The development and implementation of a high resolution, direct absorption, rapidscanning infrared diode laser spectrometer incorporating a supersonic jet expansion source is described. High sensitivity is achieved by directly modulating absorption signals at frequencies in excess of 50 kHz, enabling their separation from lower frequency mechanical and diode 1/f noise. This is accomplished by rapidly scanning the diode laser across a small frequency window (~0.5-1.5cm<sup>-1</sup>) synchronously with a pulsed supersonic expansion in a time period of 1 or 2 ms. Absorptions appear as small attenuations in the overall variation of the laser mode power across the scan window. This background profile is removed by recording the laser power without gas pulsing and subtracting. Relative frequency calibration is effected by simultaneously recording the spectrum of a reference gas and the interference fringes of an etalon. Absorption signals are recorded by means of a fast 12-bit analog-to-digital converter operating at 1 MHz. This is housed within a dedicated PC microprocessor which performs spectrometer control, data coaddition, signal processing and spectrum calibration functions. The spectrometer has been used to measure the infrared spectra of two weakly bound complexes, CO-OCS and Ne-SiH<sub>4</sub>. The infrared absorption spectrum of CO-OCS was measured in the 5μm region of the OCS ν<sub>3</sub> asymmetric stretch. In addition microwave spectra of CO-OCS and two isotopomers <sup>13</sup>CO-OCS and CO-OC<sup>34</sup>S have been recorded using a pulsed nozzle microwave Fourier transform spectrometer. The lines have been fitted to a Watson S reduction Hamiltonian yielding rotational, quartic and (for the ground states) sextic centrifugal distortion constants. A T-shaped structure is determined and this is rationalised by a simple potential model incorporating a distributed multipole analysis of the electrostatic charge distribution, distributed dispersion contribution and a cylindrical hard-core repulsion. The infrared spectrum of Ne-SiH4 was recorded in the vicinity of the SiH<sub>4</sub> ν<sub>3</sub> triply degenerate stretching vibration centred at 2189.19 cm<sup>-1</sup>. Ne-SiH<sub>4</sub> is only the second atomspherical top complex to be successfully recorded and analysed. The complex exhibits an intermolecular potential with considerably smaller anisotropy than its argon analogue Ar-SiH<sub>4</sub>. Consequently the SiH<sub>4</sub> unit is almost free to rotate within the complex, resulting in novel Coriolis interaction between the angular momentum of the SiH<sub>4</sub> unit and that of the overall complex. Individual bands are fitted to Coriolis interaction Hamiltonians, and the band centres for all the transitions of the complex are fitted to an anisotropic intermolecular potential. Finally, applications of the spectrometer to the study of air sensitive compounds and species generated by electric discharge sources are considered.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:297123 |
| Date | January 1995 |
| Creators | Brookes, Matthew Daniel |
| Contributors | Brown, John M. |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:81958380-6230-454d-bb44-bfb57d887749 |
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