Electronic spectroscopy and electronic structure of diatomic TiFe

Diatomic TiFe, a 12 valence electron molecule that is isoelectronic with Cr(2), has been spectroscopically investigated for the first time. In addition, the first computational study that includes the ground and excited electronic states is reported. Like Cr(2), TiFe has a (1)Σ(+) ground state that is dominated by the 1σ(2) 2σ(2) 1π(4) 1δ(4) configuration. Rotationally resolved spectroscopy has established a ground state bond length of 1.7024(3) Å, quite similar to that found for Cr(2) (r(0) = 1.6858 Å). Evidently, TiFe exhibits a high degree of multiple bonding. The vibronic spectrum is highly congested and intense to the blue of 20,000 cm(-1), while two extremely weak band systems, the [15.9](3)Π(1) ← X (1)Σ(+) and [16.2](3)Π(0+) ← X (1)Σ(+) systems, are found in the 16,000-18,500 cm(-1) region. The bond lengths, obtained by inversion of the B(e)' values, and vibrational frequencies of the two upper states are nearly identical: 1.886 Å and 344 cm(-1) for [15.9](3)Π(1) and 1.884 Å and 349 cm(-1) for [16.2](3)Π(0+). The measured spin-orbit splitting of the (3)Π state is consistent with its assignment to the 1σ(2) 2σ(2) 1π(4) 1δ(3) 2π(1) configuration, as is also found in the ab initio calculations.