The ν₁+ν₃ vibration band of ¹²C₂H₂ is recorded with a homemade dual-comb spectrometer S. Okubo et al., Applied Physics Express 8, 082402 (2015). The spectral resolution and the accuracy of frequency determination are high, and the bandwidth is broad enough to take spectrum of the whole band in one shot. The last remarkable competence enables us to record all the spectral lines under constant experimental conditions. The linewidth and line strength of the P(26) to R(29) transitions are determined by fitting the line profile to Lambert-Beer’s law with a Voigt function. In the course of analysis, we found the ortho-para dependence of the pressure-broadening coefficient K.Iwakuni et al., 71th ISMS, WK15K. Iwakuni et al., Physical Review Letters 117, 143902 (2016).. This time, we have determined the transition dipole moment of the ν₁+ν₃ band. It is noted that the transition dipole moment determined from the ortho lines agrees with that from the para lines.

---

Footnotes:

S. Okubo et al., Applied Physics Express 8, 082402 (2015).. K.Iwakuni et al., 71th ISMS, WK15

---

Footnotes:

40pt Figure Dual-comb spectroscopy is a powerful tool for fast broad-band spectroscopy due to the parallel interrogation of thousands of spectral lines. Here we report on the spectroscopic analysis of acetylene vapor in a pressurized gas cell using two ultra-low noise frequency combs with a repetition rate around 250 MHz. Optical referencing to a high-finesse cavity yields a sub-Hertz stability of all individual comb lines (including the virtual comb lines between 0 Hz and the carrier) and permits one to pick a small difference of repetition rate for the two frequency combs on the order of 300 Hz, thus representing an optical spectrum of 100 THz ( ∼ 3300 cm⁻¹) within half the free spectral range (125 MHz). The transmission signal is derived straight from a photodetector and recorded with a high-resolution spectrum analyzer or digitized with a computer-controlled AD converter. The figure to the right shows a schematic of the experimental setup which is all fiber-coupled with polarization-maintaining fiber except for the spectroscopic cell. The graph on the lower right reveals a portion of the recorded radio-frequency spectrum which has been scaled to the optical domain. The location of the measured absorption coincides well with data taken from the HITRAN data base. Due to the intrinsic linewidth of all contributing comb lines, each sampling point in the transmission graph corresponds to the probing at an optical frequency with sub-Hertz resolution. This resolution is maintained in coherent wavelength conversion processes such as difference-frequency generation (DFG), sum-frequency generation (SFG) or non-linear broadening (self-phase modulation), and is therefore easily transferred to a wide spectral range from the mid infrared up to the visible spectrum.

Cryogenic Ion Vibrational Spectroscopy (CIVS) is a useful technique that yields rich information about non-covalent interactions in various systems including catalytic complexes, small biologically relevant molecules, and solvent networks. Current instrumentation demands high production costs and large laboratory facilities. We have designed an affordable and compact instrument that is capable of current CIVS experiments. This setup utilizes an ion funnel and a Linear Trap Quadrupole (LTQ) which improves the ion density and allows for spectroscopic interrogation directly in the trap. Preliminary results and future innovations will be discussed.

Molecular ions are challenging to study with conventional spectroscopic methods. Laboratory discharges produce ions in trace quantities which can be obscured by the abundant neutral molecules present. The technique Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy (NICE-OHVMS) overcomes these challenges by combining the ion-neutral discrimination of velocity modulation spectroscopy with the sensitivity of Noise-Immune Cavity-Enhanced Optical Heterodyne Molecular Spectroscopy (NICE-OHMS), and has been able to determine transition frequencies of molecular ions in the mid-infrared (mid-IR) with sub-MHz uncertainties when calibrated with an optical frequency combJ. N. Hodges, A. J. Perry, P. A. Jenkins II, B. M. Siller, and B. J. McCall, J. Chem. Phys. (2013), 139, 164201. However, the extent of these studies was limited by the presence of fringes due to parasitic etalons and the speed and noise characteristics of mid-IR detectors. Recently, we have overcome these limitations by implementing up-conversion detection and dithered optics. We performed up-conversion using periodically poled lithium niobate to convert light from the mid-IR to the visible to be within the coverage of sensitive and fast silicon detectors while maintaining our heterodyne and velocity modulation signals. The parasitic etalons were removed by rapidly rotating CaF₂ windows with galvanometers, which is known as a Brewster-plate spoilerC. R. Webster, J. Opt. Soc. Am. B (1985), 2, 1464. which averaged out the fringes in detection. Together, these improved the sensitivity by more than an order of magnitudeC. R. Markus, A. J. Perry, J. N. Hodges, and B. J. McCall, Opt. Express (2017), 25, 3709-3721.nd have enabled extended spectroscopic surveys of molecular ions in the mid-IR.

