wB97X-D4BJ missing D4 gradients?

Udo · December 25, 2022, 8:49am

Hi there,

I just ran some calculation with the latest 1.7 (Git: Rev {HEAD} 6ce35a5) release (great work by the way), and it seems that something like

grad, wfn = gradient(‘wB97X-D4BJ/def2-TZVP’, return_wfn=True, dertype=‘gradient’)

does not return a proper DFT + D4 gradient (only DFT).

However,

grad, wfn = gradient(‘wB97X-D3BJ/def2-TZVP’, return_wfn=True, dertype=‘gradient’)

is doing so.

Best,

Udo

jmisiewicz · December 26, 2022, 3:53am

Please post the results of conda list, so we know which program you’re using to get the dispersion correction. The logic involving dispersion programs changed towards the end of the 1.7 development cycle, and this bug is likely a consequence of that…

Udo · December 26, 2022, 4:41am

I am using the latest 1.7 psi4conda install:

A quick guess from my side: maybe it is just a unit conversion issue relevant for the gradient only … ?

packages in environment at /home/udo/psi4conda:

jmisiewicz · December 26, 2022, 12:03pm

@loriab, I think this one is for you.

hokru · December 27, 2022, 12:12pm

There are, to my knowledge, at least 2 versions for wB97X-D4. One for the original wB97X plus added D4 and one where the V in wB97X-V is replaced by D4. Which one was your target?

Udo · December 28, 2022, 2:28am

The one that gives a lower overall error on the GMTKN55 data set, which in my understanding is the latter. Like the “wB97X-D3BJ” definition in psi4 , that returns

wB97X-V - vdW_DFT + D3BJ

So to be consistent with that definition, one might assume that “wB97X-D4BJ” is doing the same computation with D3BJ replaced by D4BJ?

hokru · December 28, 2022, 9:32am

Unfortunately psi4 automatically combines the old wB97X with added D4. Grimme made parameters for it. I added Goerigk’s -D3 versions for the (w)B97X/M-V functionals manually but not yet the -D4 variants. It requires manually definition like so:

github.com

psi4/psi4/blob/master/psi4/driver/procrouting/dft/hyb_functionals.py#L553-L574


      
          funcs.append({
              "name": "wB97X-D3BJ",
              "xc_functionals": {
                  "HYB_GGA_XC_WB97X_V": {}
              },
              "dispersion": {
                  "nlc": False,
                  "type": "d3bj2b",
                  "citation": '    A. Najib, L. Goerigk, J. Comput. Theory Chem.,14 5725, 2018\n',
                  "params": {
                      's6': 1.000,
                      's8': 0.2641,
                      'a1': 0.0000,
                      'a2': 5.4959
                  },
              },
              "description":
              '    wB97X-V with D3(BJ) instead of VV10 dispersion \n',
              "citation":
              '    A. Najib, L. Goerigk, J. Comput. Theory Chem., 14 5725, 2018)\n' +

This file has been truncated. show original

You can add the functional dictionary directly into the input file: DFT: Density Functional Theory

Btw, I could not reproduce your error with my development version.

# molecule name is "s4di" in this example
gradD4, wfn1 = gradient('wB97X-D4BJ', return_wfn=True, dertype='gradient',molecule=s4di)
grad, wfn2 = gradient('wB97X', return_wfn=True, dertype='gradient',molecule=s4di)
E, G = s4di.run_dftd4('wB97X', 'd4bj')
d_grad=grad.np-gradD4.np
compare_values(-G, d_grad, 8, 'D4 grad test1')

Udo · December 28, 2022, 1:09pm

Thanks a lot for the working resolution provided.

To put things into a somewhat broader perspective:

Our statistical analysis revealed, that ORCA:wB97X-D4, ORCA:wB97X-D3BJ and PSI4:wB97X-D3BJ all give very similar results for the gradient vectors, but PSI4:wB97X-D4 does not, so the latter gradient vector is always a clear outlier in the overall set. The source of this is now sufficiently explained with the above comments.

I also assume from the above that ORCA has implemented some kind of consistent D4 model in combination with wB97X-V that can be directly used (and trusted), even if there is no published version by Grimme yet.

For current users, that do not perform (or do not want to perform) quantitative inter-QC-code comparison and just simply type the respective keywords the discussed inconsistency might be a source of systematic error in their results.

hokru · December 28, 2022, 1:39pm

Afaik, Goerigk is ORCA developer and put his D3/D4 versions into ORCA first. So that’s the reference for those functionals. We are catching up with the implementations.

I am not sure how ORCA implements D4 but i do expect it links Grimme’s code with a library rather than a re-implementation. That should agree with what we do (using a python API to the library).

That 2 different functional names have different parameters of the functional and/or dispersion correction is not the first time
Not sure what the solution on psi4’s side could be. Goerigk’s version is preferred i think and will get into psi4.

Udo · December 29, 2022, 6:31am

Thanks again for the additional information.

I see your point of certainly having some ambiguity here with respect to the proper naming/selection of the DFT functional and the corresponding D3/D4 dispersion model.

wB97X-D4BJ missing D4 gradients?

packages in environment at /home/udo/psi4conda:

Name Version Build Channel