The “Filet” Jet

Overview

The supersonic beam apparatus used throughout this work, nicknamed the

“filet” jet, was constructed in the context of the PhD thesis of Nicole Borho⁴⁸ in 2003. Over the years, the apparatus has seen the exchange of the con-nected FTIR spectrometer and an extension of its realistic spectral range to 200–8000 cm⁻¹.^14,29,49,50 A recent account of its features and operation is given in Reference 43, together with a demonstration of its capabilities for the measurement of O–H stretching fundamental and overtone bands. The following description will thus be restricted to a brief overview of the setup, noting only important key points and changes to previously established rou-tines.

The unmatched eponymous feature of the setup is the “fine, butlengthy”

slit nozzle of 600×0.2 mm²dimensions with a throughput of up to 3 mol s⁻¹, backed by a buffer volume of up to 23 m³ and a pumping system of up to 2500 m³h⁻¹. Six solenoid valves pass the sample gas mixture from a 67 L reservoir into a pre-expansion chamber which serves to ensure a spatially homogeneous feeding of the nozzle. The large absorption pathway through the elongated expansion zone allows convenient sampling at a variable downstream distance by the mildly focused beam of an unmodified, evac-uated Bruker IFS 66v/S FTIR spectrometer and its built-in light sources.⁵¹ Measurements in the spectral OH and OD fundamental region ofca. 4000–

2400 cm⁻¹ are possible using a tungsten light source, KBr or CaF2 optics and beamsplitters, and an external LN₂-cooled 3 mm² InSb detector; for the measurement of the respective stretching overtones between 7500 and 6400 cm⁻¹, a 7 mm²InGaAs detector is available. The mid- and far-infrared

CHAPTER 1. EXPERIMENTAL AND THEORETICAL METHODS

Figure 1.1: Schematic of the “filet” jet (not to scale).

(MIR and FIR) regions are accessible by MCT detectors or a liquid helium-cooled bolometer in conjunction with KBr or Mylar beamsplitters; these were, however, not put to use for the present work. In all cases, appropriate optical filters allow to reduce the bandwidth of the detector and increase the signal-to-noise ratio. The jet valves are synchronized to the rapid scans of the FTIR spectrometer, with typical pulse durations on the order of 150 ms followed by an evacuation period of 30 to 60 s.

Sample preparation is carried out in thermostatted glass saturators by directing a stream of the carrier gas through the liquid or solid analyte. By varying the carrier gas pressure, saturator temperature, and opening/clos-ing times of the feedopening/clos-ing solenoid valves, the concentration of the sample can be controlled. For more concentration-sensitive measurements or gaseous analytes, a mixing line is available to prepare more well-defined sample mix-tures in a 50 L gas cylinder which can be fed directly into the reservoir.

One advantage of the filet jet over its size- or even conformer-selective multi-resonance siblings is the reliance on direct infrared absorption, al-lowing band positions as well as intensity information to be extracted from the recorded spectra. Both quantities provide estimates for the strength of

1.2. EXPERIMENTAL METHODS

hydrogen-bonded stretching modes (see Section 1.1) and can serve as sen-sitive benchmarks for quantum chemical predictions. Observing the weak overtone bands of hydrogen-bonded stretching vibrations, however, proves somewhat elusive due to their inherent intensity penalty outlined above. Ul-timately, this mandates the measurement times (or equivalently, the num-ber of co-added jet scans) to be increased by about one order of magnitude as compared to the fundamental bands. Moreover, determining the inten-sity ratio between fundamental and overtone bands necessitates recording a number of additional panoramic spectra over their combined spectral re-gions, using the monomer bands as an internal standard for calibration of the different optical filters and detectors. The intensity ratio thus pro-vides an additional, but somewhat remote means of assessing the interaction strength, and its determination is not a routine task even in the straightfor-wardfiletjet experiment. Within this work, the method has been put to di-rect use in ambiguous methanol-anisole experiments to validate the assign-ment of competing structural motifs,⁵²as will be presented in Section3.2.