---

Footnotes:

J. N. Hodges, A. J. Perry, P. A. Jenkins II, B. M. Siller, and B. J. McCall, J. Chem. Phys. (2013), 139, 164201.. C. R. Webster, J. Opt. Soc. Am. B (1985), 2, 1464., C. R. Markus, A. J. Perry, J. N. Hodges, and B. J. McCall, Opt. Express (2017), 25, 3709-3721.a

r0pt Figure We introduce a new approach that couples a pulsed uniform supersonic flow with high sensitivity continuous wave cavity ringdown spectroscopy (UF-CRDS) operated in the near infrared (NIR). This combination is related to the CRESUI. Sims, J. L. Queffelec, A. Defrance, C. Rebrion-Rowe, D. Travers, P. Bocherel, B. Rowe, I. W. Smith, J. Chem. Phys. 100, 4229-4241, (1994).echnique developed in France and used for many years to study reaction kinetics at low temperature, and to the microwave based chirped-pulse uniform supersonic flow spectrometer (CPUF) developed in our group which has successfully demonstrated the use of pulsed uniform supersonic flow to probe reaction dynamics at temperatures as low as 22 KC. Abeysekera, B. Joalland, N. Ariyasingha, L. N. Zack, I. R. Sims, R. W. Field, A. G. Suits, J. Phys. Chem. Lett. 6, 1599-1604, (2015). CRDSN. Suas-David, T. Vanfleteren, T. Földes, S. Kassi, R. Georges, M. Herman, J. Phys. Chem.A, 119, 10022-10034, (2015).perated with NIR permits access to the first overtones of C-H and O-H stretching/bending which, in combination with its extraordinary sensitivity opens new experiments complementary to the CPUF technique. The UF-CRDS apparatus (Figure) utilizes the pulsed uniform flow produced by means of a piezo-electric stack valveC. Abeysekera, B. Joalland, Y. Shi, A. Kamasah, J. M. Oldham, A. G. Suits, Rev. Sci. Instrum. 85, 116107, (2014).n combination with a Laval nozzle. At present, two machined aluminum Laval nozzles designed for carrier gases Ar and He generate flows with a temperature of approximately 25 K and pressure around 0.15 mbar. This flow is probed by an external cavity diode laser in the NIR (1280-1380 nm). Laval nozzles designed using a newly developed MATLAB-based program will be used in the future. A detailed illustration of the novel UF-CRDS instrumentation and its performance will be presented along with future directions and applications.

---

Footnotes:

I. Sims, J. L. Queffelec, A. Defrance, C. Rebrion-Rowe, D. Travers, P. Bocherel, B. Rowe, I. W. Smith, J. Chem. Phys. 100, 4229-4241, (1994).t C. Abeysekera, B. Joalland, N. Ariyasingha, L. N. Zack, I. R. Sims, R. W. Field, A. G. Suits, J. Phys. Chem. Lett. 6, 1599-1604, (2015).. N. Suas-David, T. Vanfleteren, T. Földes, S. Kassi, R. Georges, M. Herman, J. Phys. Chem.A, 119, 10022-10034, (2015).o C. Abeysekera, B. Joalland, Y. Shi, A. Kamasah, J. M. Oldham, A. G. Suits, Rev. Sci. Instrum. 85, 116107, (2014).i

