utilizing a sharp CO 2 absorption transition at 1.6 µm in simple ranging setups. The approach retains the advantages of FMS, including coherent detection and good rejection of broad absorption backgrounds. Extensions of this multiplexed approach to the continuous, simultaneous detection of several transitions would come by transmitting an encoded combination of frequency-modulated carriers, each tuned to detect a unique absorption transition. Signal analysis at the receiver involves a simple process of de-multiplexing that, in a general application, reveals targets at various distances and the absorption-related FMS signals in between.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Monitoring of catalyst performance in CO2 lasers using frequency modulation spectroscopy with diode lasers

Closed-cycle CO2 laser operation with removal of O2 and regeneration of CO2 can be achieved by catalytic CO-O2 recombination. Both parametric studies of the optimum catalyst formulation and long-term performance tests require on line monitoring of CO, O2 and CO2 concentrations. There are several existing methods for molecular oxygen detection. These methods are either intrusive (such as electrochemical method or mass spectrometry) or very expensive (such as CARS, UV laser absorption). Researchers demonstrated a high-sensitivity spectroscopic measurement of O2 using the two-tone frequency modulation spectroscopy (FMS) technique with a near infrared GaAlAs diode laser. Besides its inexpensive cost, fast response time, nonintrusive measurements and high sensitivity, this technique may also be used to differentiate between isotopes due to its high spectroscopic resolution. This frequency modulation spectroscopy technique could also be applied for the on-line monitoring of CO and CO2 using InGaAsP diode lasers operation in the 1.55 microns region and H2O in the 1.3 microns region. The existence of single mode optical fibers at the near infrared region makes it possible to combine FMS with optical fiber technology. Optical fiber FMS is particularly suitable for making point-measurements at one or more locations in the CO2 laser/catalyst system.

Wang, Liang-Guo↗

Time-Resolved, NIR Two-Tone Frequency Modulation Spectroscopy for Quantitative Measurement of HO 2 Radical in Fuel Oxidation Reactions

Time-resolved two-tone frequency modulation (TTFM) absorption spectroscopy has been used to measure, in situ and quantitatively, hydroperoxy (HO 2 ) radical in fuel oxidation reactions at the first overtone transitions (2v 1 ) of HO 2 near 1509nm. Typical HO 2 detection limit is on the order of 10 11 molecule cm -3 , which corresponds to a relative absorption of 10 -5 . TTFM method successfully removes low frequency thermal lensing noise in measured HO 2 kinetic time traces, which is a general noise source in fuel oxidation absorption experiments. Compared with previous works, we have upgraded the TTFM experiment with a NIR distributed feedback (DFB) diode laser, a fiber-coupled broadband phase modulator, and a two-channel wave generator, which have improve the performance of our experiment substantially.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of the sign of the population difference in a two-level system by frequency-modulation spectroscopy

Population inversions can occur in two-level systems as a result of chemical kinetic processes that involve pulsed excitation of a system with a large amount of excess energy, for example, multi-photon dissociation. In this work, we report the use of frequency-modulation (FM) spectroscopy to determine, from the phase of the FM signal, the sign of the population difference in a two-level system – specifically, whether the two-level system is inverted. Here, as a proof of principle demonstration of this technique, we show that FM signals from an inverted I 2 B 3 Π 0+u – X 1 $Σ$ $^+$$_g$ transition, prepared by a pulsed laser, have opposite phase with respect to signals from a non-inverted system, the Rb D 1 -line absorption transition.

74 ATOMIC AND MOLECULAR PHYSICS↗

One-colour (~220 nm) resonance-enhanced (S 1 –S 0 ) multi-photon dissociation of acetylene: probe of the C 2 A 1 Π u – X 1 Σ + g band by frequency-modulation spectroscopy

In a recent paper, we demonstrated that one-colour (~220 nm), resonance-enhanced (S 1 –S 0 ), photodissociation of acetylene generates strong $C_2$ Swan band ($d^3Π_g–a^3Π_u$) and $C_2$ Deslandres-d'Azambuja band ($C^1Π_g–A^1Π_u$) fluorescence, and long-lived (>3 µs) fluorescence from an electronically-excited $C_2$H * species. It was not known whether the $C_2A^1Π_u$ and $X^1Σ^+_g$ states are also directly populated in this process. In this paper, multiple vibration-rotation transitions between the $C_2A$-state v = 2 and the X-state v = 0 level are examined by time-resolved frequency-modulation (FM) spectroscopy. The photolysis laser wavelength is tuned into resonance at the one-photon level with S 1 –S 0 transitions that populate individual rotational levels of the S 1 $_{trans}$-conformer $3^2,3^3,$ and $3^4$ vibrational states. By comparing the phase of the FM signals from the $C_2A–X$ transitions with that from the Rb D 1 -line absorption transition, we determine that, for all of the probed A–X transitions, the X-state level is more populated than the A-state level. We propose that the acetylene S 1 level is excited by the second photon to an acetylene dissociation precursor state, which undergoes sequential C-H bond-breaking to produce the $C_2X$ state. The dissociation precursor is assigned as the $1^1B_g(trans-bent)/1^1B_1(cis-bent)$ valence state, which correlates to a doubly-excited configuration, $(1π_u)^2(1π_g)^2$, at linear geometry. Based on the rotational distributions of the $C_2X$-state fragments, we believe that at least one of the transition states involved in the photolysis via S 1 $3^4$ has a larger CC-H bend-angle for the departing H-atom than that involved in the S 1 $3^2$ and $3^3$ photolysis.

