An Ab Initio Electronic Structure Investigation of the Ground and Excited States of ScH+, YH+, and LaH.

Abstract

Multireference configuration interaction (MRCI), Davidson-corrected MRCI (MRCI+Q), coupled-cluster singles, doubles, and perturbative triples [CCSD(T)], and frozen-core full configuration interaction (fcFCI) calculations were carried out using large, correlation-consistent basis sets to investigate the excited states of the Sc atom and the spin-free and spin-orbit coupled potential energy profiles, energetics, spectroscopic constants, and electron populations of low-lying states of MH⁺ (M = Sc, Y, La). The core electron correlation effects, complete basis set effects, and spin-orbit coupling effects were also evaluated. The first four electronic states of all MH⁺ are 1²Δ, 1²Σ⁺, 1²Π, and 2²Σ⁺ with 1σ²1δ¹, 1σ²2σ¹, 1σ²1π¹, and 1σ²3σ¹ single-reference electron configurations, respectively. These states of MH⁺ can be represented by the M²⁺H^- ionic structure. The ground states of ScH⁺, YH⁺, and LaH⁺ are 1²Δ_3/2, 1²Σ⁺_1/2, and 1²Δ_3/2 with 55.45, 60.54, and 62.34 kcal/mol bond energies, respectively. The core electron correlation was found to be vital for gaining accurate predictions on the ground and excited state properties of MH⁺. The spin-orbit coupling effects are minor for ScH⁺ but become substantial moving to YH⁺ and LaH⁺. Overall, the results of this work are in good agreement with the limited set of experimental findings of MH⁺ available in the literature and will be of use for future investigations. Furthermore, the theoretical approaches, findings, and trends reported here are expected to aid studies of similar species.