Advanced empirical dispersion correction for DFT developed by S.Grimme - the DFT-D3 method.[1,2] Includes modification of the D3 correction for semiempirical methods[3] designed for use with the H4 hydrogen bonding correction. The interface implements also alternative damping functions that make it possible to calculate an empirical replacement of the dispersion terms in DFT-SAPT.[4]
The dispersion3 interface implements multiple damping functions – both the zero and Becke-Johnson damping parametrized by Grimme but also more recent extensions published by others:
It was found that the DZVP-DFT basis exhibits very small basis set superposition error and that DFT-D3 calculations in this basis set are as accurate as calculations in a triple-zeta basis.[9] The D3 correction with various damping functions was reparametrized for this basis and the parameters are provided in Cuby and automatically applied when this basis set is used.
More specifically, the default parameters in Cuby are these obtained in the final parametrization without the 3-body term. The 3-body correction should be used in larger systems; this setup offerrs the best overall accuracy. It is recommended to use the OP, BJ or CSO damping functions, the zero damping performs somewhat worse.
In the paper [9], parameters for B-LYP, B3-LYP, PBE, PBE0 and TPSS were reported. Parameters for additional functionals may be available in Cuby; these are obtained using exactly the same procedure as described in the paper but the testing is left to the user. So far, no other functional beats B-LYP and B3-LYP.
Cuby can be used for performing dispersion-corrected MP2 calculations with the MP2D and SCS-MP2D methods.[10,11] The input, including the parameters, is available below in Examples 3 to 5.
Cuby contains a database of methods for which D3 parameters are available, and assigns these parameters automatically by default. The parameters for DFT with zero and BJ damping were taken from the website of Stefan Grimme and from the source of the dftd3 program available therein. The other parameters come from the respective publications.
The parameters can be divided into following sets:
Method | Damping | Basis sets | Functionals |
---|---|---|---|
DFT | zero | def2-QZVP | b1b95, b1lyp, b1p86, b2gpplyp, b2plyp, b3lyp, b3p86, b3pw91, b971, b972, b97d, b98, bhlyp, blyp, bmk, bop, bp86, bpbe, camb3lyp, dsdblyp, hcth120, hcth407, hiss, hse03, hse06, lcwhpbe, lcwpbe, m05, m052x, m06, m062x, m06hf, m06l, m08hx, m11l, mn15l, mpw1b95, mpw1kcis, mpw1lyp, mpw1pw91, mpw2plyp, mpwb1k, mpwkcis1k, mpwlyp, mpwpw91, n12, o3lyp, olyp, opbe, otpss, pbe, pbe0, pbe1kcis, pbe38, pbeh1pbe, pbehpbe, pbesol, pkzb, ptpss, pw1pw, pw6b95, pw91p86, pwb6k, pwpb95, revpbe, revpbe0, revpbe38, revssb, revtpss, revtpss0, revtpssh, rpbe, rpw86pbe, scan, ssb, thcth, thcthhyb, tpss, tpss0, tpss1kcis, tpssh, wb97x, x3lyp, xlyp |
TZVPP | blyp, bp, b97d, revpbe, pbe, tpss, b3lyp, pbe0, pw6b95, tpss0, b2plyp | ||
DZVP-DFT [9] | blyp, b3lyp, pbe, pbe0, tpss, bp86, b97d | ||
B/J | def2-QZVP | b1b95, b1lyp, b1p86, b2gpplyp, b2plyp, b3lyp, b3p86, b3pw91, b971, b972, b97d, b98, bhlyp, blyp, bmk, bop, bp86, bpbe, bp, camb3lyp, dsdblyp, dsdpbeb95, dsdpbep86, hcth120, hcth407, hiss, hse03, hse06, lcwhpbe, lcwpbe, m11, mn12l, mn12sx, mn15, mpw1b95, mpw1kcis, mpw1pw91, mpw2plyp, mpwb1k, mpwkcis1k, mpwlyp, mpwpw91, n12sx, o3lyp, olyp, opbe, otpss, pbe, pbe0, pbe1kcis, pbe38, pbeh1pbe, pbehpbe, pbesol, ptpss, pw6b95, pw91, pwb6k, pwpb95, revpbe, revpbe0, revpbe38, revssb, revtpss, revtpss0, revtpssh, rpbe, rpw86pbe, scan, sogga11x, ssb, thcth, thcthhyb, tpss, tpss0, tpss1kcis, tpssh, x3lyp, xlyp | |
DZVP-DFT [9] | blyp, b3lyp, pbe, pbe0, tpss, bp86, b97d | ||
CSO [5] | def2-QZVPa | blyp, b3lyp, bp86, pbe0, pbe, pw6b95, tpss, b2plyp | |
DZVP-DFT [9] | blyp, b3lyp, pbe, pbe0, tpss, bp86, b97d | ||
OP [6] | def2-QZVPa | blyp, b3lyp, b97d, b97h, revpbe, revpbe0, tpss, tpssh, ms2, ms2h | |
DZVP-DFT [9] | blyp, b3lyp, pbe, pbe0, tpss, bp86, b97d | ||
HF | zero, B/J | def2-QZVP | |
AM1, PM3, PM6, RM1, OM3 | |||
SCC-DFTB |
a These methods were parametrized with even larger basis set but we list them under def2-QZVP (which is large enough for parctical use) for compatibility with zero and BJ damping
The D3 dispersion can be used as computationally efficient replacement for the dispersion terms in DFT-SAPT.[4] In this case, the damping function is different than the one used in DFT-D. The following input performs such a calculation using the recommended parameters:
job: interaction
interface: dispersion3
d3_damping: TT
d3_hybridization: fixed
d3_a1: -0.436
d3_a2: 4.757
d3_s8: 0.869