The extension of the mid IR towards the far IR spectral range below 400 cm⁻¹is of great interest for molecular vibrational analysis for inorganic and organometallic chemistry, for geological, pharmaceutical, and physical applications, polymorph screening and crystallinity analysis as well as for matrix isolation spectroscopy. In these cases, the additional far infrared region offers insight to low energy vibrations which are observable only there. This includes inorganic species, lattice vibrations or intermolecular vibrations in the ordered solid state. The spectral range of a FTIR spectrometer is defined by the major optical components such as the source, beamsplitter, and detector. The globar source covers a broad spectral range from 8000 to 20 cm⁻¹. However a bottle neck exists with respect to the beamsplitter and detector. To extend the spectral range further into the far IR and THz spectral ranges, one or more additional far IR beam splitters and detectors have been previously required. Two new optic components have been incorporated in a spectrometer to achieve coverage of both the mid and far infrared in a single scan: a wide range MIR-FIR beam splitter and the wide range DLaTGS detector that utilizes a diamond window. The use of a standard SiC IR source with these components yields a spectral range of 6000 down to 50 cm⁻¹in one step for all types of transmittance, reflectance and ATR measurements. Utilizing the external water cooled mercury arc high power lamp the spectral range can be ultimately extended down to 10 cm⁻¹. Examples of application will include emission in MIR-THz range, identification of pigments, additives in polymers, and polymorphism studies.

We have developed a portable photoacoustic spectrometer for high precision measurements of the ¹³CO₂/¹²CO₂ isotope ratio and the absolute molar concentration of each isotope. The spectrometer extends on our previous work at 1.57 μm [1], and now employs two separate intensity modulated distributed feedback lasers and a fiber amplifier, operating in the 2.0 μm wavelength region. Each DFB is selected to probe individual spectrally isolated ro-vibrational transitions for ¹²CO₂ and ¹³CO₂. The spectrometer is actively temperature controlled, mitigating variations in the two spectral line intensities and the temperature dependent system response. For measurements of ambient concentrations of carbon dioxide at nominally natural abundance in dry air, we demonstrate a measurement precision of 140 ppb for ¹²CO₂ with a 1 s averaging time and 10 ppb for ¹³CO₂ with a 60 s averaging time. Precision in δ13C of better than 0.1 permil is demonstrated. The analyzer response is calibrated in terms of certified gas mixtures and compared to characterization by cavity ringdown spectroscopy. We also investigate how water vapor affects the photoacoustic signals by promoting collisional relaxation for each isotope. [1] Z.D. Reed, B. Sperling, et al. App. Phys. B. 117, 645-657, 2014

Due to their age, fossil fuels and their byproducts are almost entirely depleted in radiocarbon (¹⁴C). As a result, measurements of radiocarbon provide a unique tracer for determining the origin of products and emissions. Recent efforts at NIST have applied mid-infrared cavity ring-down spectroscopy to measurements of radiocarbon dioxide to allow for more rapid and less expensive measurements than are possible with traditional techniques such as accelerator mass spectrometry. I will discuss our present measurement detection limits and precision as well as discuss limiting noise sources and plans to further improve the instrument’s stability and reproducibility.

Fundamental understanding of catalysts under the reaction conditions is key for designing new catalysts, and improving catalysts and catalytic conversion processes. Such understanding can be achieved only by characterization of catalysts under the reaction conditions because catalyst structures and the mechanisms of catalytic reactions depend on the reaction environment. Raman spectroscopy is one of the few instrumental methods that in a single measurement can provide information about both solid catalysts and the molecules reacting on them. However, its sensitivities for the surface species and the surface changes under catalytic reaction are limited. Infrared spectroscopy is also a wide spectral range (6000-50 cm-1) technique that enables examination of the nature of molecular species, identification of solid phases. Unfortunately, most of the heterogeneous catalysts consist of oxides as the active components or as the supports, which strong IR adsorption (below 1200 cm-1) limits the in situ IR to measure only the surface species (4000 900 cm-1). In this presentation, we will present our new developments of in-situ infrared spectroscopies with a spectral range of 4000 400 cm-1, for both the reflection adsorption infrared spectroscopy (IRAS) and transparent infrared spectroscopy (FTIR, unpublished data), that are capable of measuring both the surface species and changes specific to the surface.

