Relativistic GVVPT2 Multireference Perturbation Theory Description of the Electronic States of Y₂ and Tc₂

Abstract

The multireference generalized Van Vleck second-order perturbation theory (GVVPT2) method is used to describe full potential energy curves (PECs) of low-lying states of second-row transition metal dimers Y₂ and Tc₂, with scalar relativity included via the spin-free exact two-component (sf-X2C) Hamiltonian. Chemically motivated incomplete model spaces, of the style previously shown to describe complicated first-row transition metal diatoms well, were used and again shown to be effective. The studied states include the previously uncharacterized 2¹Σ_g⁺ and 3¹Σ_g⁺ PECs of Y₂. These states, together with 1¹Σ_g⁺, are relevant to discussion of controversial results in the literature that suggest dissociation asymptotes that violate the noncrossing rule. The ground state of Y₂ was found to be X⁵Σ_u^– (similar to Sc₂) with bond length <i>R</i>_e = 2.80 Å, binding energy <i>D</i>_e = 3.12 eV, and harmonic frequency ω_e = 287.2 cm^–1, whereas the lowest 1¹Σ_g⁺ state of Y₂ was found to lie 0.67 eV above the quintet ground state and had spectroscopic constants <i>R</i>_e = 3.21 Å, <i>D</i>_e = 0.91 eV, and ω_e = 140.0 cm^–1. Calculations performed on Tc₂ include study of the previously uncharacterized relatively low-lying 1⁵Σ_g⁺ and 1⁹Σ_g⁺ states (i.e., 0.70 and 1.84 eV above 1¹Σ_g⁺, respectively). The ground state of Tc₂ was found to be X³Σ_g^– with <i>R</i>_e = 2.13 Å, <i>D</i>_e = 3.50 eV, and ω_e = 336.6 cm^–1 (for the most stable isotope, Tc-98) whereas the lowest ¹Σ_g⁺ state, generally accepted to be the ground state symmetry for isovalent Mn₂ and Re₂, was found to lie 0.47 eV above the X³Σ_g^– state of Tc₂. The results broaden the range of demonstrated applicability of the GVVPT2 method