The correlation factor model for the

exchange-correlation energy and its

application to transition metal compounds

Cite as: J. Chem. Phys. 150, 084107 (2019); https://doi.org/10.1063/1.5083840

Submitted: 30 November 2018 . Accepted: 06 February 2019 . Published Online: 26 February 2019

Rodrigo Wang, Yongxi Zhou, and Matthias Ernzerhof

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J. Chem. Phys. 150, 084107 (2019); https://doi.org/10.1063/1.5083840 150, 084107

© 2019 Author(s).
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The correlation factor model

for the exchange-correlation energy
and its application to transition
metal compounds
Cite as: J. Chem. Phys. 150, 084107 (2019); doi: 10.1063/1.5083840
Submitted: 30 November 2018 • Accepted: 6 February 2019 •
Published Online: 26 February 2019

Rodrigo Wang, Yongxi Zhou, and Matthias Ernzerhof a)

AFFILIATIONS
Département de Chimie, Université de Montréal, C.P. 6128 Succursale A, Montréal, Québec H3C 3J7, Canada

a)
Author to whom correspondence should be addressed: Matthias.Ernzerhof@UMontreal.ca.

ABSTRACT
In the recently developed correlation factor (CF) model [Precechtelova et al., J. Chem. Phys. 143, 144102 (2015)], the exchange-
correlation (XC) hole is approximated. Since various constraints satisfied by the XC-hole are known, approximations to it can be
designed which largely avoid empirical adjustments. In the CF approach, the XC-hole is written as a product of an exchange hole
times a CF. An important constraint satisfied by the CF model is that it correctly reproduces the exact exchange energy in the
high density limit. This is achieved by employing the exact exchange-energy per particle (X (r)) as an input variable, i.e., the CF
model builds on exact exchange. Variations of the initial CF model are proposed which ensure that the exact answer is obtained
in the homogeneous limit. Furthermore, we apply a correction to the depth of the XC-hole that is designed to capture strong
correlation. EC functionals that build on exact exchange, such as hybrids, often fail for systems that exhibit sizeable electron
correlation. Despite this fact and despite the reduction of empiricism to a single parameter within CF, accurate atomization
energies are obtained for strongly-correlated transition metal compounds. The CF model significantly improves upon widely
used functionals such as Perdew-Burke-Ernzerhof (PBE), PBE hybrid, and Tao-Perdew-Staroverov-Scuseria (TPSS).
Published under license by AIP Publishing. https://doi.org/10.1063/1.5083840

I. INTRODUCTION the XC-hole starting from an X-hole model ρX (r, u) which

Many improvements to existing exchange-correlation
(XC) density functionals (EXC [ρ]) can be obtained by replac-
ing difficult-to-approximate contributions to the exchange-
correlation (XC) energy EXC [ρ] through wave function calcula-
tions. Hybrid functionals1–5 are the standard example for this
strategy, the X-energy is evaluated exactly and ad-mixed to a
density functional approximation of EXC [ρ]. Non-withstanding
the enormous success of this approach, it is plagued by vari-
ous shortcomings, some of which are rooted in the fact that a
constant fraction of exact exchange is used and thus, the cor-
rect answer is not recovered if EC is negligible and EXC reduces
to EX . Various strategies have been employed to address this
problem.6–13 In recent years,14–16 we developed an approxi-
mation that is characterized by the fact that it approximates
reproduces the exact X-energy per particle. Thus, the exact
X-energy per particle  X (r) is employed as an input variable.
Instead of an additive correlation term, ρX (r, u) is then multi-
plied by a correlation factor (CF) that turns the X-hole into an
XC-hole,
ρXC (r, u) = fC (r, u)ρX (r, u).
The challenges of this approach are the construction of the
model X-hole ρX (r, u) and the CF f C (r, u). Additionally, in the
construction of approximations, we aim at reducing empiri-
cism to a minimum; by using known exact constraints on the
XC-hole, we can avoid empirical parameters almost entirely.
In previous articles about the CF model (CFM),14–16 we
advanced this approach to the point where it is comparable to

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conventional global hybrids, e.g., PBE hybrid,5 for atomization At a given position r, ρXC (r, u) is a function of the electron-
energies. electron separation u and it describes the reduction in the
In the present work, we present a new implementation electron density due to exchange-correlation effects. Approx-
of the CFM in which  X (r) is calculated exactly (within a imations to ρXC (r, u) are of interest in themselves; they are
given basis set) without invoking the resolution of the iden- often the starting point for various developments in DFT, such
tity approximation.17,18 The calculation of  X (r) is described in as range-separation methods.31–39
the Appendix. The previously presented CFM is then further As already described, our ansatz for ρXC (r, u) follows
explored in various ways. The original CFM does not recover the CF decomposition where ρXC (r, u) is expressed as an
the correct EXC of the homogeneous electron gas (HEG). approximate X-hole ρX (r, u) times the CF f C (r, u),
Here we develop a modification of the CFM that does rec- CF
tify this shortcoming. Furthermore, strong correlation is a ρXC (r, u) = fC (r, u)ρX (r, u). (2)
problem that presently receives attention and there are sig- The CFs that we employ in our work are determined using
nificant advances made in the development of functionals various conditions as explained below in Sec. II D, after we
that can cope with strong correlation.10,11,19 We explore the discussed details about ρX (r, u).
potential of the CF approach to describe strongly-correlated
systems and we consider transition metal (TM) dimers to A. The exchange-hole models employed
benchmark various CFMs. Recently, Furche and Perdew20 in the CF approach
assessed the performance of semilocal and hybrid density
functionals to describe TM compounds. They demonstrated The straightforward procedure would be to calculate
that the generalized gradient approximation (GGA), more the exact X-hole and build the correlation factor of Eq. (2)
specifically PBE,21 BP86,22,23 and the meta-GGA (MGGA) Tao- for it; instead we employ a simple model hole which has a
Perdew-Staroverov-Scuseria (TPSS)24 have a better cost- predictable, non-oscillatory shape. The exact X-hole can be
per-performance than hybrid functionals (B3LYP,22,25 TPSS rather complex, greatly complicating the task of designing
hybrid26,27 ). Hybrid functionals underestimate static corre- a compatible correlation factor. The X-hole model that we
lation. In contrast, semi-local functionals often overestimate employ is the generalized (G) version of the Becke-Roussel
static correlation and consequently they tend to overesti- X-hole model (BR),40
mate the bond energies, but to a lesser extent than hybrids GBR c f g
under estimate them. This is not a universal observation, a ρXσ (r, u) = − 2 (a|b − u| + 1)e−a|b−u| − (a|b + u | + 1)e−a|b+u| ,
2a bu
recent study28 of certain TM compounds found that hybrids
(3)
performed better than semi-local functionals.
In general, for a density functional theory (DFT) approach where a, b, and c are parameters determined through exact
that starts from exact exchange, such as hybrids and CF, the constraints. In detail, we impose two conditions in all X-hole
TM compounds pose an enormous challenge. Exact exchange models, the first is the on-top condition,
by itself is a very bad approximation to EXC , meaning that the
correlation contributions to the atomization energies are very ρXσ (r, r) = −ρσ (r), (4)
large. The well established global hybrid schemes, such as PBE
which sets the depth of the X-hole model at the reference
hybrid5 or B3LYP,22,25 perform poorly for strongly correlated
point r. The second condition aims at reproducing a given
TM compounds, and one might expect this to carry over to the
exchange energy per particle,
CF approach as well. However, as we show, remarkable accu-

