RESUMEN
Neutral lanthanum clusters are studied by photoionization time-of-flight mass spectroscopy, laser threshold photoionization spectroscopy, and density functional theory (DFT). Mass abundance spectra (MS) registered at multiple photoionization wavelengths in the range of 195-230 nm by single photon ionization reveal the production of all sizes, Lan (n ≥ 50), in good abundance, nullifying previously predicted low abundances for certain sizes in the 3-14 size range. Also, the MS do not reveal the extraordinary stability of any specific size, as one would expect, from previous theoretical predictions of 7- and 13-atom clusters as magic. Ionization energies (IEs) are measured for Lan (n = 2-14) clusters. DFT has been used to determine the stable geometric isomers for 2- to 10-atom clusters and to calculate their IEs. The theoretical IEs of 2-7 atom clusters are in decent agreement with their experimental values; however, the theoretical IEs are somewhat lower by â¼0.4 eV for n ≥ 8 than their experimental IEs.
RESUMEN
Wavelength-resolved fluorescence spectra of jet-cooled LaH were obtained from D1, E1, and 0(+)((3)Σ(-)) states by exciting isolated rotational levels. The observation of a(3)Δ(1) and a(3)Δ(2) states at 1259.5(5) and 1646(1) cm(-1), respectively, established the missing energy link between the singlet and triplet manifolds. The low-energy b(3)Π(0,1) and B(1)Δ(2) states predicted earlier from ab initio studies were also observed for the first time. Vibrational constants ω(e) = 1418(2) cm(-1), ω(e)x(e) = 15.6(7) cm(-1) for the ground and ΔG(1∕2) = 1326.1(7) and 1312(1) cm(-1), respectively, for the a(3)Δ(1) and b(3)Π(1) states were also determined. Vibrational frequencies were found to be in excellent agreement with earlier ab initio values. However, ab initio term energies and spin-orbit separation of (3)Δ(2)-(3)Δ(1) and (3)Π(1)-(3)Π(0) were found to be in poor agreement with the present observations. Also, the (3)Π state that was predicted to be inverted is observed to be regular.