Many schemes for decomposing quantum chemical calculations of intermolecular
interaction energies into physically meaningful components can be found in the
literature, but the definition of the charge-transfer (CT) contribution has
proven particularly vexing to define in a satisfactory way and typically
depends strongly on the choice of basis
(2014), 15, pp. 2682. , 928 J. Chem. Theory Comput.
(2015), 11, pp. 528. , 616 J. Chem. Theory Comput.
(2016), 12, pp. 2569. because as virtual orbitals on monomer start to extend significantly over monomer as the basis set approaches completeness, the distinction between polarization (excitations localized on , introduced by the perturbing influence of ) and CT (excitations from to ) becomes blurred. 616 J. Chem. Theory Comput.
(2016), 12, pp. 2569. This ambiguity renders orbital-dependent definitions of CT highly dependent on the choice of atomic orbital basis set. On the other hand, constrained density functional theory (cDFT, Section 5.13), 526 Chem. Rev.
(2012), 112, pp. 321. by means of which a CT-free reference state can be defined based on “promolecule” densities, affords a definition of CT that is scarcely dependent on the basis set and is in accord with chemical intuition in simple cases. 616 J. Chem. Theory Comput.
(2016), 12, pp. 2569.
For intermolecular interactions, the cDFT definition of CT can be combined with
a definition of the remaining components of the interaction energy
(electrostatics, induction, Pauli repulsion, and van der Waals interactions)
based on symmetry-adapted perturbation theory (SAPT, Section 12.13).
In traditional SAPT, the CT interaction energy resides within the induction
energy (also known as the polarization energy), which is therefore itself
highly dependent upon the basis set. However, using cDFT to define the CT
component and subtracting this out of the SAPT induction energy, both the CT
and the remaining induction energies are largely independent of basis
J. Chem. Theory Comput.
(2016), 12, pp. 2569. SAPT/cDFT therefore provides a stable and physically-motivated energy decomposition.
While the cDFT definition of CT exhibits only a very mild basis-set dependence, its quantitative details
do depend upon how the charge constraints in cDFT are defined relative to
fragment populations (Section 5.13). For SAPT/cDFT,
both atomic Becke
J. Chem. Phys.
(1988), 88, pp. 2547. and fragment-based Hirshfeld 928 J. Chem. Theory Comput.
(2015), 11, pp. 528. (FBH) charge partitioning methods are available. The former involves construction of atomic cell functions that amount to smoothed Voronoi polyhedra centered about each atom. A switching function defines the atomic cell of atom , and falls rapidly from near the nucleus for atom , to near any other nucleus. Becke 74 J. Chem. Phys.
(1988), 88, pp. 2547. defined atomic cell functions that are products of switching functions and that can be used to define the cDFT integration weight for monomer by summing over atoms :
The sum in the denominator runs over all atoms in both monomers, and .
Becke populations, however, are rooted in a somewhat arbitrarily-defined topology, based
in part on assumed atomic radii, whereas FBH partitioning
derives physical significance from isolated monomer densities
The cDFT weight function for monomer is
J. Chem. Theory Comput.
(2015), 11, pp. 528.
which is the same “stockholder” scheme used to define atomic Hirshfeld populations (Section 10.2.1), but applied here to the entire monomer. In the language of cDFT, the denominator in this expression would be called the promolecule density for the dimer . In order to set a molecular fragment constraint, simply retain the existing syntax in the $cdft input section (as described in Section 5.13) and specify all atoms within a given molecular fragment.
Due to the fact that Becke populations are rooted in a topological scheme based in part on assumed atomic
radii, it is highly recommended that if CDFT_POP is set to BECKE, the rem variable
BECKE_SHIFT should be set to use either the
empirically derived Bragg-Slater radii
J. Chem. Phys.
(1964), 41, pp. 3199. or ab initio derived radii based on the universal density criterion 828 J. Comput. Chem.
(1995), 16, pp. 133. (see Section 10.2.1 for more details). Using the UNSHIFTED (default) scheme can lead to highly unphysical results, including a charge-transfer vector that points in the opposite direction.
To perform SAPT/cDFT energy decomposition analysis, the user must request a normal SAPT or XSAPT calculation (JOBTYPE = XSAPT), and in addition specify the keyword CDFT-EDA in the $sapt input section. Users of this method are asked to cite Ref. 616.
As shown in the example below, a $cdft input section is also required in order to specify the
monomer charges and spins for the cDFT part of the calculation.
The CDFT_POP variable may be set (in the $rem section) in order to specify
the electron-counting mechanism for cDFT. The options are either to use atomic Becke populations
(as in traditional cDFT calculations
(2012), 112, pp. 321. ), summed up for each monomer, or else fragment-based Hirshfeld partitioning in which promolecule densities for the monomers are used to obtain a whole-molecule version of Hirshfeld atomic charges.
$molecule 0 1 -- 0 1 O -0.702196054 -0.056060256 0.009942262 H -1.022193224 0.846775782 -0.011488714 H 0.257521062 0.042121496 0.005218999 -- 0 1 O 2.220871067 0.026716792 0.000620476 H 2.597492682 -0.411663274 0.766744858 H 2.593135384 -0.449496183 -0.744782026 $end $rem JOBTYPE XSAPT EXCHANGE gen BASIS aug-cc-pvdz LRC_DFT true CDFT_POP FBH ! Fragment-Based Hirshfeld charge partitioning $end $xpol embed none print 3 dft-lrc $end $sapt algorithm AO Dispersion aiD3 order 2 basis dimer cdft-eda print 3 $end $xc_functional x wPBE 1.0 c PBE 1.0 $end $lrc_omega 500 500 $end $cdft 0 1 1 3 0 1 1 3 s $end