DSD-PBEP86-NL and DOD-PBEP86-NL functionals for noncovalent interactions: Basis set effects and tentative applications to large noncovalent systems

Abstract

Basis set effects on the DSD‐PBEP86‐NL and DOD‐PBEP86‐NL functionals for noncovalent interactions have been extensively studied in this work. The cc‐pVXZ (X = D, T, Q, 5, 6) and augmented aug‐cc‐pVXZ (X = D, T, Q) basis sets are systematically tested without counterpoise (CP) corrections against the well‐known S66 database. Additionally, the basis sets of def2‐TZVPP and def2‐TZVPPD are also examined. Based on our computations, the performances of the aug‐cc‐pVQZ, cc‐pV5Z, and cc‐pV6Z basis sets are very approximate to those obtained with the def2‐QZVP basis set for both the DSD‐PBEP86‐NL and DOD‐PBEP86‐NL functionals. Note that the short‐range attenuation parameters for these two functionals were directly optimized using the def2‐QZVP basis set without CP corrections against the S66 database. Generally speaking, the cc‐pVXZ (X = D, T, Q), aug‐cc‐pVXZ (X = D, T, Q), def2‐TZVPP, and def2‐TZVPPD basis sets favor half CP correction for these two functionals. Nevertheless, the aug‐cc‐pVQZ basis set already performs well without any CP correction, especially for the DOD‐PBEP86‐NL functional. With respect to accuracy and computational cost, the cc‐pVTZ and def2‐TZVPP basis sets with half CP corrections are recommended for these two functionals to evaluate interaction energies of large noncovalent complexes.

Reactivity Trends in the Gas-Phase Addition of Acetylene to the N-Protonated Aryl Radical Cations of Pyridine, Aniline, and Benzonitrile

“…Initial calculations used the M06-2X functional and 6-31G­(2df,p) basis set. Prereactive complexes were recalculated using M06-2X-D3(0)/6-31++G­(2df,p) geometries and DSD-PBEP86-NL/aug-cc-pVQZ energies to better capture long-range charge and electron interactions originating from noncovalent bonding of these complexes . The DSD-PBEP86-NL functional is a double hybrid specifically designed and benchmarked to accurately calculate transition and minimum structures involving such long-range interactions .…”

“…Prereactive complexes were recalculated using M06-2X-D3(0)/6-31++G(2df,p) geometries and DSD-PBEP86-NL/aug-cc-pVQZ energies to better capture long-range charge and electron interactions originating from noncovalent bonding of these complexes. 33 The DSD-PBEP86-NL functional is a double hybrid specifically designed and benchmarked to accurately calculate transition and minimum structures involving such long-range interactions. 34 Calculations for postaddition potential energy schemes were recalculated using the composite G3X-K method, which is designed and benchmarked for accurate transition state energy determination.…”

l-Alanine capping of ZnO nanorods: increased carrier concentration in ZnO/CuI heterojunction diode

“…CCSD(T) calculations were carried out on the M05-2X/TZVP and B2PLYP/def2-TZVP optimized geometries using polarized valence triple-zeta basis set TZVP. 31 Domain based local pair natural orbital CCSD(T) [DLPNO-CCSD(T)] 36 calculations using the extended def2-TZVP 31 basis set, including auxiliary def2-TZVP/J 33 and def2-TZVP/C, 37 were also performed for the alanine–ZnO complex structures. The suitability of the DLPNO-CCSD(T)/def2-TZVP method to predict the relative energies was tested by performing rigorous CCSD(T)/QZVP calculations on the M05-2X/TZVP optimized structures A and B of the alanine–ZnO complex.…”

“…The above basis sets were reported to yield reliable results in quantum chemical studies. 33 In order to accurately predict the relative energies of the alanine-ZnO structures, single-point coupled-cluster calculations with single, double and perturbative triple excitations CCSD(T) 34,35 were performed. This method was considered to be the "Gold Standard" method in quantum chemistry.…”

Reactivity Trends in the Gas Phase Addition of Acetylene to N-protonated Aryl Radical Cations

“…Pre-reactive complexes were recalculated using M06-2X-D3(0)/6-31++G(2df,p) geometries and DSD-PBEP86-NL/aug-cc-pVQZ energies to better capture long-range charge and electron interactions originating from non-covalent bonding of these complexes. 26 The DSD-PBEP86-NL functional is a double hybrid specifically designed and benchmarked to accurately calculate transition and minimum structures involving such long-range interactions. 27 Calculations for post-addition potential energy schemes were recalculated using the composite G3X-K method, which is designed and benchmarked for accurate transition state energy determination.…”