The MC-DFT approach including the SCS-MP2 energies to the new minnesota-type functionals

Abstract

We have applied the multicoefficient density functional theory (MC-DFT) to four recent Minnesota functionals, including M06-2X, M08-HX, M11, and MN12-SX on the performance of thermochemical kinetics. The results indicated that the accuracy can be improved significantly using more than one basis set. We further included the SCS-MP2 energies into MC-DFT, and the resulting mean unsigned errors (MUEs) decreased by approximately 0.3 kcal/mol for the most accurate basis set combinations. The M06-2X functional with the simple [6-311+G(d,p)/6-311+G(2d,2p)] combination gave the best performance/cost ratios for the MC-DFT and MC-SCS-MP2|MC-DFT methods with MUE of 1.58 and 1.22 kcal/mol, respectively.

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

“…We have shown in our previous work that MC‐DFT methods can provide accurate prediction on the thermochemical kinetics data at relatively low computational cost. [ 47–49 ] In the current study, we have tested the basis set combinations apdz/aptz and pdz/apdz/aptz using the functionals MPW1B95, MPW1PW91, B98, B3LYP, B2GP‐PLYP, DSD‐BLYP, and BMK. The energies were computed according to Equations ) and ().…”

“…It has been shown to be a very economical way to achieve good accuracy on thermochemical kinetics. [ 49,50 ] In the current study, we have combined the hybrid functionals MPW1B95, MPW1PW91, B98, B3LYP, B2GP‐PLYP, DSD‐BLYP, and BMK using the aptz basis set with MP2 calculation using the pdz, apdz, ptz, and aptz basis sets. The energies were computed according to Equation ).…”

“…The MC‐DFT method [ 47–49 ] uses more than one basis set (B1, B2, B3, etc.) to extrapolate the Born‐Oppenheimer energies according to the following formulas: where c 1 and c 2 are empirical coefficients to be determined by minimizing the mean unsigned errors (MUEs) against the standard NGBE or MGAE109 database.…”

“…Of course, many interesting noble‐gas‐containing cations have been observed or theoretically predicted, [ 34,39–46 ] which will be included in future studies. In addition, to test 16 frequently used wavefunction‐based and density functional theories (DFTs) with different basis sets, we have also developed the new multi‐coefficient density functional theory (MC‐DFT, ie, DFT methods using more than one basis set) [ 47–49 ] and the doubly hybrid (DH; ie, DFT + MP2) methods [ 49,50 ] for predicting the bond energies of noble‐gas‐containing molecules and other main‐group molecules. The new database and benchmark results would benefit future theoretical prediction and experimental exploration in the field of noble gas chemistry.…”

Theoretical studies of organotin(IV) complexes derived from ONO-donor type schiff base ligands

“…This functional is stated to perform well for the investigation of non-covalent interactions [44,49] and charge transfer excitation calculations [44,47], and gives accurate geometries for some ruthenium based transition metal compounds [54]. MN-12SX was benchmarked in some recent studies [55,56] as including thermo-chemistry and intermolecular interactions, and seems a very competitive functional.…”