rate atomization energies are obtained with certain CF func- GBRy y
2π duuρXσ (r, u) = Xσ (r). (5)
tionals while reducing empiricism to a minimum. To the best
of our knowledge, for the atomization energies of TM dimers,
the CF method yields the best results among the functionals The label y indicates which -approximate or exact- exchange
that rely predominantly on a first principles construction. energy per particle is employed. For the present work,
y = {LSD, PBE, Exact}, where LSD and PBE stand, respectively,
for local-spin29 and Perdew-Burke-Ernzerhof21 density func-
II. THE CORRELATION FACTOR MODEL tional approximations, while Exact indicates that the exact
AND EXTENSIONS THEREOF quantity is used.
In this section, we begin with a review of the key concepts The remaining parameter is determined from one of the
of the CF approach.15,16 Subsequently, further developing the following two conditions:
CF, we show how to impose the HEG limit and how to modify 
the CF to account for strong correlation. The central notion 4π duu2 ρXσ (r, u) = −1, (6)
of the proposed approximation is the XC-hole ρXC (r, u)29,30 of
DFT. The exchange-correlation energy is obtained in terms of or
the XC-hole through 1 2 1
 2 
1 (∇ρσ (r)) +
  ∇r0 ρXσ (r, r0 )|r0 =r = − ∇2 ρσ (r) − γ *2τσ (r) + .
ρXC (r, u) 3! 6 2 ρσ (r) -
EXC [ρ] = d3 rρ(r) d3 u . (1)
 , 
2u (7)

J. Chem. Phys. 150, 084107 (2019); doi: 10.1063/1.5083840 150, 084107-2

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In this equation, γ is a scaling parameter whose value is 1 in the
present context. Enforcing either condition, Eq. (6) or Eq. (7),
BRyN BRyC
results in different model holes, ρXσ and ρXσ , respectively,
y BRyN
both of which reproduce the same Xσ . Compared to ρXσ ,
BRyC
ρXσ is more localized around the reference point r. Exchange
energies per particle that are small in absolute value are repre-
BRyC
sented by ρXσ through a localized hole which has a normal-
BRyN
ization integral that is smaller than one. With ρXσ , the same
y
low value of |Xσ | is achieved through de-localization of the
exchange hole. There are thus two options to represent a given
exchange energy per particle, either through a de-localized,
normalized hole or a localized, un-normalized hole. The two
BRyC
X-hole models are key elements of the CF approach. ρXσ is
BRyN
more localized than ρXσ ,
and in a density functional context
it is expected that this X-hole is easier to transform into an
XC-hole. On the other hand, there is a risk of over-localization
BRyN
of the XC-hole. ρXσ is fairly de-localized, and again, this ten-
dency can carry over to the XC-hole. In Sec. II C, we attempt
to find a balance between localization and de-localization of
the XC-hole. First, however, we present a modification of the
X-hole designed to recover the homogeneous limit for the
exchange-correlation energy obtained with the CF approach.
B. Correlation factor model satisfying
the homogeneous electron gas limit
In its original form,40 the hydrogen-atom derived Becke-
Roussel hole does not reproduce the homogeneous limit: if,
in the determination of a, b, c, the curvature condition is
used in conjunction with the on-top condition and the con-
dition to reproduce the exchange energy per particle of the
HEG,41–43 then the normalization condition is not satisfied. In
the CF approach, the normalization is enforced as the final
step, thus the CFM EXC cannot, in general, reduce to exact EX .
To cure this problem, the input curvature can be modified40
such that the exchange hole parameters that reproduce the
HEG exchange energy also result in a normalized hole; i.e., the
parameter γ in Eq. (7) is set to 0.797 039, and the resulting X-
BRy,HEG
hole is referred to as ρXσ
BRy,HEG
. A CFM building on ρXσ can
be designed and this version of the CF recovers the correct
XC-energy in the HEG limit.
C. Adjusting the locality of the exchange hole model
In Sec. II A, two different X-hole models are intro-
duced, satisfying the normalization or the curvature condition,
respectively. Since there is no reason to choose one condi-
tion over the other, we use an average of the two X-holes,
i.e., we adjust the locality of the resulting averaged X-hole and
therefore the amount of static correlation that is introduced
through the normalization of the X-hole in the last step of the
CF approach. In detail, ρXAV (r, u) is given by
BRyN BRyC
ρXAV (r, u) = λρX (r, u) + (1 − λ)ρX (r, u),
where λ is the weighting factor with 0 ≤ λ ≤ 1. In the calcula-
tions reported below in Sec. IV, λ is determined empirically
J. Chem. Phys. 150, 084107 (2019); doi: 10.1063/1.5083840
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ARTICLE scitation.org/journal/jcp
by minimization of the mean absolute error of atomization
energies of main-group and transition metal compounds.
As mentioned above, the on-top value [Eq. (4)] and
exchange-energy per particle [Eq. (5)] condition are enforced
for the two X-holes models employed in the averaged X-hole.
BRyN
Additionally, the ρXσ satisfies the normalization condition
BRyC
Eq. (6), while ρXσ respects the curvature condition Eq. (7),
but neither of these conditions is satisfied by ρXAV (r, u).
D. The correlation factor
The starting point for the construction of the CF is the
expression used in our previous work,15,16
fC (r, u) = (A + Bu + Cu2 + Du4 )e−µu .
2
(9)
The coefficients A, B, C, D, and µ in this expression are func-
tions of r, and they are determined using various conditions
that are described now. The conversion of the X-hole into
an XC-hole has to account for the essential physical char-
acteristics of electron correlation. The on-top value of the
exchange-hole, representing same-spin electron exclusion,
has to be lowered further to include opposite-spin electron
repulsion.44 This is achieved through the constant A. Further-
more, to account for the cusp44 around an electron, we intro-
duce a linear term in u with a coefficient B. In mathematical
terms, A and B are determined through
CF LSD
ρXC (r, u = 0) = ρXC (r, u = 0) (10)
and