Modifications

Some minor changes to the setup were made during the course of this thesis.

First, a Teflon coating was applied to the inside of the reservoir in order to prevent issues from corrosion of the stainless-steel tank. However, a certain amount of adsorption of the sample gas by the coating itself is detectable, and the reservoir must be thoroughly evacuated after measurements and before changing sample mixtures. Second, the standard 12 V, 50 W tungsten lamps employed previously were exchanged for higher-power 24 V, 150 W analogs in order to facilitate fundamental and overtone experiments. The resulting signal-to-noise capabilities of the two light sources can be judged from a standardized “NOTCH” (“Noise Test Challenge”) noise level analy-sis. In this routine, the jet setup is run up to a normal measurement-ready state in the desired configuration. 1-minute background and sample scans are recorded through the empty jet chamber, and the resulting absorbance spectrum is sent to a custom-made FORTRAN program which calculates a quadratic fit to the spectral baseline and its root-mean-square error (RMSE) in a 50 cm⁻¹ moving window. Its negative decadic logarithm is stored for each window center position as a figure of merit for the noise level in the ac-cording region, allowing direct comparison of measurement configurations and different spectrometers as well as long-term stability monitoring.

Figure 1.2 shows a set of NOTCH curves obtained using external InSb and InGaAs detectors in typical measurement configurations with 150 W and 50 W tungsten lamps. Two measurements were carried out for each, and

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1.2. EXPERIMENTAL METHODS

the original data (gray curves) were smoothed to a 200-point moving mean (∼100 cm⁻¹, with red and blue curves for 150 and 50 W lamps, respectively).

The yellow shading marks regions in which residual water and methane bands impair the analysis. The lower traces in each graph shows averaged 150 W/50 W RMSE ratios and demonstrate the advantage of the stronger light source across both spectral regions by a factor of∼1.5 in the noise level.

Additional details on these measurements are given in AppendixA.

The standard 80 kHz velocity setting for the scanning interferometer mirror had previously been reduced to 60 kHz in overtone measurements due to unfavorable noise impairments at the higher setting. For the over-tone measurements conducted within this work, the 80 kHz option was re-visited with the 150 W tungsten source. Two independent error sources were isolated which produced excessive baseline noise in the near-infrared region through ill-defined compensation of water vapor bands between the back-ground and sample scans. It can be assumed that the measures undertaken to eliminate these problems also take effect in the fundamental region, and they have thus been implemented permanently.

First, the scanning mirror is reset to an initial position by the control-ling software at the beginning of each measurement cycle; its motion is then started, and a number of background scans is recorded. This stopping-starting event apparently leads to mechanical vibrations of the mirror which spoil the first background scans, consequently causing artifacts in all ab-sorbance spectra. To circumvent this problem, a “Wait 5000” command line was added to the top of the TRS routine that controls the synchronization of the spectrometer with the jet setup. This pre-scan delay leads to five sec-onds of “blind” mirror motion, thus allowing the disturbances to settle before commencing the data acquisition for the background scans.

Second, the front face of the nozzle base plate attached to the pre-expansion chamber partially extends into the IR beam under typical ex-perimental conditions. Although the respective part of the construction is blackened, a portion of this light still appears to be scattered either back into the interferometer or into the detector chamber. Upon releasing the jet

Figure 1.2 (opposite): NOTCH curves for 150 W (red) and 50 W (blue) tung-sten lamp comparison using InSb (top) and InGaAs (bottom) detectors and appropriate optical filters. The lower traces in each graph show averaged 150 W/50 W RMSE ratios. Yellow shading indicates regions where residual water and methane bands may impair the noise level analysis.

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gas pulse, the nozzle starts to vibrate, modulating this scattered light and leaving similar noise artifacts as described above. These artifacts vanish when removing the nozzle from the beam or reducing the vibrations by low-ering the stagnation pressure. As a simple solution, it is sufficient to block the offending part of the IR beam from entering the jet chamber by partially covering the entrance window.