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

Abstract

We have developed a new database of structures and bond energies of 59 noblegas-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. K E Y W O R D S doubly hybrid method, multi-coefficient density functional theory, noble gas chemistry, noblegas molecule, noble gas bond energies

Long‐bonding and effects of carbon hybridization on the bonding of MNgC compounds (M = Cu, Ag, Au)

“…For AuNgCCH the bond lengths of DSD‐BLYP‐D3 and MPW1B95 are close to the CCSD(T) results, but the B3LYP‐D3 bond lengths are generally larger than the CCSD(T) results. A benchmark study of DFT methods on predicting bond energy and bond length of noble‐gas containing molecules shows that the methods DSD‐BLYP/aug‐cc‐pVTZ and MPW1B95/6‐311+G(2df, 2pd) are the most recommended methods for both bond energy and bond length based on the reference results of the CCSD(T)/aug‐cc‐pVTZ method [38, 39]. It seems that the structural parameters of DSD‐BLYP‐D3 are more reliable than those of the other methods used in this work.…”

“…It has been shown that for noble gases compounds MPW1B95/6-311+G(2df, 2pd) and DSD-BLYP/aug-cc-pVTZ are preferred, as CCSD(T)/augcc-pVTZ taken as reference [38,39]. So in this work we performed geometry optimizations and frequency calculations using the MPW1B95 [40], B3LYP-D3 [41,42], MP2 [43,44], and DSD-BLYP-D3 [42,45] methods with Dunning's augmented correlation consistent basis sets aug-cc-pVTZ [46][47][48].…”

Theoretical prediction of donor–acceptor type novel complexes with strong noble gas–boron covalent bond

“…38,39 Consequently, these compounds are extremely important due to their wide range of applications in various fields of chemistry. 40–65 The electron deficiency of the boron compounds and the affinity of Ng atoms to strongly bind with electrophiles prompted the exploration of various donor–acceptor type compounds containing the Ng–B bonding motif, 66–75 e.g. , the recent theoretical investigation of NgBO + (Ng = He–Rn) 76 ions with strong Ng–B covalent bonding by our group.…”

Stability-Order Reversal in FSiY and FYSi (Y = N and P) Molecules after the Insertion of a Noble Gas Atom

“…The domain of the noble gas chemistry has expanded after the discovery of the first stable molecule of argon (HArF) characterized using the infrared absorption spectroscopic technique supported by ab initio quantum chemical calculations by Räsänen and co-workers in 2000. , Following this revolutionized work, various noble gas-containing neutral and charged chemical compounds − ,− have been predicted theoretically and prepared via suitable experimental techniques. In general, these metastable compounds are obtained by inserting a noble gas atom into a stable molecule having either astronomical significance such as HCO + , HCS + , and HN 2 + or environmental importance such as HOX (X = F, Cl, and Br) and H 3 O + .…”