∂ρXC
CF (r, u) 1
LSD
= dλ λ{ρ(r) + ρXC,λ (r, u = 0)}. (11)
∂u 0
u=0
The parameter µ in the exponent of the CF sets the range of
the XC-hole. As detailed in our previous work,15,16 we use the
LSD approximation to determine µ: building on ρXσ BRLSDN (r, u),
D is temporarily set to zero and µ is determined such that
the XC-energy of the HEG is recovered. The parameter D also
has an impact on the range of the XC-hole, we use the PBE
functional21 to determine its value through the condition15,16

CF PBE
2π du uρXC (r, u) = XC (r), (12)
BRyN
where the underlying X-hole ρXσ (r, u) is constraint to repro-
duce the PBE X-energy per electron, i.e., y = PBE. D modifies
the oscillatory character of the XC-hole, this provides a way to
reduce the resulting correlation energy and to account for the
fact that the gradient correction of PBE reduces correlation
compared to LSD. Finally, the parameter C serves to enforce
the normalization of the XC-hole,

4π du u2 ρXCCF
(r, u) = −1. (13)
(8) In general, for systems that are qualitatively described
by the Kohn-Sham determinant, the LSD approximation to
the on-top value [Eq. (10)] is fairly accurate. For strongly-
correlated systems, however, this approximation predicts an
150, 084107-3
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on-top value that is too high. A typical example of strong-
correlation is provided by the stretched H2 molecule. It is easy
to see that the on-top value of this system is simply the nega-
tive of the electron density, i.e., the lowest possible value. This
result is clearly not reproduced by the LSD approximation, a
problem that is addressed next.
E. Static-correlation correction of the on-top value
In this section, we propose a correction to the on-top hole
depth and, correspondingly, to the cusp condition employed
in the CF. The LSD on-top hole value is remarkably accurate
for a wide range of systems which are sometimes referred to
as normal systems.45 Normal systems are describable by a sin-
gle Slater determinant. However, if a single determinant does
not provide a qualitatively correct description, strong cor-
relation is present and the LSD on-top value approximation
for the XC-hole is often inaccurate. In these cases, we want
to apply a correction to the LSD on-top value. To determine
where strong correlation is significant, we employ the nor-
malization of the projected exchange hole NB03 Xσ
(r), proposed
by Becke.6 NB03 (r) is close to one if static correlation is weak
Xσ
and less than one if it is strong. For instance, in the stretched
H2 NB03
Xσ
(r) = 1/2 everywhere. A simple ansatz to correct the
depth of the on-top value of the CF exchange-correlation hole
is
OC LSD
ρXC (r, u = 0) = ρXC (r, u = 0) − ∆(r),
where OC denotes on-top correction, and furthermore
LSD
∆(r) = ω(r)[ρ(r) + ρXC (r, u = 0)].
The function ∆(r) deepens the LSD on-top hole density at r
according to the local index ω(r)
ω(r) = 1 − NB03
X (r),
where
(1 + ζ(r)) B03 (1 − ζ(r)) B03
NB03
X (r) = NX↑ (r) + NX↓ (r)
2 2
is a spin-averaged normalization of the X-hole. In regions
where strong correlation is important NB03X
(r) is less than one,
ω(r) is greater than zero, and consequently, the on-top hole
density in Eq. (14) gets deepened. Although our ansatz Eq. (15)
is not unique, it provides a simple model to account for non-
dynamical correlation in the CF approach. The slope of the
cusp depends on the on-top hole and a correction to the lat-
ter necessitates a correction to the cusp. The resulting explicit
expression is
∂ρXC
OC (r, u) ∂[ρXC
LSD (r, u) − ∆(r)]
=
∂u ∂u
u=0 u=0
4 LSD
= rs H(rs )[ρ(r) + ρxc (r, u = 0) − ∆(r)],
3πκ
where rs is the Wigner-Seitz radius and the value of κ and
the function H(rS ) are given in Ref. 44. Static correlation is
J. Chem. Phys. 150, 084107 (2019); doi: 10.1063/1.5083840
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then incorporated in the CF approach by replacing the on-
top [Eq. (10)] and cusp [Eq. (11)] conditions by their corrected
counterparts defined in Eqs. (14) and (18).
Building on the CFX and CFXN approach of our previ-
ous work, we introduced the corresponding versions, CFXHEG
and CFXNHEG which respect the HEG limit. Similarly, the
on-top correction leads to two further variations, CFXOC
and CFXNOC . Of course, the on-top correction can also be
applied to CFXHEG and CFXNHEG , resulting in CFXHEG−OC and
CFXNHEG−OC . Finally, CFX and CFXN, as well as their variants,
can be combined in averaged schemes (CFXAV). All the CF
methods discussed above are now assessed for the atomiza-
tion energies of main group and transition metal compounds.
III. COMPUTATIONAL DETAILS
The calculations reported are performed with a modified
version of the Gaussian program system.46 The geometries of
the main group molecules are optimized with the PBE func-
tional21 using 6-311 + G(3df, 2p) basis sets.47–50 The geometries
of the TM compounds have also been obtained with PBE but
with QZVP basis sets.51 All approximations proposed in this
work are assessed through post-PBE calculations, employing
the same basis sets as in the geometry optimizations.
The PBE orbitals employed in the post Kohn-Sham cal-
culations of the TM compounds have been obtained with the
experimental value of the spin projection (SZ value) through
(14) open-shell, broken-symmetry calculations. The final elec-
tronic states as well as the optimized geometries obtained in
these calculations agree with those reported by Furche and
(15) Perdew.20 The Gaussian Ultrafine grid has been used in all
calculations reported.
IV. THE CORRELATION FACTOR MODEL
FOR ATOMIZATION ENERGIES OF MAIN GROUP
AND TRANSITION METAL COMPOUNDS
(16)
There are various differences between the implementa-
tion and the calculations reported in the first accounts15,16 of
our CF approach and the implementation and the calculations
(17) of the present article. In the original work, the atomization
energies are obtained in a non-self-consistent, post-Hartree-
Fock approach, whereas now, all calculations are performed
in a post-PBE fashion. Furthermore, as already mentioned, the
exact exchange-energy per particle is now calculated (see the
Appendix) without the additional approximation of the reso-
lution of the identify17,18 used in our previous work. First, we
compare our new implementation of the CFM (Table I) to the
original version (Table III in Ref. 16), the atomization energies
of a small set of molecules obtained with CFX are better, with
a mean absolute error (MAE) of 4.5 kcal/mol, than the results
obtained with the new implementation (7.0 kcal/mol). How-
ever, if the CFXAV is employed, the current post-PBE imple-
mentation yields a MAE of 3.5 kcal/mol, very similar to the
original implementation with a MAE of 3.1 kcal/mol. In all the
(18) calculations using the averaged X-hole of Eq. (8), the param-
eter λ has been determined by minimizing, for each version
of the CF functionals, the MAE of the calculated atomization
energies of the main-group and TM compounds.
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TABLE I. Atomization energies in kcal/mol for a set of small, single- and multiple-bonded molecules. MAE denotes mean
absolute error.