74 ATOMIC AND MOLECULAR PHYSICS↗

Time-resolved Hyperspectral Fluorescence Spectroscopy using Frequency Modulated Excitation

An intensity-modulated excitation light source is used together with a micro channel plate intensified CCD (ICCD) detector gated at a slightly different frequency to generate a beat frequency from a fluorescent sample. The addition of a spectrograph produces a hyperspectral time-resolved data product where the resulting beat frequency is detected with a low frame rate camera. Measuring the beat frequency of the spectrum as a function of time allows separation of the excited fluorescence from ambient constant light sources. The excitation and detector repetition rates are varied over a range of discrete frequencies, and the phase shift of the beat wave maps out the emission decay rate(s).

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Frequency stabilization of a 1083 nm fiber laser to {sup 4}He transition lines with optical heterodyne saturation spectroscopies

Two kinds of optical heterodyne saturation spectroscopies, namely, frequency modulation spectroscopy (FMS) and modulation transfer spectroscopy (MTS), are demonstrated for locking a fiber laser to the transition lines of metastable {sup 4}He atoms around 1083 nm. The servo-loop error signals of FMS and MTS for stabilizing laser frequency are optimized by studying the dependence of the peak-to-peak amplitude and slope on the optical power of pump and probe beams. A comparison of the stabilization performances of FMS/MTS and polarization spectroscopy (PS) is presented, which shows that MTS exhibits relatively superior performance with the least laser frequency fluctuation due to its flat-background dispersive signal, originated from the four-wave mixing process. The Allan deviation of the stabilized laser frequency is 5.4 × 10{sup −12}@100 s with MTS for data acquired in 1000 s, which is sufficiently applicable for fields like laser cooling, optical pumping, and optical magnetometry.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Kinetic Study of the OH + Ethylene Reaction using Frequency Modulated Laser Absorption Spectroscopy

The pressure dependence of the OH + C 2 H 4 addition reaction has been investigated using frequency modulated laser absorption spectroscopy to monitor OH kinetics. Bimolecular rate coefficients for the title reaction are reported in argon bath gas at room temperature and total pressures ranging from 2–361Torr. The pressure dependent rate coefficients measured here agree well with the majority of published kinetic studies under similar conditions. Previous high-level ab initio calculations have identified a pre-reaction complex on the OH + C 2 H 4 potential energy surface. In conclusion, the influence of this complex on the OH + C 2 H 4 kinetics has been investigated using one-dimensional master equation analyses of the current and previous experimental measurements

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-tone and two-tone AM-FM spectral calculations for tunable diode laser absorption spectroscopy

A generalized theory for optical heterodyne spectroscopy with phase modulated laser radiation is used which allows the calculation of signal line shapes for frequency modulation spectroscopy of Lorentzian gas absorption lines. In particular, synthetic spectral line shapes for both single-tone and two-tone modulation of lead-salt diode lasers are presented in which the contributions from both amplitude and frequency modulations are included.

Chou, Nee-Yin↗

Investigating the photodissociation of H 2 O 2 using frequency modulation laser absorption spectroscopy to monitor radical products

In this study, the photodissociation of H 2 O 2 dilute in argon at 193 nm has been investigated using near infrared frequency modulation laser absorption spectroscopy on selected rotational lines of the OH vibrational overtone bands between 6500 and 7100 cm -1 to detect the OH and HO 2 radical products with the same laser. Sequential OH and HO 2 time-dependent profiles have been measured at room temperature and total pressures ranging from 3 to 56 Torr. Kinetic analysis gives the product distribution following H 2 O 2 photolysis of (82±1) % OH and (18±1)% HO 2 under the present conditions, in excellent agreement with previously reported measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A discharge with a magnetic X-point as a negative hydrogen ion source

