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Phys. Chem. Chem. Phys., 2008, 10, 4006 - 4013, DOI: 10.1039/b803975e
The ionization energy of Be2, and spectroscopic characterization of the (1)3
+u, (2)3
g, and (3)3g statesJeremy M. Merritt, Alexey L. Kaledin, Vladimir E. Bondybey and Michael C. Heaven
Low lying electronic states of the beryllium dimer were investigated by laser induced fluorescence (LIF) and resonance enhanced multiphoton ionization (REMPI) techniques. Be2 was formed by pulsed laser ablation of Be metal in the presence of helium carrier gas, followed by a free jet expansion into vacuum. Several previously unobserved states of the dimer were characterized. These included transitions of the triplet manifold (2)3
g 
(1)3
+u and (3)3g (1)3+u, for which rotationally resolved bands were obtained. In addition, transitions to the v
= 10–18 vibrational levels of the A
1u state were recorded. Photoionization efficiency (PIE) measurements were used to determine an accurate ionization energy (IE) for Be2 of 7.418(5) eV and the term energy for (1)3+u. Above the ionization threshold the PIE spectrum was found to be highly structured, consisting of overlapping Rydberg series that converged on excited vibrational levels of Be2+. Analysis of these series yielded a vibration frequency for the X2+u state of 498(20) cm-1. The bond dissociation energy for Be2+, deduced from the IE measurement, was 16072(40) cm-1. Multi-reference configuration interaction (MRCI) calculations were carried out for Be2 and Be2+, yielding results that were in excellent agreement with the experimental observations.
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