Is near-“spectroscopic accuracy” possible for heavy atoms and coupled cluster theory? An investigation of the first ionization potentials of the atoms Ga–Kr

Abstract

Recent developments in ab initio coupled cluster (CC) theory and correlation consistent basis sets have ushered in an era of unprecedented accuracy when studying the spectroscopy and thermodynamics of molecules containing main group elements. These same developments have recently seen application to heavier inorganic or transition metal-containing species. The present work benchmarks conventional single reference coupled cluster theory (up to full configuration interaction for valence electron correlation and coupled cluster with up to full pentuple excitations (CCSDTQP) for core-valence correlation) and explicitly correlated coupled cluster methods [CC with single, double, and perturbative triple substitutions (CCSD(T)-F12)] for the atomic ionization potentials of the six 4p elements (Ga-Kr), a property with experimental error bars no greater than a few cm(-1). When second-order spin orbit coupling effects are included, a composite methodology based on CCSD(T) calculations yielded a mean signed error of just -0.039 kcal mol(-1) and a mean unsigned error of 0.043 kcal mol(-1). Inclusion of post-CCSD(T) correlation corrections reduced both of these values to -0.008 kcal mol(-1) and 0.025 kcal mol(-1), respectively, with the latter corresponding to an average error of just 9 cm(-1). The maximum signed error in the latter scheme was just -0.043 kcal mol(-1) (15 cm(-1)).