Electronic states and spin-orbit splitting of lanthanum dimer.

Lanthanum dimer (La2) was studied by mass-analyzed threshold ionization (MATI) spectroscopy and a series of multi-configuration ab initio calculations. The MATI spectrum exhibits three band systems originating from ionization of the neutral ground electronic state, and each system shows vibrational frequencies of the neutral molecule and singly charged cation. The three ionization processes are La2+ (a2∑g+) ← La2 (X1∑g+), La2+ (b2Π3/2, u) ← La2 (X1∑g+), and La2+ (b2Π1/2, u) ← La2 (X1∑g+), with the ionization energies of 39 046, 40 314, and 40 864 cm-1, respectively. The vibrational frequency of the X1Σg+ state is 207 cm-1, and those of the a2Σg+, b2Π3/2, u and b2Π1/2, u are 235.7, 242.2, and 240 cm-1. While X1Σg+ is the ground state of the neutral molecule, a2Σg+ and b2Πu are calculated to be the excited states of the cation. The spin-orbit splitting in the b2Πu ion is 550 cm-1. An X4Σg- state of La2+ was predicted by theory, but not observed by the experiment. The determination of a singlet ground state of La2 shows that lanthanum behaves differently from scandium and yttrium. [ABSTRACT FROM AUTHOR]