The study presents first results from investigations of a novel low-pressure plasma source, intended for a negative hydrogen ion production. The source utilizes a dc magnetic field, shaped to form a cusp with a magnetic null-point (X-point). Beside the common role of filtering out the high energy electrons, this magnetic field configuration ensures in the present case also an interesting mechanism of coupling the RF power to the plasma. Investigations performed using radio frequency modulation spectroscopy (RFMOS) reveal that the main power coupling to the electrons is confined in the region on one side of the X-point. The modulation of the light intensity indicates also the presence of a strong dc drift close to the plane of the X-point. Several hypothesises for its explanation are raised: an azimuthal diamagnetic drift due to strong axial gradients of the electron energy, the excitation of a standing helicon wave, which couples to the radial magnetic field in the plane of the X-point, or a Trivelpiece-Gould wave which is resonantly absorbed near the plane of the X-point.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Real Time Quantitative 3-D Imaging of Diffusion Flame Species

A low-gravity environment, in space or ground-based facilities such as drop towers, provides a unique setting for study of combustion mechanisms. Understanding the physical phenomena controlling the ignition and spread of flames in microgravity has importance for space safety as well as better characterization of dynamical and chemical combustion processes which are normally masked by buoyancy and other gravity-related effects. Even the use of so-called 'limiting cases' or the construction of 1-D or 2-D models and experiments fail to make the analysis of combustion simultaneously simple and accurate. Ideally, to bridge the gap between chemistry and fluid mechanics in microgravity combustion, species concentrations and temperature profiles are needed throughout the flame. However, restrictions associated with performing measurements in reduced gravity, especially size and weight considerations, have generally limited microgravity combustion studies to the capture of flame emissions on film or video laser Schlieren imaging and (intrusive) temperature measurements using thermocouples. Given the development of detailed theoretical models, more sophisticated studies are needed to provide the kind of quantitative data necessary to characterize the properties of microgravity combustion processes as well as provide accurate feedback to improve the predictive capabilities of the computational models. While there have been a myriad of fluid mechanical visualization studies in microgravity combustion, little experimental work has been completed to obtain reactant and product concentrations within a microgravity flame. This is largely due to the fact that traditional sampling methods (quenching microprobes using GC and/or mass spec analysis) are too heavy, slow, and cumbersome for microgravity experiments. Non-intrusive optical spectroscopic techniques have - up until now - also required excessively bulky, power hungry equipment. However, with the advent of near-IR diode lasers, the possibility now exists to obtain reactant and product concentrations and temperatures non-intrusively in microgravity combustion studies. Over the past ten years, Southwest Sciences has focused its research on the high sensitivity, quantitative detection of gas phase species using diode lasers. Our research approach combines three innovations in an experimental system resulting in a new capability for nonintrusive measurement of major combustion species. FM spectroscopy or high frequency Wavelength Modulation Spectroscopy (WMS) have recently been applied to sensitive absorption measurements at Southwest Sciences and in other laboratories using GaAlAs or InGaAsP diode lasers in the visible or near-infrared as well as lead-salt lasers in the mid-infrared spectral region. Because these lasers exhibit essentially no source noise at the high detection frequencies employed with this technique, the achievement of sensitivity approaching the detector shot noise limit is possible.

Kane, Daniel J.↗

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x , TiO 2 , and Al 2 O 3 ) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiO 2 - and Al 2 O 3 -coated Si electrodes are negative relative to samples with native SiO x , indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2 O 3 . Adding a Pt catalyst to SiO x /Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x /Si.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Accuracy of tip-sample interaction measurements using dynamic atomic force microscopy techniques: Dependence on oscillation amplitude, interaction strength, and tip-sample distance

Atomic force microscopy (AFM) is a versatile surface characterization method that can map a sample’s topography with high spatial resolution while simultaneously interrogating its surface chemistry through the site-specific high-resolution quantification of the forces acting between the sample and the probe tip. Thanks to considerable advances in AFM measurement technology, such local measurements of chemical properties have gained much popularity in recent years. To this end, dynamic AFM methodologies are implemented where either the oscillation frequency or the oscillation amplitude and phase of the vibrating cantilever are recorded as a function of tip-sample distance and subsequently converted to reflect tip-sample forces or interaction potentials. Such conversion has, however, been shown to produce non-negligible errors when applying the most commonly used mathematical conversion procedures if oscillation amplitudes are of the order of the decay length of the interaction. Extending on these earlier findings, the computational study presented in this paper reveals that the degree of divergence from actual values may also critically depend on both the overall strength of tip-sample interaction and the distance at which the interaction is obtained. These systematic errors can, however, be effectively eliminated by using oscillation amplitudes that are sufficiently larger than the decay length of the interaction potential.

Electrical properties and parameters↗