Spectroscopy of diatomic ZrF and ZrCl: 760 – 555 nm

Abstract

The optical spectrum of diatomic ZrF has been investigated, with transitions recorded in the range from 14,700 to 18,000 cm(-1). Many bands have been observed, several of which can be grouped into three band systems. Rotationally resolved investigations are hampered by perturbations that are rampant among the excited states, but three unperturbed bands have revealed that the ground state of ZrF has Ω" = 3/2, with a bond length of r(e)'' = 1.854(1) Å. Hot bands originating from v" = 1 provide the ground state vibrational interval, ΔG(1/2)'' = 691.45(2) cm(-1) for (90)Zr(19)F. Based on comparisons to ZrCl and ligand-field considerations, the ZrF ground state is assigned as a (2)Δ(3/2) level deriving from the 3σ(2) 1δ(1) configuration, in agreement with a previous study. In addition to the measurements on ZrF, vibronically resolved spectra of ZrCl have been recorded over the 13,000 to 18,000 cm(-1) range, and four band systems have been identified.

Near-infrared spectrum of ZrF by intracavity laser absorption spectroscopy

“…Our work described herein reports a new vibrational band of the CX = 3/2-X 2 D 3/2 transition in ZrF with a red degraded bandhead at 13 527 cm À1 . This assignment is consistent with the work of Martinez and Morse [8].…”

“…These were calculated using the transition energies, vibrational constants, and anharmonicity constants reported by Martinez and Morse [8]. The predicted bandhead positions are provided in Table 1; the location of the (1, 1) bandhead (at 13 527 cm À1 ) of the C-X transition is consistent with the observed transition.…”

“…A 2007 computational study by Cheng et al. [6] predicted a ground state symmetry of X 2 D 3/2 , and in 2011 two separate spectroscopic studies were published that confirmed the X 2 D 3/2 ground state symmetry and identified several electronic transitions [7,8].…”

“…Four other transitions at 22 944 cm À1 , 22 105 cm À1 , 21 801 cm À1 , and 21 285 cm À1 were assigned as the (2, 0) 2 U-X 2 D, (1, 0) 2 D-X 2 D, (3, 0) 4 P-a 4 R À , and (2, 0) 4 P-a 4 R À transitions, respectively. Also in 2011, Martinez and Morse [8] examined spectra of ZrF and ZrCl in the 555-760 nm region using resonant two-photon ionization (R2PI) spectroscopy with TOF detection. A total of 93 vibrational transitions of ZrF were observed.…”

“…The (4, 0), (5, 0), (5, 1), and (6, 0) vibrational bands of this system were fully resolved, and a complete analysis of the (4, 0) band was performed to obtain molecular constants. Comparison of the molecular constants for the (5, 0) and (5, 1) bands of the C-X transitions allowed for precise determination of the ground state vibrational interval; DG 00 1=2 = 691.45(2) cm À1 for 90 Zr 19 F [8]. Our work described herein reports a new vibrational band of the CX = 3/2-X 2 D 3/2 transition in ZrF with a red degraded bandhead at 13 527 cm À1 .…”