Molecules PBEa PBE0b CFXc CFXNd CFXAVe CFXOC f CFXNOC g CFXAVOC h Exacti

H2 105.0 104.0 106.4 105.3 106.1 107.6 106.6 107.1 109.0

LiH 53.0 53.0 57.6 52.6 56.4 59.5 54.5 57.3 58.0
CH4 418.0 417.0 415.9 407.9 413.5 422.1 414.3 418.1 419.0
NH3 301.0 294.0 295.1 274.5 289.7 304.8 284.4 295.1 297.0
H2 O 233.0 227.0 232.0 205.1 225.3 242.6 215.9 230.5 232.0
HF 141.0 136.0 143.3 121.4 138.1 151.0 129.2 141.3 141.0
Li2 20.0 19.0 21.4 16.6 20.2 22.3 17.4 20.1 24.0
LiF 136.0 131.0 148.3 113.1 139.9 159.8 124.8 144.4 139.0
Be2 7.0 5.0 9.0 −2.8 6.2 10.3 −1.4 5.1 3.0

MAE 2.9 4.4 3.1 14.2 3.9 7.1 8.5 2.1 0.0

C2 H2 411.0 402.0 413.9 372.7 403.5 427.3 386.5 408.6 405.0

C2 H4 567.0 561.0 565.2 536.7 557.7 577.6 549.3 564.2 563.0
HCN 322.0 309.0 324.2 270.1 310.7 341.3 287.5 316.8 312.0
CO 265.0 253.0 270.7 218.3 258.0 287.4 235.3 264.0 259.0
N2 239.0 222.0 238.8 178.2 223.7 257.6 197.4 230.3 229.0
NO 163.0 147.0 168.3 104.3 152.7 187.0 123.4 158.5 153.0
O2 136.0 120.0 144.6 76.4 128.2 163.0 95.0 132.9 121.0
F2 47.0 31.0 52.4 −16.8 36.2 70.0 1.1 39.9 39.0
P2 117.0 109.0 121.0 85.5 112.1 129.3 94.0 113.1 117.0
Cl2 62.0 57.0 61.5 40.7 56.5 64.9 44.2 55.7 58.0

MAE 7.3 4.5 10.5 39.0 3.1 24.9 24.2 4.0 0.0
Total MAE 5.2 4.5 7.0 27.3 3.5 16.5 16.8 3.1 0.0
a Reference 21.
b Reference 5.
c CF model based on the generalized BR exchange hole.
d CF model based on the normalized BR exchange hole.
e Averaged CF model with λ = 0.225.
f CF model based on the generalized BR exchange hole with on-top value correction.
g CF model based on the normalized BR exchange hole with on-top value correction.
h Averaged CF model with on-top value corrections and λ = 0.425.
i Reference 21.

Next, we consider the effect that the on-top correction
has on the atomization energies. Overall, the on-top correc-
tion increases the magnitude of the correlation energy. Since
the atomization energies at the CFX level are already overes-
timated, the MAE of CFXOC worsens. CFXN typically underes-
timate the atomization energies and therefore CFXNOC repre-
sents an improvement over CFXN. If the CFXAVOC is regarded,
the MAE is considerably reduced to a value of 3.1 kcal/mol.
We stress that the PBE hybrid exhibits a MAE of 4.5 kcal/mol
and therefore, the CFXAVOC improves significantly upon PBE
hybrid.
Another addition to the original work is the construction
of a CF approach which satisfies the homogeneous limit, as
described in Sec. II B. As can be seen in Table II, this mod-
ification increases the MAE of atomization energies consid-
erably. Also the CFXAVHEG , satisfying the homogeneous limit,
has a slightly increased MAE of 3.6 kcal/mol compared to
CFXAV.
If the on-top correction is used in conjunction with
the HEG constraint, at the CFXHEG−OC level, the atomization
energies are too large. Both, the HEG constraint as well
as the on-top correction tend to increase the atomization
energies, and therefore it is not surprising to obtain a large
overestimation if both conditions are enforced. Again, the
CFXAVHEG−OC approach, balancing the locality of the X-hole
or equivalently the amount of static correlation, results in
atomization energies that are comparable in accuracy to PBE
hybrid.
Next, we turn to TM compounds, some of which are
strongly correlated and pose a significant challenge to any
method that employs exact exchange (e.g., the PBE hybrid,
CF approach). Not surprisingly, global hybrid schemes are
not the DFT method of choice for TM compounds and often
LSD, GGAs, and meta-GGAs are preferred. As described in
the Introduction, a benchmark set that includes the atom-
ization energies of TM hydrides, nitrides, oxydes, fluorides,
and homonuclear dimers has been compiled by Furche and
Perdew,20 we use it to assess the models proposed in Sec. II.
In Tables III and IV, we compare CF approximations to PBE,21
PBE hybrid,5 B1310,11 and TPSS.24

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TABLE II. Atomization energies in kcal/mol for a set of small, single- and multiple-bonded molecules. MAE denotes mean
absolute error.

Molecules CFXAVa CFXHEG b CFXNc CFXAVHEG d CFXHEG − OC e CFXNOC f CFXAVHEG − OC g Exacth

H2 106.1 106.4 105.3 106.0 107.6 106.6 106.9 109.0

LiH 56.4 57.9 52.6 56.4 59.9 54.5 56.6 58.0
CH4 413.5 427.5 407.9 421.4 436.5 414.3 424.1 419.0
NH3 289.7 305.0 274.5 295.6 319.4 284.4 300.3 297.0
H2 O 225.3 241.6 205.1 230.6 257.4 215.9 234.8 232.0
HF 138.1 149.3 121.4 141.0 161.0 129.2 143.8 141.0
Li2 20.2 22.0 16.6 20.5 23.0 17.4 19.6 24.0
LiF 139.9 155.0 113.1 142.7 171.1 124.8 145.4 139.0
Be2 6.2 11.2 −2.8 7.1 12.8 −1.4 4.2 3.0

