Femtosecond Laser Ablation Molecular Isotopic Spectrometry for Zirconium Isotope Analysis

• Published in: Analytical chemistry (Washington) Vol. 87; no. 9; pp. 4788 - 4796
• Main Authors: Hou, Huaming, Chan, George C.-Y, Mao, Xianglei, Zorba, Vassilia, Zheng, Ronger, Russo, Richard E
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05-05-2015
• Subjects: Band theory; Bands; Calibration; Emission analysis; Laser ablation; Molecules; Phase transitions; Scientific imaging; Spectra; Spectroscopy; Zirconium
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/acs.analchem.5b00056

Laser ablation molecular isotopic spectrometry (LAMIS) for rapid isotopic analysis of zirconium at atmospheric pressure was studied with a femtosecond-laser system operated under high repetition rate (1 kHz) and low pulse energy (160 μJ). The temporal evolution of zirconium neutral-atomic and ionic lines, as well as zirconium oxide molecular bands, were studied. Six molecular bands, belonging to the d3Δ−a3Δ (i.e., the α system) and E1Σ+–X1Σ+ transitions, were observed with appreciable isotopic shifts. The assignments of the isotopic bandheads were first based on theoretical predictions of the band origins and the associated isotopic shifts of various dipole-allowed ZrO electronic transitions, followed by an experimental confirmation with a 94Zr-enriched ZrO2 sample. In this work, the α­(0,1) band from the d3Δ3–a3Δ3 subsystem was utilized for Zr isotope analysis based on a compromise between the magnitude of isotopic shifts in emission wavelengths, emission strengths, signal-to-background ratios, and spectral interferences. The analysis was performed in a standardless calibration approach; the isotopic information was extracted from the experimentally measured molecular spectra through theoretical spectral fitting. The results demonstrate the feasibility to obtain isotopic information for a spectrally complicated element like zirconium, without the need to use isotopically labeled calibration standards. The availability of comprehensive molecular constants will further improve the analytical accuracy of this standardless calibration approach.