The visible spectrum of zirconium dioxide, ZrO2

Abstract

The electronic spectrum of a cold molecular beam of zirconium dioxide, ZrO2, has been investigated using laser induced fluorescence (LW) in the region from 17 000 cm(-1) to 18 800 cm(-1) and by mass-resolved resonance enhanced multi-photon ionization (REMPI) spectroscopy from 17 000 cm(-1)-21 000 cm(-1). The LIF and REMPI spectra are assigned to progressions in the (A) over tilde (1) B-2(v(1), v(2), v(3)) <- (X) over tilde (1) A(1)(0, 0, 0) transitions. Dispersed fluorescence from 13 bands was recorded and analyzed to produce harmonic vibrational parameters for the (X) over tilde (1) A(1) state of omega(1) = 898(1) cm(-1), omega(2) = 287(2) cm(-1), and omega(3) = 808(3) cm(-1). The observed transition frequencies of 45 bands in the LIF and REMPI spectra produce origin and harmonic vibrational parameters for the (A) over tilde (1) B-2 state of T-e = 16 307(8) cm(-1), omega(1) = 819(3) cm(-1), omega(2) = 149(3) cm(-1), and omega(3) = 518(4) cm(-1). The spectra were modeled using a normal coordinate analysis and Franck-Condon factor predictions. The structures, harmonic vibrational frequencies, and the potential energies as a function of bending angle for the (A) over tilde (1) B-2 and (X) over tilde (1) A(1) states are predicted using time-dependent density functional theory, complete active space self-consistent field, and related first-principle calculations. A comparison with isovalent TiO2 is made. (C) 2011 American Institute of Physics. [doi:10.1063/1.3632053]