Post-CCSD(T) Thermochemistry of Chlorine Fluorides as a Challenging Test Case for Evaluating Density Functional Theory and Composite Ab Initio Methods.

Abstract

Quantum chemistry plays a key role in exploring the chemical properties of highly reactive chlorine polyfluoride compounds (ClF_n). Here, we investigate the thermochemical properties of ClF_n species (n=2-6) by means of high-level thermochemical procedures approximating the CCSDT(Q) and CCSDTQ5 energies at the complete basis set limit. We consider total atomization energies (TAEs), Cl-F bond dissociation energies (BDEs), F₂ elimination energies (F₂ elim.), ionization potentials (IPs), and electron affinities (EAs). The TAEs have significant contributions from post-CCSD(T) correlation effects. The higher-order triple excitations, CCSDT-CCSD(T), are negative and amount to -0.338 (ClF₂), -0.727 (ClF₃), -0.903 (ClF₄), -1.335 (ClF₅), and -1.946 (ClF₆) kcal/mol. However, the contributions from quadruple (and, where available, also quintuple) excitations are much larger and positive and amount to +1.335 (ClF₂), +1.387 (ClF₃), +2.367 (ClF₄), +2.399 (ClF₅), and +3.432 (ClF₆) kcal/mol. Thus, the contributions from post-CCSD(T) excitations exceed the threshold of chemical accuracy in nearly all cases. Due to their increasing hyper-valency and multireference character, the ClF_n series provides an interesting and challenging test case for both density functional theory and low-level composite ab initio procedures. Here, we highlight the limitations in achieving overall chemical accuracy across all DFT and most composite ab initio procedures.