Relativistic calculations of electronic states of PdH

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Abstract
Complete active space MCSCF(CASSCF)/first‐order configuration interaction (FOCI) calculations followed by relativistic configuration interaction (RCI) calculations are carried out on 2Σ+, 2Π, 2Δ, and 2Σ+(II) λ–s states and 1/2, 3/2, 1/2(II), 3/2(II), and 5/2 ω–ω states of PdH. Our calculations predict that the ground state is 2Σ+ 1/2. The spin–orbit splitting and contamination of the excited states (2Π and 2Δ) are quite large. The two 3/2 states are quite mixed [3/2(I): 66% 2Δ3 / 2, 29% 2Π3 / 2] in character. The spectroscopic properties (R e , T e , D e , and ω e ) of all the above states are calculated and compared with available experimental results on the ground state of PdD. The Mulliken population analysis of the low‐lying states of PdH shows that the 2Σ+ state is ionic (Pd+H−) but the excited 2Π and 2Δ states are a bit more ionic with the same polarity as the ground state. The 3/2 state exhibits an interesting avoided crossing.