The accurate wavefunction of the active space of the rhenium dimer resolved using the ab initio Brueckner coupled-cluster method

Abstract

Rhenium is a unique metal in the 5d-series of transition metals having the highest boiling point in the periodic table. It is also known to exist in poly-coordinated states with other rhenium atoms. Based on the existence of strikingly unusual states of elements in astrophysical bodies of nebulae, interstellar debris, exoplanets and other part of the universe, a set of ab initio calculations of the rhenium dimer has been conducted to provide detailed description of its molecular properties that are applicable to the astrochemical research. Ab initio calculations and NBO analysis revealed that rhenium forms quintuple bond in its diatomic state and that it displays preferred state of triplet configuration with high-lying electrons. Calculations also revealed that the two states of rhenium dimer vary in their bonding nature. The singlet spin space is composed of five single bonds, while the triplet state comprises four bonds and two additional lone pairs. Interestingly, while these two states vary in subdivision of electrons at the highest d-level, they share the same frequencies while having different zero-point energies. The calculations reveal intrinsic synergy between the atoms composed of natural bond orbitals, the bonding pattern and the thermochemical properties of Re2, all features being of significant importance to physical and chemical sciences.