MAE 3.9 7.0 14.2 2.4 14.6 8.5 3.3 0.0

C2 H2 403.5 429.9 372.7 412.7 448.6 386.5 413.0 405.0

C2 H4 557.7 585.2 536.7 570.4 603.1 549.3 572.8 563.0
HCN 310.7 336.9 270.1 316.8 360.3 287.5 318.8 312.0
CO 258.0 282.2 218.3 263.2 304.9 235.3 265.4 259.0
N2 233.7 247.7 178.2 226.8 273.9 197.4 230.7 229.0
NO 152.7 178.3 104.3 156.4 205.0 123.4 159.2 153.0
O2 128.2 155.8 76.4 132.5 182.5 95.0 133.7 121.0
F2 36.2 60.7 −16.8 38.1 85.0 1.1 37.5 39.0
P2 112.1 126.8 85.5 114.6 138.3 94.0 112.8 117.0
Cl2 56.5 67.9 40.7 60.0 73.5 44.2 56.9 58.0

MAE 3.1 21.5 39.0 4.7 41.9 24.2 5.8 0.0

Total MAE 3.5 14.7 27.3 3.6 29.0 16.8 4.6 0.0
a Averaged CF model with λ = 0.225.
b CF model based on the generalized BR exchange hole modified to reproduce the HEG limit.
c CF model based on the normalized BR exchange hole.
d Averaged CF model reproducing the HEG limit and λ = 0.275.
e CF model based on the generalized BR exchange hole, reproducing the HEG limit and including the on-top

value correction.
f CF model based on the normalized BR exchange hole, including the on-top value correction.
g Averaged CF model with on-top value corrections, respecting the HEG limit, λ = 0.600.
h Reference 21.

A. Hydrides through the re-normalization procedure performed in the last

step of the CFM, the additional amount of static correlation
Since the bond distances are rather short, the exchange
included by the on-top correction lowers the total energy of
hole is not significantly de-localized and the static correlation
molecules further and increases the over binding. On the con-
energy of the molecules is not excessive. The characteris-
trary, CFXNOC incorporates an important amount of left-right
tics of the X-hole models are reflected in the results where
correlation that is missing in CFXN and yields quite accurate
we find that CFXN performs better compared to CFX, CFXN
atomization energies with a MAE of 5.7 kcal/mol close to the
does not at all account for static correlation. Another indi-
B13 MAE of 4.5 kcal/mol. The CFXAVOC also yields good results
cation for the lack of static correlation in the hydrides is the
for the atomization energies. Imposing the HEG limit, as a
fact that the PBE hybrid performs fairly well for these com-
general observation, increases the atomization energies com-
pounds. It is known that PBE hybrid, having a sizeable fixed
pared to the corresponding CF version without this constraint.
amount of exact exchange, underestimates atomization ener-
Again, also at this level, the CFXAVHEC results in good overall
gies of systems with strong static correlation. The CFXAV
atomization energies.
yields a MAE of 6.9 kcal/mol and is outperformed only by
B13. Atomization energies obtained with the static-correlation
corrections developed in Sec. II are also reported in Table III, B. Nitrides
showing that with CFXOC over-binding increases compared The nitrides, described with PBE hybrid, exhibit large
to CFX, while the underestimation of CFXN is reduced by under-binding indicating that there is considerable static cor-
about 1.0 kcal/mol upon addition of the on-top correction relation in these systems. At the CFX level, this static corre-
(CFXNOC ). Since CFX accounts for some static correlation lation is overestimated. The CFXAV again provides the right

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TABLE III. Atomization energies in kcal/mol for a set of transition metal compounds. MAE denotes mean absolute error.

Molecules PBEa PBE0b B13c TPSSd CFXe CFXNf CFXAVg CFXOC h CFXNOC i CFXAVOC j Exactk

KH 40.7 39.3 44.3 43.5 43.7 37.3 42.3 46.5 40.0 43.8 42.2
CaH 46.6 45.4 41.0 53.2 45.7 41.5 44.8 47.2 43.0 45.5 41.0
ScH 60.5 50.3 57.9 64.8 62.8 44.3 58.6 66.6 48.1 58.7 47.5
TiH 63.1 50.6 57.9 68.8 63.4 54.3 61.3 66.9 57.8 62.9 50.0
VH 59.2 57.2 58.3 65.2 61.7 49.6 58.9 65.6 53.5 60.4 51.4
CrH 52.4 48.7 48.8 57.4 54.2 38.1 50.5 58.2 42.2 51.4 46.8
MnH 45.4 66.9 37.5 52.3 43.0 35.5 41.5 43.5 35.9 40.5 31.1
FeH 56.9 60.5 37.5 60.6 56.2 44.9 53.6 59.4 48.2 54.5 39.2
CoH 61.8 55.1 52.1 64.3 63.5 35.1 57.0 68.2 39.9 56.1 48.4
NiH 66.6 57.9 67.3 69.0 70.0 50.5 65.4 73.9 54.5 65.5 61.3
CuH 64.5 59.6 66.0 67.3 68.4 45.2 63.0 72.5 49.3 62.5 63.4

MAE 9.0 8.1 4.5 13.1 10.0 6.9 6.9 13.3 5.7 7.4 0.0

ScN 121.5 94.6 100.8 112.8 128.0 29.1 105.0 151.5 52.9 108.7 113.0
TiN 140.1 111.8 127.4 128.9 149.8 40.4 124.0 176.3 67.4 128.6 124.0
VN 132.3 88.9 117.3 123.8 141.8 11.1 111.3 171.3 41.2 114.7 117.0
CrN 106.2 69.4 82.8 97.2 114.3 −29.1 80.9 145.0 2.2 82.9 97.0

MAE 12.3 21.6 7.5 3.0 20.7 99.9 7.5 48.3 71.8 6.3 0.0

CaO 123.3 102.1 110.6 117.7 129.5 44.2 109.8 153.1 68.0 116.3 110.8
ScO 182.3 160.9 171.1 171.6 190.0 104.4 170.0 213.1 127.8 176.0 163.0
TiO 183.1 160.4 171.2 173.9 194.2 97.7 171.6 220.1 123.9 178.1 161.0
VO 168.4 141.4 153.0 158.9 177.4 63.4 152.9 205.5 91.9 158.2 150.0
CrO 120.7 92.3 101.6 113.6 130.1 13.5 103.0 158.5 42.3 108.2 103.0
MnO 127.5 117.1 93.8 120.1 132.9 −0.9 102.3 160.0 26.5 102.7 89.5
FeO 128.2 110.9 99.1 119.1 136.3 24.6 110.4 161.9 50.6 113.8 97.4
CoO 115.6 80.6 87.6 105.8 133.4 7.7 104.4 162.0 36.7 107.9 92.1
NiO 112.6 80.5 82.4 104.4 128.5 −3.3 98.2 157.8 26.4 101.2 90.4
CuO 77.7 62.0 57.8 73.0 85.1 10.5 67.9 101.9 27.4 69.7 66.6

