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12.5 Locally-Projected SCF and First-Generation ALMO-EDA Methods

12.5.2 Roothaan-Step Corrections and FRAGMO Initial Guess

(September 1, 2024)

Locally-projected SCF cannot quantitatively reproduce the full SCF intermolecular interaction energies for systems with significant charge-transfer between the fragments (e.g., hydrogen bonding energies in water clusters). Good accuracy in the intermolecular binding energies can be achieved if the locally-projected SCF-MI iteration scheme is combined with a charge-transfer perturbative correction. 646 Khaliullin R. Z., Head-Gordon M., Bell A. T.
J. Chem. Phys.
(2006), 124, pp. 204105.
Link
To account for charge-transfer, one diagonalization of the full Fock matrix is performed after the locally-projected SCF equations are converged and the final energy is calculated as infinite-order perturbative correction to the locally-projected SCF energy. This procedure is known as single Roothaan-step (RS) correction. 646 Khaliullin R. Z., Head-Gordon M., Bell A. T.
J. Chem. Phys.
(2006), 124, pp. 204105.
Link
, 779 Liang W. Z., Head-Gordon M.
J. Phys. Chem. A
(2004), 108, pp. 3206.
Link
, 780 Liang W. Z., Head-Gordon M.
J. Chem. Phys.
(2004), 120, pp. 10379.
Link
It is performed if FRGM_LPCORR is set to RS. To speed up evaluation of the charge-transfer correction, second-order perturbative correction to the energy can be evaluated by solving the linearized single-excitation amplitude equations. This algorithm is called the approximate Roothaan-step correction and can be requested by setting FRGM_LPCORR to ARS.

Both ARS and RS corrected energies are very close to the full SCF energy for systems of weakly interacting fragments but are less computationally expensive than the full SCF calculations. To test the accuracy of the ARS and RS methods, the full SCF calculation can be done in the same job with the perturbative correction by setting FRGM_LPCORR to RS_EXACT_SCF or to ARS_EXACT_SCF. It is also possible to evaluate only the full SCF correction by setting FRGM_LPCORR to EXACT_SCF.

The iterative solution of the linear single-excitation amplitude equations in the ARS method is controlled by a set of NVO keywords described below.

Restrictions. Only single point HF and DFT energies can be evaluated with the locally-projected methods. Geometry optimization can be performed using numerical gradients. Wave function correlation methods (MP2, CC, etc..) are not implemented for the absolutely-localized molecular orbitals. SCF_ALGORITHM cannot be set to anything but DIIS, however, all SCF convergence algorithms can be used on isolated fragments (set SCF_ALGORITHM in the $rem_frgm section).

Example 12.7  Comparison between the RS corrected energies and the conventional SCF energies can be made by calculating both energies in a single run.

$molecule
0 1
--
0 1
O      -1.56875     0.11876     0.00000
H      -1.90909    -0.78106     0.00000
H      -0.60363     0.02937     0.00000
--
0 1
O       1.33393    -0.05433     0.00000
H       1.77383     0.32710    -0.76814
H       1.77383     0.32710     0.76814
$end

$rem
   METHOD          HF
   BASIS           AUG-CC-PVTZ
   FRGM_METHOD     GIA
   FRGM_LPCORR     RS_EXACT_SCF
$end

$rem_frgm
   SCF_CONVERGENCE 2
   THRESH          5
$end

For some systems good accuracy for the intermolecular interaction energies can be achieved without converging SCF-MI calculations and applying either the RS or ARS charge-transfer correction directly to the FRAGMO initial guess. Set FRGM_METHOD to NOSCF_RS or NOSCF_ARS to request the single Roothaan correction or approximate Roothaan correction, respectively. To get a somewhat better energy estimate set FRGM_METHOD to NOSCF_DRS and NOSCF_RS_FOCK. In the case of NOSCF_RS_FOCK, the same steps as in the NOSCF_RS method are performed followed by one more Fock build and calculation of the proper SCF energy. In the case of the double Roothaan-step correction, NOSCF_DRS, the same steps as in NOSCF_RS_FOCK are performed followed by one more diagonalization. The final energy in the NOSCF_DRS method is evaluated as a perturbative correction, similar to the single Roothaan-step correction.

Charge-transfer corrections applied directly to the FRAGMO guess are included in Q-Chem to test accuracy and performance of the locally-projected SCF methods. However, for some systems they give a reasonable estimate of the binding energies at a cost of one (or two) SCF step(s).