Hi everyone,
I am having trouble with the charge transfer methodology of SAPT implemented in Psi4.
I did calculations with an external decontracted basis set generated by ORCA4 (as discussed here) at SAPT0/TZVP. SAPT0 trends beautifully agree with EDA calculations performed with ADF 2016 (ZORA-BP86-D3/TZ2P).
But I would like to use the charge transfer methodology and it has just worked for one compound so far.
I keep getting “not a number” issues.
This is a typical input:
memory 29 gb
molecule dimer {
0 1
Te 0.00000 -0.00000 3.05800
C 1.47926 1.51846 3.26142
H 1.29403 2.28304 2.51234
H 2.44452 1.05067 3.08494
H 1.43690 1.92765 4.26757
C -1.66964 1.30621 3.26157
H -1.58882 2.08868 2.51242
H -1.68241 1.71746 4.26769
H -2.56342 0.71309 3.08529
--
0 1
I 0.00000 0.00000 0.00000
Cl -0.01030 0.15341 -2.65615
units angstrom
}
set globals {
maxiter 500
relativistic DKH
df_scf_guess false
scf_type direct
# guess gwh
}
basis {
assign oldDKHtzvp
}
df_basis_sapt {
assign oldDKHtzvp-ri
}
energy('sapt0-ct')
And the corresponding output (rather long, some parts suppressed):
...
//>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>//
// SAPT Charge Transfer //
//<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<//
//>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>//
// Dimer Basis SAPT //
//<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<//
*** tstart() called on tarsus.cdi.unifran.br
*** at Thu Apr 13 08:54:39 2017
SAPT0
Ed Hohenstein
6 June 2009
Orbital Information
--------------------------
NSO = 390
NMO = 390
NRI = 1992
NOCC A = 35
NOCC B = 35
FOCC A = 0
FOCC B = 0
NVIR A = 355
NVIR B = 355
Elst10,r = -0.071295970477 [Eh]
Exch10 = 0.101705542455 [Eh]
Exch10 (S^2) = 0.095167728553 [Eh]
Iter Energy [mEh] dE [mEh] Residual Time [s]
1 -339.31922137 339.319221372 86.019096848 1
2 -428.41275195 89.093530581 27.015253835 2
...
EVERYTHING GOES FINE AT THIS POINT
...
CHF Iterations converged
...
Total HF -22.66371892 [mEh] -14.22169893 [kcal/mol] -59.50359402 [kJ/mol]
Total SAPT0 -38.92147546 [mEh] -24.42359561 [kcal/mol] -102.18833383 [kJ/mol]
Special recipe for scaled SAPT0 (see Manual):
Electrostatics sSAPT0 -71.29597048 [mEh] -44.73889879 [kcal/mol] -187.18757049 [kJ/mol]
Exchange sSAPT0 101.70554245 [mEh] 63.82119409 [kcal/mol] 267.02790171 [kJ/mol]
Induction sSAPT0 35.08726412 [mEh] 22.01759156 [kcal/mol] 92.12161194 [kJ/mol]
Dispersion sSAPT0 -15.12940925 [mEh] -9.49384804 [kcal/mol] -39.72226399 [kJ/mol]
Total sSAPT0 50.36742684 [mEh] 31.60603883 [kcal/mol] 132.23967917 [kJ/mol]
--------------------------------------------------------------------------------------------------------
*** tstop() called on tarsus.cdi.unifran.br at Thu Apr 13 08:56:14 2017
Module time:
user time = 633.67 seconds = 10.56 minutes
system time = 37.93 seconds = 0.63 minutes
total time = 95 seconds = 1.58 minutes
Total time:
user time = 4432.58 seconds = 73.88 minutes
system time = 48.71 seconds = 0.81 minutes
total time = 578 seconds = 9.63 minutes
//>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>//
// Monomer Basis SAPT //
//<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<//
*** tstart() called on tarsus.cdi.unifran.br
*** at Thu Apr 13 08:56:14 2017
SAPT0
Ed Hohenstein
6 June 2009
Orbital Information
--------------------------
NSO = 390
NSO A = 230
NSO B = 160
NMO = 390
NMO A = 230
NMO B = 160
NRI = 1992
NOCC A = 35
NOCC B = 35
FOCC A = 0
FOCC B = 0
NVIR A = 195
NVIR B = 125
Elst10,r = -nan [Eh]
Exch10 = -nan [Eh]
Exch10 (S^2) = -nan [Eh]
Iter Energy [mEh] dE [mEh] Residual Time [s]
1 -nan -nan -nan 0
CHF Iterations did not converge
...
EVERY NUMBER NOW IS A NAN
...
Total HF -23.85721138 [mEh] -14.97062679 [kcal/mol] -62.63710849 [kJ/mol]
Total SAPT0 -nan [mEh] -nan [kcal/mol] -nan [kJ/mol]
Special recipe for scaled SAPT0 (see Manual):
Electrostatics sSAPT0 -nan [mEh] -nan [kcal/mol] -nan [kJ/mol]
Exchange sSAPT0 -nan [mEh] -nan [kcal/mol] -nan [kJ/mol]
Induction sSAPT0 -nan [mEh] -nan [kcal/mol] -nan [kJ/mol]
Dispersion sSAPT0 -nan [mEh] -nan [kcal/mol] -nan [kJ/mol]
Total sSAPT0 -nan [mEh] -nan [kcal/mol] -nan [kJ/mol]
--------------------------------------------------------------------------------------------------------
*** tstop() called on tarsus.cdi.unifran.br at Thu Apr 13 08:56:46 2017
Module time:
user time = 232.98 seconds = 3.88 minutes
system time = 9.27 seconds = 0.15 minutes
total time = 32 seconds = 0.53 minutes
Total time:
user time = 4665.56 seconds = 77.76 minutes
system time = 57.98 seconds = 0.97 minutes
total time = 610 seconds = 10.17 minutes
SAPT Charge Transfer Analysis
------------------------------------------------------------------------------------------------
SAPT Induction (Dimer Basis) -56.1102 [mEh] -35.2097 [kcal/mol] -147.3174 [kJ/mol]
SAPT Induction (Monomer Basis) nan [mEh] nan [kcal/mol] nan [kJ/mol]
SAPT Charge Transfer nan [mEh] nan [kcal/mol] nan [kJ/mol]
*** Psi4 exiting successfully. Buy a developer a beer!
But the following input (pretty much the same!) works (it gives me a -30.2 kcal/mol charge transfer term):
memory 29 gb
molecule dimer {
-1 1
I 0.000 0.00000 3.069
--
0 1
I 0.00000 0.00000 0.00000
I 0.000 0.0000 -3.069
units angstrom
}
set globals {
maxiter 500
relativistic DKH
df_scf_guess false
scf_type direct
guess gwh
}
basis {
assign oldDKHtzvp
}
df_basis_sapt {
assign oldDKHtzvp-ri
}
energy('sapt0-ct')
I don’t believe it has something to do with either the initial guess (I have tested both the default, which sometimes gives me convergence problems for the dimer calculation, and gwh, which works fine overall) or the scf_type keyword (I have tested both pk, which sometimes gives me storage problems, and direct).
And since the basis set is the same, I doubt it has something to it too.
It would be very nice if someone could give me advice on this.
Thanks in advance!
All the best,
Felipe