MAE 21.6 9.8 5.0 13.4 31.4 76.2 6.9 57.0 50.2 10.8 0.0

KF 119.7 112.4 119.7 118.5 126.6 92.2 118.7 139.3 110.0 124.5 117.5
CaF 139.8 131.2 132.9 137.7 143.2 104.3 134.2 155.5 122.0 138.8 127.2
ScF 155.6 142.2 147.7 151.4 163.0 105.4 149.7 178.7 127.1 153.9 143.3
TiF 145.0 137.5 139.1 142.4 152.4 107.4 141.9 167.2 127.4 147.7 137.0
CrF 119.1 109.1 110.8 117.8 124.8 76.8 113.8 140.1 98.7 119.5 106.3
CuF 101.5 92.5 96.3 99.4 106.8 63.9 96.9 120.3 83.9 101.7 102.8

MAE 8.2 4.0 4.2 6.7 13.8 30.7 5.5 27.8 10.8 9.0 0.0

K2 13.3 11.6 14.2 14.7 14.4 5.4 12.1 15.4 6.4 11.3 12.0
Ti2 68.7 27.8 56.1 61.4 88.4 −73.2 50.4 116.9 −43.9 46.6 36.1
V+2 91.7 23.3 86.5 81.9 118.3 −145.5 56.5 164.8 −97.7 50.3 73.2
V2 71.3 8.7 71.6 64.4 105.4 −157.7 43.9 156.1 −105.7 42.1 64.3
Cr2 34.8 −18.8 55.0 31.0 58.3 −205.5 −2.7 107.8 −154.8 −5.8 33.9
Fe2 57.0 21.4 10.4 44.2 81.3 −137.4 31.2 120.8 −97.0 27.2 26.9
Co2 58.9 −6.2 21.0 48.6 97.7 −173.1 35.7 148.7 −121.2 32.7 39.4
Ni+2 69.5 46.3 66.5 68.2 87.7 −46.3 57.1 106.4 −27.3 49.0 52.2
Ni2 62.3 20.0 33.5 57.8 83.9 −89.7 44.2 114.4 −58.8 40.0 48.1
Cu2 48.9 41.0 47.3 47.7 53.2 14.2 44.1 59.0 20.1 42.1 46.7

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TABLE III. (Continued.)
Molecules PBEa PBE0b B13c TPSSd CFXe
MAE 14.4 25.8 12.8 9.3 35.6
Total MAE 13.6 13.5 6.9 10.3 23.1
a Reference 20.
b PBE hybrid atomization energies obtained self-consistently.
c Reference 52.
d Reference 20.
e CF model based on the generalized BR exchange hole model.
f CF model based on the normalized BR exchange hole model.
g Averaged CF model with λ = 0.225.
h CF model based on the generalized BR exchange hole with on-top value correction.
i CF model based on the normalized BR exchange hole with on-top value correction.
j Averaged CF model with on-top value corrections and λ = 0.425.
k Reference 20.
amount of locality and the atomization energies obtained are
a big improvement over PBE and PBE hybrid. It is as good as
B13 which also yields a MAE of 7.5 kcal/mol. The TPSS func-
tional does surprisingly well for this class of compounds and
the MAE is a mere 3.0 kcal/mol.
The MAE of atomization energies obtained with CFXOC is
more than twice that of CFX while the corrections applied
to CFXN reduces the MAE from 99.9 kcal/mol (CFXN) to
71.8 kcal/mol (CFXNOC ). Once again, the CFXAVOC results in
good atomization energies with a MAE of 6.3 kcal/mol. The
above discussion about the HEG constraints also applies to the
nitrides; the HEG constraint increases the atomization ener-
gies, whereas the CFXAVHEC approach corrects for much of
the overestimation. The same observations hold if the HEG
constraint is combined with the on-top correction.
C. Oxides and fluorides
As indicated by the relative good performance of PBE
hybrid, the static correlation in these systems is not exces-
sively large; the fluorides exhibiting smaller errors at the PBE
hybrid level than the oxides. As already observed repeatedly,
the on-top correction and the imposition of the HEG limit
tend to worsen the over binding of the CFX approach and
reduce the under binding of CFXN. The CFXAV again yields a
good balance of local and non-local effects (Table III). A simi-
lar discussion applies to CFHEG and CFHEG−OC , as well as to the
corresponding averaged CFMs.
Comparing the best CFMs, i.e., the ones based on the
averaged exchange hole, to the other functionals consid-
ered, we find that CFXAV improves upon the functionals PBE
and TPSS; the results are, however, worsened by the on-top
correction and the HEG constraint.
D. Dimers
Again using the under binding tendency of the PBE hybrid
as a measure of strong correlation, among the systems consid-
ered in this study, the TM dimers represent the biggest chal-
lenge. For several dimers, no binding at all is obtained with PBE
hybrid. The dimers are a prime example for why functionals
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CFXNf CFXAVg CFXOC h CFXNOC i CFXAVOC j Exactk
144.2 10.8 67.8 111.3 11.9 0.0
69.8 7.7 42.8 49.5 9.5 0.0
employing exact exchange are rarely employed in computa-
tional modelling of TM compounds. The small overlap between
some atomic d-orbitals of different atoms is generating weak
bonds with large static-correlation contributions.
The CFX approach strongly overestimates static correla-
tion in the dimers and the CFXAV is again surprisingly accurate
and comparable to the best functional, namely, TPSS. The on-
top correction worsens the CFX and improves upon the CFXN;
the CFXAVOC is almost as accurate as the CFXAV of the uncor-
rected version. We take this as an indication that for systems
with strong-static correlation, the on-top correction becomes
increasingly realistic; this point is further investigated below
in Sec. V. Again, imposing the HEG limit increases the binding
energies.
E. Overall
The overall tendency is that the CFX model strongly over-
estimates most dissociation energies with the largest MAE
observed for the TM dimers. CFXN exhibits the opposite
behaviour to CFX and drastically underestimates the binding
energies of the majority of the molecules with a huge MAE
for TM dimers. As expected, B13, which was constructed for
the purpose of describing strong correlated systems, has the
best overall performance followed by CFXAV, CFXAVHEG , and
CFXAVOC . The corrections to the on-top value are intended to
yield CF XC-holes that are increasingly localized. We expect
an increase in overestimation and a decrease in underesti-
mation of bond energies by CFX and CFXN, respectively. In
Table III, we observed that this is indeed the case where CFXOC
overbinding increases and its total MAE is almost twice as high
as that of CFX. The CFXNOC reduces the errors in atomization
energies by 20 kcal/mol relative to CFXN.
The results obtained for the main and the transition group
elements indicate that the CF variants that built on the aver-
aged exchange hole, in particular, the CFXAV approach, are
highly accurate; CFXAV is surpassed only by the B13 func-
tional. B13 also builds on exact exchange; it has been designed
to address strong correlation and in its applications the sin-
glet species are spin-restricted, ensuring the correct spin
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TABLE IV. Atomization energies in kcal/mol for a set of transition metal compounds. MAE denotes mean absolute error.

