Accurate Treatment of Large Supramolecular Complexes by Double-Hybrid Density Functionals Coupled with Nonlocal van der Waals Corrections

Abstract

In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL), as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly-interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogenous set of reference interaction energies were computed for the supramolecular complexes constituting the L7 and SL12 data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (especially for the S12L set) have been determining for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 This is a previous version of the article published in Journal of Chemical Theory and Computation. 2015, 11(3): 932-939. doi:10.1021/acs.jctc.5b00002 2 evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy.Overall, the nonlocal van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly-bonded supramolecular systems.

Partnering dispersion corrections with modern parameter-free double-hybrid density functionals

“…Note that previous results from literature provided a MAD of 11.8 kcal/mol for the B2-PLYP method [68], with the def2-TZVP basis set but counterpoise corrected, and thus much higher than that obtained here. Interestingly, the use of the D3(BJ) correction leads now to a very low MSD (MAD) of only 1.3 (1.9) kcal/mol, and very close to that provided by other dispersion-corrected DH methods (e.g.…”

“…These systems are known to push theoretical methods to their accuracy limit [68], as it is also evidenced by current difficulties to obtain benchmark results at the Complete Basis Set (CBS) limit and with a method as accurate as CCSD(T). This issue was recently solved by resorting to the domain-based pair natural orbital DLPNO-CCSD(T) approach at the CBS limit, offering nearly CCSD(T) accuracy at a reduced computational cost [69], and thus avoiding the use of previously published QCISD(T)/CBS values [67].…”

Comparison of one‐parameter and linearly scaled one‐parameter double‐hybrid density functionals for noncovalent interactions

“…As shown in Table , the MADs of our optimized 1DH‐DFs and LS1DH‐DFs for noncovalent interactions against the L7 database are within 1.10–1.68 kcal/mol. Note that the recently revised reference interaction energies at the DLPNO‐CCSD(T)/CBS level of theory are utilized in Table . The performances of the 1DH‐PWB95‐NC and LS1DH‐PWB95‐NC functionals are approximate to those of the revPBE0‐DH‐NL and B2PLYP‐NL functionals .…”

“…Note that the recently revised reference interaction energies at the DLPNO‐CCSD(T)/CBS level of theory are utilized in Table . The performances of the 1DH‐PWB95‐NC and LS1DH‐PWB95‐NC functionals are approximate to those of the revPBE0‐DH‐NL and B2PLYP‐NL functionals . Compared with the revPBE0‐DH‐NL + E ABC , B2PLYP‐NL + E ABC , and B2PLYP‐D3(BJ) functionals, our optimized 1DH‐DFs and LS1DH‐DFs for noncovalent interactions perform worse on the L7 database.…”

Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions

“…The VV10NL correlation energy functional was based on electron density, and only a short‐range attenuation parameter needed to be fitted in general. The VV10NL correlation energy functional was widely used with different kinds of density functionals, and the density functionals including this nonlocal correlation energy functional showed very good performances on noncovalent interactions …”