Ten gaseous transient metal-containing molecules have been synthesized and studied by high resolution spectroscopy. Transient molecules are molecules with a short lifetime, and they play an important role in chemistry because they are reaction intermediates. One of the difficulties faced in studying transient molecules is their typically low concentrations under laboratory conditions. Three types of sources were used to generate these molecules: 1) an emission source that combines a high temperature furnace with an electrical discharge was used to generate SbH, SbD, TeH, TeD, CdH2, CdD2, HZnCl and BeF2; 2) a King furnace (carbon tube furnace) was used to synthesize CoS; 3) a Broida-type oven (metal flow reactor) was used to generate SrOD. Two spectroscopic techniques were employed to study these molecules: 1) Fourier transform infrared emission spectroscopy was used to study SbH, SbD, TeH, TeD, CdH2, CdD2, HZnCl, BeF2, and CoS. 2) Laser-induced fluorescence spectroscopy was employed to study SrOD. One or two lasers were used to excite the SrOD molecules from the ground state to excited electronic states and then these SrOD molecules relaxed back to the ground state by emitting fluorescence, which was detected by a photomultiplier tube. Significantly-improved spectroscopic constants have been obtained for SbH, SbD, TeH and TeD. For SbH and SbD, the infrared X 3– vibration-rotation bands and the near infrared b 1+ – X 3– transition were observed and rotationally analyzed, and a Hund’s case (a) fit was performed for each of the four observed SbH isotopologues. For TeH and TeD, the X 23/2 vibration-rotation bands and the near infrared X 21/2– X 23/2 transition have been observed and rotationally analyzed, and Hund’s case (a) and case (c) fits were performed for each of the ten observed TeH isotopologues. New spectroscopic constants were obtained for HZnCl, CdH2 and CdD2. These three molecules have been successfully generated in the gas phase for the first time. The fundamental band and one hot band were obtained for the H–Zn stretching mode (1) and for the antisymmetric stretching mode (3) of CdH2 and CdD2. A least-squares fit was performed for each of the four observed HZnCl isotopologues and the twelve observed CdH2 isotopologues For the first time, a complete set of molecular constants for all three vibrational frequencies was experimentally determined for BeF2. Thirteen new hot bands were rotationally analyzed and the 1, 2, and3 vibrational frequencies were directly determined by fitting nineteen bands together. The traditional equilibrium vibrational and rotational constants were obtained for BeF2 by simultaneously fitting the observed vibrational term values and B rotational constants. New spectroscopic constants were obtained for two electronic states of CoS and SrOD, respectively. The A 4i – X 4i and B 4i – X 4i transitions of CoS and the and transitions of SrOD were observed for the first time. Hund’s case (c) fits were performed for the CoS transitions and Hund’s case (a) fits were performed for the SrOD transitions.

