12.4 Locally-Projected SCF Methods

12.4.3 Automated Evaluation of the Basis-Set Superposition Error

(June 30, 2021)

Evaluation of the basis-set superposition error (BSSE) is automated in Q-Chem. To calculate BSSE-corrected binding energies, specify fragments in the $molecule section and set JOBTYPE to BSSE. The BSSE jobs are not limited to the SCF energies and can be evaluated for multi-fragment systems at any level of theory. Q-Chem separates the system into fragments as specified in the $molecule section and performs a series of jobs on (a) each fragment, (b) each fragment with the remaining atoms in the system replaced by the ghost atoms, and (c) on the entire system. Q-Chem saves all calculated energies and prints out the uncorrected and the BSSE corrected binding energies. The $rem_frgm section can be used to control calculations on fragments, however, make sure that the fragments and the entire system are treated equally. It means that all numerical methods and convergence thresholds that affect the final energies (such as SCF_CONVERGENCE, THRESH, PURECART, XC_GRID) should be the same for the fragments and for the entire system. Avoid using $rem_frgm in the BSSE jobs unless absolutely necessary.

Important. It is recommended to include PURECART keyword in all BSSE jobs. GENERAL basis cannot be used for the BSSE calculations in the current implementation. Use MIXED basis instead.

Example 12.7  Evaluation of the BSSE corrected intermolecular interaction energy

$molecule
0 1
--
0 1
O          -0.089523    0.063946    0.086866
H           0.864783    0.058339    0.103755
H          -0.329829    0.979459    0.078369
--
0 1
O           2.632273   -0.313504   -0.750376
H           3.268182   -0.937310   -0.431464
H           2.184198   -0.753305   -1.469059
--
0 1
O           0.475471   -1.428200   -2.307836
H          -0.011373   -0.970411   -1.626285
H           0.151826   -2.317118   -2.289289
$end

$rem
   JOBTYPE         BSSE
   METHOD          MP2
   BASIS           6-31(+,+)G(d,p)
   GEN_SCFMAN      FALSE
$end

View output