Molecules CFXAVa CFXHEG b CFXNc CFXAVHEG d CFXHEG − OC e CFXNOC f CFXAVHEG − OC g Exacth

KH 42.3 44.0 37.3 42.3 46.9 40.0 42.9 42.2

CaH 44.8 47.0 41.5 45.6 48.9 43.0 45.7 41.0
ScH 58.6 63.7 44.3 58.3 68.7 48.1 56.9 47.5
TiH 61.3 62.6 54.3 60.2 66.4 57.8 61.4 50.0
VH 58.9 60.8 49.6 57.7 65.7 53.5 58.9 51.4
CrH 50.5 53.7 38.1 49.4 59.7 42.2 50.4 46.8
MnH 41.5 45.3 35.5 42.8 48.3 35.9 42.5 31.1
FeH 53.6 58.3 44.9 54.6 63.7 48.2 55.6 39.2
CoH 57.0 65.9 35.1 57.3 77.2 39.9 58.5 48.4
NiH 65.4 71.6 50.5 65.6 78.0 54.5 65.1 61.3
CuH 63.0 69.6 45.2 62.8 77.0 49.3 62.1 63.4

MAE 6.9 10.9 6.9 6.9 16.2 5.7 7.3 0.0

ScN 105.0 138.4 29.1 107.4 170.3 52.9 103.5 113.0

TiN 124.0 156.1 40.4 122.9 192.4 67.4 121.4 124.0
VN 111.3 147.2 11.1 108.4 190.4 41.2 107.2 117.0
CrN 80.9 119.7 −29.1 77.3 167.2 2.2 76.3 97.0

MAE 7.5 27.6 99.9 8.8 67.3 71.8 10.6 0.0

CaO 109.8 141.1 44.2 113.7 171.7 68.0 112.6 110.8

ScO 170.0 201.3 104.4 173.7 231.8 127.8 172.5 163.0
TiO 171.6 201.7 97.7 171.9 235.2 123.9 171.5 161.0
VO 152.9 186.8 63.4 152.5 224.8 91.9 151.2 150.0
CrO 103.0 136.2 13.5 101.4 177.4 42.3 102.5 103.0
MnO 102.3 144.9 −0.9 103.8 190.2 26.5 101.6 89.5
FeO 110.4 146.8 24.6 112.1 188.1 50.6 113.5 97.4
CoO 104.4 140.9 7.7 103.2 184.6 36.7 103.3 92.1
NiO 98.2 136.6 −3.3 97.1 183.4 26.4 98.2 90.4
CuO 67.9 90.4 10.5 67.8 116.7 27.4 67.9 66.6

MAE 6.9 40.3 76.2 7.7 78.0 50.2 7.2 0.0

KF 118.7 133.0 92.2 121.4 150.5 110.0 125.7 117.5

CaF 134.2 151.2 104.3 137.9 168.6 122.0 140.1 127.2
ScF 149.7 170.3 105.4 151.9 191.7 127.1 152.1 143.3
TiF 141.9 157.4 107.4 143.1 177.1 127.4 146.6 137.0
CrF 113.8 129.5 76.8 114.6 151.1 98.7 119.1 106.3
CuF 96.9 113.0 63.9 99.0 132.8 83.9 102.9 102.8

MAE 5.5 20.0 30.7 6.9 39.6 10.8 8.7 0.0

K2 12.1 15.2 5.4 12.2 16.4 6.4 10.2 12.0

Ti2 50.4 96.8 −73.2 48.0 143.4 −43.9 39.4 36.1
V+2 56.5 129.4 −145.5 50.5 209.0 −97.7 40.5 73.2
V2 43.9 114.8 −157.7 36.7 199.0 −105.7 32.4 64.3
Cr2 −2.7 67.0 −205.5 −10.4 156.1 −154.8 −10.1 33.9
Fe2 31.2 95.4 −137.4 29.6 172.6 −97.0 31.0 26.9
Co2 35.7 109.1 −173.1 29.3 203.1 −121.2 31.2 39.4
Ni+2 57.1 90.5 −46.3 51.8 130.4 −27.3 46.9 52.2
Ni2 44.2 90.9 −89.7 39.8 149.5 −58.8 39.3 48.1
Cu2 44.1 56.8 14.2 44.6 67.8 20.1 41.6 46.7

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TABLE IV. (Continued.)

Molecules CFXAVa CFXHEG b CFXNc CFXAVHEG d CFXHEG − OC e CFXNOC f CFXAVHEG − OC g Exacth

MAE 10.8 43.3 144.2 13.0 101.4 111.3 14.5 0.0

Total MAE 7.7 29.0 69.8 8.8 60.5 49.5 9.6 0.0
a Averaged CF model with λ = 0.225.
b CF model based on the generalized exchange hole with the HEG limit.
c CF model based on the normalized BR exchange hole.
d Averaged CF model respecting the HEG limit, λ = 0.275.
e CF model based on the generalized BR exchange hole, with on-top value correction and respecting the HEG

limit.
f CF model based on the normalized BR exchange hole, with on-top value correction.
g Averaged CF model with on-top value correction, respecting the HEG limit, λ = 0.600.
h Reference 20.