Ten gaseous transient metal-containing molecules have been synthesized and studied by high resolution spectroscopy. Transient molecules are molecules with a short lifetime, and they play an important role in chemistry because they are reaction intermediates. One of the difficulties faced in studying transient molecules is their typically low concentrations under laboratory conditions. Three types of sources were used to generate these molecules: 1) an emission source that combines a high temperature furnace with an electrical discharge was used to generate SbH, SbD, TeH, TeD, CdH2, CdD2, HZnCl and BeF2; 2) a King furnace (carbon tube furnace) was used to synthesize CoS; 3) a Broida-type oven (metal flow reactor) was used to generate SrOD. Two spectroscopic techniques were employed to study these molecules: 1) Fourier transform infrared emission spectroscopy was used to study SbH, SbD, TeH, TeD, CdH2, CdD2, HZnCl, BeF2, and CoS. 2) Laser-induced fluorescence spectroscopy was employed to study SrOD. One or two lasers were used to excite the SrOD molecules from the ground state to excited electronic states and then these SrOD molecules relaxed back to the ground state by emitting fluorescence, which was detected by a photomultiplier tube. Significantly-improved spectroscopic constants have been obtained for SbH, SbD, TeH and TeD. For SbH and SbD, the infrared X 3– vibration-rotation bands and the near infrared b 1+ – X 3– transition were observed and rotationally analyzed, and a Hund’s case (a) fit was performed for each of the four observed SbH isotopologues. For TeH and TeD, the X 23/2 vibration-rotation bands and the near infrared X 21/2– X 23/2 transition have been observed and rotationally analyzed, and Hund’s case (a) and case (c) fits were performed for each of the ten observed TeH isotopologues. New spectroscopic constants were obtained for HZnCl, CdH2 and CdD2. These three molecules have been successfully generated in the gas phase for the first time. The fundamental band and one hot band were obtained for the H–Zn stretching mode (1) and for the antisymmetric stretching mode (3) of CdH2 and CdD2. A least-squares fit was performed for each of the four observed HZnCl isotopologues and the twelve observed CdH2 isotopologues For the first time, a complete set of molecular constants for all three vibrational frequencies was experimentally determined for BeF2. Thirteen new hot bands were rotationally analyzed and the 1, 2, and3 vibrational frequencies were directly determined by fitting nineteen bands together. The traditional equilibrium vibrational and rotational constants were obtained for BeF2 by simultaneously fitting the observed vibrational term values and B rotational constants. New spectroscopic constants were obtained for two electronic states of CoS and SrOD, respectively. The A 4i – X 4i and B 4i – X 4i transitions of CoS and the and transitions of SrOD were observed for the first time. Hund’s case (c) fits were performed for the CoS transitions and Hund’s case (a) fits were performed for the SrOD transitions.

abstract: This thesis describes the studies for two groups of molecules in the gas-phase: (a) copper monofluoride (CuF) and copper hydroxide (CuOH); (b) thorium monoxide (ThO) and tungsten carbide (WC). Copper-containing molecules (Group a) are selected to investigate the ionic bonding in transition metal-containing molecules because they have a relatively simple electronic state distribution due to the nearly filled 3d-orbital. ThO and WC (Group b) are in support of particle physics for the determination of electron electric dipole moment (eEDM), de, the existence of which indicates new physics beyond the Standard Model. The determination of the tiny eEDM requires large electric fields applied to the electron. The 3(Delta)1 states for heavy polar molecules were proposed [E. R. Meyer, J. L. Bohn, and M. P. Deskevich, Phys. Rev. A 73, 062108 (2006)] to determine de with the following attractive features: (1) large electric dipole moments; (2) large internal electric fields, Eeff, experienced by valence electrons; (3) nearly degenerate omega-doublets; (4) extremely small magnetic dipole moments. The H3(Delta)1 state for ThO and the X3(Delta)1 state for WC are both good candidates. Spectroscopic parameters (i.e. molecular electric and magnetic dipole moments, omega-doubling parameters, etc) are required for the 3(Delta)1 states of ThO and WC. High resolution optical spectra (linewidth ~50 MHz) of CuF, CuOH, ThO and WC were recorded field-free and in the presence of a static electric field (or magnetic field) using laser ablation source/supersonic expansion and laser induced fluorescence (LIF) detection. The spectra were modeled by a zero-field effective Hamiltonian operator and a Stark (or Zeeman) Hamiltonian operator with various molecular parameters. The determined molecular parameters are compared to theoretical predictions. The small omega-doubling parameter was well determined using the pump/probe microwave optical double resonance (PPMODR) technique with a much higher resolution (linewidth ~60 kHz) than optical spectroscopy. In addition to the above mentioned studies of the two groups of molecules, a resonance enhanced multi-photon ionization (REMPI) combined with a time-of-flight mass spectrometer (TOFMS) has been developed to identify the molecules responsible for observed LIF signals. The operation of this spectrometer has been tested by recording the mass spectrum of Ti/O2 and the REMPI spectrum for TiO using a two-color excitation scheme. / Dissertation/Thesis / Ph.D. Chemistry 2012