Electronic Transitions and Spin-Orbit Splitting of Lanthanum Dimer

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Lanthanum dimer (La_2) was studied by mass-analyzed threshold ionization (MATI) spectroscopy and a series of high-level multi-configuration ab initio calculations (CASSCF, CASPT2, and MRCI). The MATI spectrum exhibits three band systems originating at 39044, 40312, and 40862 Cm-1, respectively. Above the band origin, the first band system displays a vibrational progression of ˜232 Cm-1, and the other two show vibrational progression with the same interval of ˜240 Cm-1. Below the band origin, the three systems exhibit the same vibrational interval of ˜207 Cm-1. These band systems are assigned to three electronic transitions from the ground state of La_2 to the low-lying electronic states of La_2^+: ^2Σ^+_g ← ^1Σ^+_g, ^2Πu,1/2 ← ^1Σ^+_g, and ^2Πu,3/2 ← ^1Σ^+_g. The spin-orbit splitting in the ^2ΠU ion state is 550 Cm-1. In addition, the electronic states and bonding of La_2 will be compared with those of Sc_2 and Y_2.

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