Theo Guillaume’s research while affiliated with University of Birmingham and other places

We present the development of a new astrochemical research tool, HILTRAC, the Highly Instrumented Low Temperature ReAction Chamber. The instrument is based on a pulsed form of the CRESU (Cinétique de Réaction en Écoulement Supersonique Uniforme, meaning reaction kinetics in a uniform supersonic flow) apparatus, with the aim of collecting kinetics and spectroscopic information on gas phase chemical reactions important in interstellar space or planetary atmospheres. We discuss the apparatus design and its flexibility, the implementation of pulsed laser photolysis followed by laser induced fluorescence, and the first implementation of direct infrared frequency comb spectroscopy (DFCS) coupled to the uniform supersonic flow. Achievable flow temperatures range from 32(3) to 111(9) K, characterizing a total of five Laval nozzles for use with N2 and Ar buffer gases by impact pressure measurements. These results were further validated using LIF and direct frequency comb spectroscopy measurements of the CH radical and OCS, respectively. Spectroscopic constants and linelists for OCS are reported for the 10⁰1 band near 2890–2940 cm⁻¹ for both OC³²S and OC³⁴S, measured using DFCS. Additional peaks in the spectrum are tentatively assigned to the OCS-Ar complex. The first reaction rate coefficients for the CH + OCS reaction measured between 32(3) and 58(5) K are reported. The reaction rate coefficient at 32(3) K was measured to be 3.9(4) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ and the reaction was found to exhibit no observable temperature dependence over this low temperature range.

Laval nozzles are used in the CRESU (“Cinétique de Réaction en Écoulement Supersonique Uniforme”) method to generate a collimated low temperature (5–200 K), low pressure (30–500 Pa), high Mach number (1 < M < 20) supersonic jet. Laval nozzles have been designed using the Method of Characteristics (MOC) since the development of CRESU, which is an analytical method that assumes inviscid, isentropic flow, and is routinely used to design nozzle profiles for a particular gas and temperature with a uniform shock free exit. This study aims to provide a robust computational framework to overcome the limitations of the MOC while also providing recommendations on the numerical model setup required to model a low-temperature supersonic jet. It also discusses the blockage effects when using the Pitot tube method for flow characterization, the influence of inlet turbulence and reservoir size. Numerical results are validated using two different experimental apparatuses from research groups at the University of Leeds and the University of Birmingham. Finally, a MATLAB framework was developed and has been provided as an open source toolbox to allow any user to perform computational fluid dynamics on any Laval nozzle, with the ability to change nozzle geometry, operating conditions and bath gas. The toolbox has been rigorously tested against many benchmark cases, which shows that steady-state Reynolds-averaged Navier–Stokes with the k-omega-shear stress transport turbulence model can be used to accurately predict global quantities, such as average temperature in the stable region of the supersonic jet.

We present the development of a new astrochemical research tool HILTRAC, the Highly Instrumented Low Temperature ReAction Chamber. The instrument is based on a pulsed form of the CRESU (Cin\'etique de R\'eaction en \'Ecoulement Supersonique Uniforme, meaning reaction kinetics in a uniform supersonic flow) apparatus, with the aim of collecting kinetics and spectroscopic information on gas phase chemical reactions important in interstellar space or planetary atmospheres. We discuss the apparatus design and its flexibility, the implementation of pulsed laser photolysis followed by laser induced fluorescence (PLP-LIF), and the first implementation of direct infrared frequency comb spectroscopy (DFCS) coupled to the uniform supersonic flow. Achievable flow temperatures range from 32(3) - 111(9) K, characterising a total of five Laval nozzles for use with N2 and Ar buffer gases by pressure impact measurements. These results were further validated using LIF and DFCS measurements of the CH radical and OCS, respectively. Spectroscopic constants and linelists for OCS are reported for the 1001 band near $2890 - 2940 cm^{-1}$ for both $OC^{32}S$ and $OC^{34}S$, measured using DFCS. Additional peaks in the spectrum are tentatively assigned to the OCS-Ar complex. The first reaction rate coefficients for the CH + OCS reaction measured between 32(3) K and 58(5) K are reported. The reaction rate coefficient at 32(3) K was measured to be $3.9(4) \times 10^{10} cm^3 molecule^{-1} s^{-1}$ and the reaction was found to exhibit no observable temperature dependence over this low temperature range.

Experimental studies of the products of elementary gas-phase chemical reactions occurring at low temperatures (<50 K) are very scarce, but of importance for fundamental studies of reaction dynamics, comparisons with high-level quantum dynamical calculations, and, in particular, for providing data for the modeling of cold astrophysical environments, such as dense interstellar clouds, the atmospheres of the outer planets, and cometary comae. This study describes the construction and testing of a new apparatus designed to measure product branching fractions of elementary bimolecular gas-phase reactions at low temperatures. It combines chirped-pulse Fourier transform millimeter wave spectroscopy with continuous uniform supersonic flows and high repetition rate laser photolysis. After a comprehensive description of the apparatus, the experimental procedures and data processing protocols used for signal recovery, the capabilities of the instrument are explored by the study of the photodissociation of acrylonitrile and the detection of two of its photoproducts, HC3N and HCN. A description is then given of a study of the reactions of the CN radical with C2H2 at 30 K, detecting the HC3N product, and with C2H6 at 10 K, detecting the HCN product. A calibration of these two products is finally attempted using the photodissociation of acrylonitrile as a reference process. The limitations and possible improvements in the instrument are discussed in conclusion.

HCN and its unstable isomer HNC are widely observed throughout the interstellar medium, with the HNC/HCN abundance ratio correlating strongly with temperature. In very cold environments HNC can even appear more abundant than HCN. Here we use a chirped pulse Fourier transform spectrometer to measure the pressure broadening of HCN and HNC, simultaneously formed in situ by laser photolysis and cooled to low temperatures in uniform supersonic flows of helium. Despite the apparent similarity of these systems, we find the HNC–He cross section to be more than twice as big as the HCN–He cross section at 10 K, confirming earlier quantum calculations. Our experimental results are supported by high-level scattering calculations and are also expected to apply with para-H2, demonstrating that HCN and HNC have different collisional excitation properties that strongly influence the derived interstellar abundances. HCN and its isomer HNC are both observed in the interstellar medium and inelastic collisions with helium and other species strongly influence their derived abundances. Now it has been shown experimentally and theoretically that HNC is much more strongly excited than HCN in collisions with helium at the low temperatures of interstellar space.

This thesis presents research work on the construction and development of a new instrument and its utilization in the framework of the CPUF technique (Chirped Pulse in Uniform Flow) to study low-temperature collisional processes of astrochemical interest. The thesis details the characteristics of the CRESUCHIRP apparatus and the technical development related to its utilization as a CPUF instrument. The new CRESU (Cinétique de Réaction en Écoulement supersonique Uniforme) apparatus and the supporting instrumentation are described. The characterization of an E-band (60-90 GHz) CP-FTmmW spectrometer (Chirped Pulse-Fourier Transform millimeter Wave) is presented with its coupling to the rest of the instrument. The capability of the spectrometer as a spectroscopic tool is presented with the measurement of pressure broadening coefficients at room temperature for the system OCS + He. Experiments using the CPUF technique are presented with the measurement of the difference in collisional interaction of isomers at low temperatures: HCN and HNC with He. Studies of the potential of the instrument for application to kinetics measurement at low temperature are presented for the reactions CN + ethane at 10 K and CN + acetylene at 30 K. Tentative calibrations of these two reactions are presented. The strengths and weaknesses of the new instrument are discussed, as well as potential improvements to the technique.