A new database and benchmark of the bond energies of noble‐gas‐containing molecules

Abstract

AbstractWe have developed a new database of structures and bond energies of 59 noble‐gas‐containing molecules. The structures were calculated by CCSD(T)/aug‐cc‐pVTZ methods and the bond energies were obtained using the CCSD(T)/complete basis set method. Many wavefunction‐based and density functional theory methods have been benchmarked against the 59 accurate bond energies. Our results show that the MPW1B95, B2GP‐PLYP, and DSD‐BLYP functionals with the aug‐cc‐pVTZ basis set excel in predicting the bond energies of noble‐gas molecules with mean unsigned errors (MUEs) of 2.0 to 2.1 kcal/mol. When combinations of Dunning's basis sets are used, the MPW1B95, B2GP‐PLYP, DSD‐BLYP, and BMK functionals give significantly lower MUEs of 1.6 to 1.9 kcal/mol. Doubly hybrid methods using B2GP‐PLYP and DSD‐BLYP functionals and MP2 calculation also provide satisfactory accuracy with MUEs of 1.4 to 1.5 kcal/mol. If the Ng bond energies and the total atomization energies of a group of 109 main‐group molecules are considered at the same time, the MPW1B95/aug‐cc‐pVTZ single‐level method (MUE = 2.7 kcal/mol) and the B2GP‐PLYP and DSD‐PLYP functionals with combinations of basis sets or using the doubly hybrid method (MUEs = 1.9‐2.2 kcal/mol) give the overall best result.