The original implementation of the projector-based embedding in Q-Chem was through the “EmbedMan” module, which was based on the old SCF module that is no longer the default. This implementation applies a level-shift projection operator to enforce the orthogonality between orbitals belonging to fragments 1 and 2. For the 1-in-2 case, the Fock matrix can be written as
| (11.91) |
where is the level-shift projection operator constructed as:
| (11.92) |
where is the localized density of fragment 2, and is the AO overlap matrix. Upon convergence, an energy correction term is added to the final energy to account for the level-shift projection operator contribution to the Fock matrix energy. The correction term is calculated as the following:
| (11.93) |
Once the KS-DFT energy of fragment 1-in-2 is computed, a post-SCF method can be applied to this converged density to obtain the high-level QM additive energy of fragment 1. The same procedure can be repeated for fragment 2-in-1, without continuing to a post-SCF method to yield the low-level QM additive energy of the fragment 2. These energies are then summed to yield the total energy.
To run an embedding calculation through the “EmbedMan” module, one must split the super-molecular system into two fragments indexed 1 and 2, and set EMBEDMAN to 1. This is done through the standard Q-Chem fragment input syntax. Two separate jobs must be run to find the total energy of fragment 1-in-2 at a high level QM theory, and fragment 2-in-1 at a low level QM theory. The order of the fragments in the $molecule section determines which fragment will undergo the high level QM. The user must submit a separate job for the 2-in-1 low-level QM calculation, with the order of the fragments reversed and EMBED_THEORY set to 0, which is the default value. The user must then add the final energies of the calculations to determine the total QM/QM embedded energy.
For the current Q-Chem implementation of density embedding, it is necessary to specify the basis as MIXED, which requires to define the basis for each individual atom. When using CCSD(T), one should specify CCMAN2 as TRUE, for Q-Chem’s most updated coupled-cluster code. The current implementation of density embedding only works in combination with the following settings: SCF_ALGORITHM = DIIS, INCFOCK = 0, and PURECART = 222. It is also recommended that users disable symmetry for calculations with SYMMETRY = FALSE, and SYM_IGNORE = TRUE. Refer to the sample input for correct job settings.
EMBEDMAN
Turns density embedding on.
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
0
Do not use density embedding.
1
Turn on density embedding.
RECOMMENDATION:
Use EMBEDMAN for QM/QM density embedded calculations.
EMBED_THEORY
Specifies post-DFT method performed on fragment one.
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
0
No post HF method, only DFT on fragment one.
1
Perform CCSD(T) calculation on fragment one.
2
Perform MP2 calculation on fragment one.
RECOMMENDATION:
This should be 1 or 2 for the high-level QM calculation of fragment
1-in-2, and 0 for fragment 2-in-1 low-level QM calculation.
EMBED_MU
Specifies exponent value of projection operator scaling factor, [Eq.
(11.91) and (11.93)].
TYPE:
INTEGER
DEFAULT:
7
OPTIONS:
n
.
RECOMMENDATION:
Values of 2 - 7 are recommended. A higher value of leads to better
orthogonality of the fragment MOs but introduces numerical
noise. results in non-additive terms becoming too large. Energy
corrections are fairly insensitive to changes in within the range of
.
EMBED_THRESH
Specifies threshold cutoff for AO contribution used to determine which MOs
belong to which fragments
TYPE:
INTEGER
DEFAULT:
500
OPTIONS:
n
Threshold
RECOMMENDATION:
Acceptable values range from 0 to 1000. Should only need to be tuned for
non-highly localized MOs
Example 11.31 Input for a MP2/PBE density embedding calculation of He-in-HF. The sum of the final energies for these two jobs will yield the total QM/QM energy.
$molecule 0 1 -- 0 1 He -4.63032 2.10289 -1.62399 -- 0 1 F -8.00612 1.74605 -1.25581 H -7.40964 1.84462 -0.47756 $end $rem EXCHANGE PBE CORRELATION PBE BASIS mixed ! Must specify basis sets per atom in $basis section below PURECART 222 MAX_SCF_CYCLES 100 SCF_ALGORITHM DIIS INCFOCK 0 SYMMETRY false SYM_IGNORE true CC_SYMMETRY false EMBEDMAN 1 ! Turning density embedding on EMBED_THEORY 2 ! Running MP2 on fragment 1 in 2, or He in FH EMBED_MU 7 ! Default value EMBED_THRESH 500 ! Default value for assigning MOs to fragments $end $basis he 1 6-31G **** f 2 6-31G **** h 3 6-31G **** $end @@@ $molecule 0 1 -- 0 1 F -8.00612 1.74605 -1.25581 H -7.40964 1.84462 -0.47756 -- 0 1 He -4.63032 2.10289 -1.62399 $end $rem EXCHANGE PBE CORRELATION PBE BASIS mixed PURECART 222 MAXSCF 100 SCF_ALGORITHM DIIS INCFOCK 0 SYMMETRY false SYM_IGNORE true EMBEDMAN 1 EMBED_THEORY 0 ! There will be no post-DFT calculations for HF-in-He $end $basis f 1 6-31G **** h 2 6-31G **** he 3 6-31G **** $end