symmetry. As opposed to CFXAV, which has one empirical
parameter, and the CF approach in general, the B13 relies on
various empirical parameters. The on-top correction that we
introduced to address strongly correlated systems does not
result in a significant worsening of the results at the aver-
aged level, the improvement that we might have expected is
not obtained even for the TM dimers whose atomization ener-
gies are the most likely to be impacted by strong correlation.
The satisfaction of the HEG constraint results in an additional
slight worsening of the atomization energies (compared to
CFXAV) if the averaged scheme is employed. The TM diatomics
are surprisingly well described by the CFXAV functional. The
latter is only outperformed by the TPSS functional, which does
not built on exact exchange. The question arises if there are
systems for which the on-top correction yields an improved
description. A standard test case for strong correlation is the
stretched H2 molecule and this is the system which we address
in Sec. V.
V. HYDROGEN MOLECULE STRETCHED TO INFINITE
DISTANCE
The hydrogen molecule, stretched to infinity, is equiva-
lent to two hydrogen atoms with half an up and half a down
spin electron on each of them. This spin-averaged configura-
tion of the H atoms is represented by
(1sα )1/2 (1sβ )1/2 ,
whereas the ground-state electron configuration of the H
atom is
(1sα )1 (1sβ )0 .
α and β denote up and down spin orbitals, respectively. These
two configurations have the same energy, however, popu-
lar functionals and Hartree-Fock are unable to recover this
result.11,19,53 In local and semi-local functionals, the XC-hole
is localized around the reference electron, meaning that it
does correctly localize around the separated hydrogen atoms.
However, since the degree of this localization is underesti-
mated, the magnitude of the correlation energy is underes-
timated as well. The principal reason for this underestima-
tion is the insufficient depth of the on-top XC-hole value
which is, explicitly or implicitly, built into many local and
semilocal functionals. At the exact exchange level, the hole
of the spin-unpolarized H atom is completely de-localized,
it is split into two identical halfs, one on each of the two
H atoms. Since the H atoms are infinitely separated, the
hole around one atom does not contribute to the exchange
energy around the other. Any method that starts from exact
exchange has to localize (and deepen) the hole around the
respective atom. To quantify the potential of approximations
to describe strong correlation, we define the de-polarization
energy ∆E,
spin-averaged spin-polarized
∆E = Etotal − Etotal . (21)
In Table V, we compare ∆E obtained with LSD, PBE, and
PBE hybrid to the various CF approximations. Not surpris-
ingly, CFXN shows the largest errors; to account for strong
correlation, the X-hole model has to be localized and this
is assured within the ρXσ BRExactC model whereas the ρBRExactN
Xσ
model, underlying the CFXN, yields a fairly de-localized hole.
The less severe errors of the LSD and PBE, compared to CFXN,
(19) are a consequence of the insufficient depth of the underlying
XC-hole, it is, however, localized. At the PBE hybrid level, the
errors increase compared to LSD and PBE, this is because of
the increased de-localization of the XC-hole, i.e., to the reduc-
(20) tion of static correlation. CFX gives small errors compared to
LSD, PBE, and PBE hybrid and further significant improve-
ments are obtained if the HEG limit and the on-top correction
are used. These results confirm the basic idea behind the on-
top correction; it is indeed this correction which drastically

TABLE V. Errors for the spin-averaged H atom defined by Eq. (21) in kcal/mol.

Method LSD PBE PBE0 CFX CFXHEG CFXOC CFXHEG − OC CFXN CFXNOC CFXAV CFXAVHEG CFXAVOC CFXAVHEG − OC

∆E 37.0 27.6 42.8 11.3 10.6 3.8 3.0 55.2 48.3 23.2 25.8 24.8 32.3

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improves the description of the stretched H2 . It appears that APPENDIX: CALCULATING THE EXCHANGE ENERGY
the impact of correlation on the atomization energies of the PER PARTICLE  Xσ (r)
TM compounds is not strong enough to require a correction The exact exchange energy per particle ( X σ (r)) employed
of the on-top hole depth. For stretched H2 , as described, the in the present implementation of the correlation factor model
on-top value of the LSD approximation is clearly in error and is calculated avoiding any approximation other than the repre-
correcting it, we obtain a significant improvement for the spin sentation of operators in the finite, one-particle basis set. Our
de-polarization energy. implementation builds on the PRISM algorithm54 as imple-
Using the averaged CF approaches increases the errors mented in the Gaussian program system.46 In particular,
in ∆E for stretched H2 . This is not surprising since the CFXN we use the electrostatic-potential routines to calculate the
approach is ad-mixed. CFXN is the worst performer for the exchange energy density
de-polarization energy. 
1 X χν (r0 )χτ (r0 ) 0
Xσ (r) = − Dµν σ Dκ τ σ χµ (r)χκ (r) dr ,
VI. CONCLUSIONS 2ρσ (r) µν κ τ |r − r0 |

The development of the correlation factor model is in its (A1)

early stages and the amount of work invested in this approach
where Dµν σ is a density matrix elements and χ µ an atomic
is small compared to established types of approximations
orbital. Denoting
such as GGAs, meta-GGAs, hybrids, etc. There are countless

avenues that can be explored in the further pursuit of the CF χν (r0 )χτ (r0 ) 0
approach. Neither the general form of the CF nor that of the Aντ (r) = dr (A2)
|r − r0 |
X-hole model are unique and alternative expressions might
well turn out to be superior. Furthermore, there are various and defining X
exact conditions, other than the ones used in this work, that Fτ σ (r) = Dκ τ σ χκ (r), (A3)
can be invoked to determine the parameters in the CF and κ
we have
to improve the accuracy of the CFM. In this work, we refine
the initial CF approach, use the exact exchange-energy per 1 X
Xσ (r) = − Fτ σ (r)Fν σ (r)Aντ (r). (A4)
particle, and explore an additional constraint (HEG limit) as 2ρσ (r) ντ
well as physically motivated modifications (on-top value and
cusp corrections). We find that the CF approach, in particu- It is convenient to define a new effective, r-dependent density
lar, the CFXAV variant, albeit being minimally parametrized, matrix,
yields surprisingly accurate results for the atomization ener- Pτν σ (r) = Fτ σ (r)Fν σ (r), (A5)
gies of main and TM compounds. This is noteworthy since any so that the exact exchange energy per particle is given through
approach that builds on exact exchange is extremely chal- an expression analogous to the one for the electrostatic
lenged when applied to atomization energies of TM com- potential54
pounds. While CFXAV performs slightly worse than the B13
functional, it has only one empirical parameter. We show that 1 X
Xσ (r) = − Pτν σ (r)Aντ (r). (A6)
the satisfaction of the HEG limit does not provide a con- 2ρσ (r) ντ
sistent improvement of atomization energies. Similarly, the
The quantity Aντ (r) is evaluated with the PRISM algorithm.54
on-top correction does also not result in an improved accu-
The matrix Pτν σ (r) plays the key role in our implementa-
racy for atomization energies; at the CFXAVOC level, a slight
tion of  X σ (r). To verify that within our code Pτν σ (r) is cor-
overall worsening, compared to CFXAV, is obtained for atom-
rectly constructed we note that the spin density is obtained
ization energies. The example of the stretched H2 demon-
from Pτν σ (r) according to
strates, however, that an on-top correction is needed for X
systems where strong-correlation by far dominates dynamic ρ(r) = Dµ κ χµ (r)χκ (r), (A7)
correlation. µκ
A key result of the present work is that the CFXAV
approach performs remarkably well for main and transition which after some simple algebra becomes
metal compounds. This underlines the potential of the cor-
X
ρ(r) = Pτν σ (r)Sντ , (A8)
relation factor approach. As mentioned, there are numerous ντ
additional exact constraints that can be explored to further
improve upon CFXAV. An example being a self-correlation free where S is the overlap matrix. This expression provides a
version of CFXAV which will be developed in future work. simple verification for the correctness of Pτν σ (r).

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