Picosecond four-wave mixing is used to measure temporally and Picosecond four-wave mixing is used to measure temporally and spatially resolved electric field in a nanosecond pulse dielectric discharge sustained in room air and in an atmospheric pressure hydrogen diffusion flame. Measurements of the electric field, and more precisely the reduced electric field (E/N) in the plasma is critical for determination rate coefficients of electron impact processes in the plasma, as well as for quantifying energy partition in the electric discharge among different molecular energy modes. The four-wave mixing measurements are performed using a collinear phase matching geometry, with nitrogen used as the probe species, at temporal resolution of about 2 ns . Absolute calibration is performed by measurement of a known electrostatic electric field. In the present experiments, the discharge is sustained between two stainless steel plate electrodes, each placed in a quartz sleeve, which greatly improves plasma uniformity. Our previous measurements of electric field in a nanosecond pulse dielectric barrier discharge by picosecond 4-wave mixing have been done in air at room temperature, in a discharge sustained between a razor edge high-voltage electrode and a plane grounded electrode (a quartz plate or a layer of distilled water). Electric field measurements in a flame, which is a high-temperature environment, are more challenging because the four-wave mixing signal is proportional to the to square root of the difference betwen the populations of N2 ground vibrational level (v=0) and first excited vibrational level (v=1). At high temperatures, the total number density is reduced, thus reducing absolute vibrational level populations of N2. Also, the signal is reduced further due to a wider distribution of N2 molecules over multiple rotational levels at higher temperatures, while the present four-wave mixing diagnostics is using spectrally narrow output of a ps laser and a high-pressure Raman cell, providing access only to a few N2 rotational levels. Because of this, the four-wave mixing signal in the flame is lower by more than an order of magnitude compared to the signal generated in room temperature air plasma. Preliminary experiments demonstrated four-wave mixing signal generated by the electric field in the flame, following ns pulse discharge breakdown. The electric field in the flame is estimated using four-wave mixing signal calibration vs. temperature in electrostatic electric field generated in heated air. Further measurements in the flame are underway.

This work presents time-resolved measurements of nitrogen vibrational temperature, translational-rotational temperature, and absolute OH number density in lean hydrogen-air mixtures excited in a diffuse filament nanosecond pulse discharge, at a pressure of 100 Torr and high specific energy loading. The main objective of these measurements is to study a possible effect of nitrogen vibrational excitation on low-temperature kinetics of HO2 and OH radicals. N2 vibrational temperature and gas temperature in the discharge and the afterglow are measured by ns broadband Coherent Anti-Stokes Scattering (CARS). Hydroxyl radical number density is measured by Laser Induced Fluorescence (LIF) calibrated by Rayleigh scattering. The results show that the discharge generates strong vibrational nonequilibrium in air and H2-air mixtures for delay times after the discharge pulse of up to   1 ms, with peak vibrational temperature of Tv ≈ 2000 K at T ≈ 500 K. Nitrogen vibrational temperature peaks ≈ 200 μs after the discharge pulse, before decreasing due to vibrational-translational relaxation by O atoms (on the time scale of a few hundred μs) and diffusion (on ms time scale). OH number density increases gradually after the discharge pulse, peaking at t   100-300 μs and decaying on a longer time scale, until t   1 ms. Both OH rise time and decay time decrease as H2 fraction in the mixture is increased from 1% to 5%. OH number density in a 1% H2-air mixture peaks at approximately the same time as vibrational temperature in air, suggesting that OH kinetics may be affected by N2 vibrational excitation. However, preliminary kinetic modeling calculations demonstrate that OH number density overshoot is controlled by known reactions of H and O radicals generated in the plasma, rather than by dissociation by HO2 radical in collisions with vibrationally excited N2 molecules, as has been suggested earlier. Additional measurements at higher specific energy loadings and kinetic modeling calculations are underway.