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Density Functional Theory for d- and f-Electron Materials
and Compounds
Ann E. Mattsson*[a] and John M. Wills[b]
The fundamental requirements for a computationally tractable
Density Functional Theory-based method for relativistic f- and
(nonrelativistic) d-electron materials and compounds are pre-
sented. The need for basing the Kohn–Sham equations on the
Dirac equation is discussed. The full Dirac scheme needs
exchange-correlation functionals in terms of four-currents, but
ordinary functionals, using charge density and spin-
magnetization, can be used in an approximate Dirac treat-
ment. The construction of a functional that includes the addi-
Introduction and Motivation
The evolution of society is closely correlated with advance-
ments in engineering. In Figure 1, this is illustrated by a mod-
ern bridge structure taking its technological starting point in a
log that some industrious ancient put over a creek. However, a
closer look at the Tacoma Narrows bridge in the illustration
reveals a severely twisted central span, and indeed this bridge
collapsed soon after this photo was taken.[1] The knowledge
and experience needed to build a bridge like the Tacoma
bridge has been gathered over many generations of engineers,
but new materials, new applications, and new situations, can
lead to failure. The list of bridge failures is long. Many of these
bridge failures can be traced to when bridges started to be
made from iron, and experience with this material’s response
to the environment was not very developed. Failures often
lead to new policies, such as, that soldiers could not march in
sync over bridges, to avoid hitting the self-harmonics that
would resulting in damage. The 1940 Tacoma Narrows bridge
disaster,[1] led to the new policy of testing new bridge designs
in wind tunnels.
In addition to bridges, many other objects are tested in
wind tunnels, such as airplanes, space shuttles, cars, and racing
bikes. In Figure 2, we see a reduced scaled model of a space
shuttle being tested in a wind tunnel.
As indicated in Figure 2, recent advances in computational
fluid dynamics (CFD) algorithms and increased computing
power, have made a transition to virtual wind tunnels possible.
Preliminary studies can be made in the virtual wind tunnel
and the more expensive real wind tunnel experiments can be
prepared and optimized for maximum information gathering
in the virtual wind tunnel.
However, the CFD equations are based on a limited set of
conservation laws and only conserve quantities such as energy,
momentum, and mass, and to close the system of equations
additional information about how materials respond to
834 International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
tional confinement physics needed for these materials is
illustrated using the subsystem-functional scheme. If future
studies show that a full Dirac, four-current based, exchange-
correlation functional is needed, the subsystem functional
scheme is one of the few schemes that can still be used for
constructing functional approximations. VC 2016 Wiley Periodi-
cals, Inc.
DOI: 10.1002/qua.25097
changes need to be added. These thermodynamical and con-
stitutive relations/materials models provide the part of a CFD
simulation that is materials specific. To give an explicit exam-
ple, a thermodynamic equation of state of each material in the
simulation needs to provide how the pressure is changing
when volume is compressed. Other models that might be
needed are fracture and strength models and rate equations.
Historically, materials models have been constructed based
on more or less empirical functional forms with materials
dependent parameters fitted to experimental data. The success
of virtual wind tunnels is, in fact, largely based on that, for
example, airplane aluminum is thoroughly characterized
experimentally.
In Figure 3, we illustrate how new materials models might
be constructed. The need for bridging length and time scales
is integral to the process since the materials response on the
macroscopic scale is determined by the physics at much
smaller scales, such as bond breaking. In an empirical materials
model fitted to experimental data, this dependence on scale is
implicit, but if we want to construct predictive theoretical
models without empiricism, we need to have control over the
full upscaling process.
In Figure 3, boxes depict areas of established theory frame-
works, such as Density Functional Theory (DFT) or Molecular
Dynamics (MD). Since such a framework has formalized the
physics into a mathematical formulation, large and well-
established codes usually are available. It is, however, a sub-
stantial challenge to perform the upscaling or bridging
(depicted by bridges in Fig. 3) needed for the creation of
[a] A. E. Mattsson
Center for Computing Research MS 1322, Sandia National Laboratories,
Albuquerque, New Mexico, 87185-1322
E-mail: aematts@sandia.gov
[b] J. M. Wills
T-1 MS B221, PO Box 1663, Los Alamos National Laboratory, Los Alamos,
New Mexico, 87545
C 2016 Wiley Periodicals, Inc.
V
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 WWW.Q-CHEM.ORG TUTORIAL REVIEWS

measurements can be performed, these final states have

largely been determined by extrapolation from the nonexplod-
ing region. However, despite the problems posed by explosive
materials being governed by van der Waals’ forces in equilib-
rium, we have devised a scheme that can accurately calculate
these points using MD with forces calculated with standard
DFT using the Armiento-Mattsson 2005 (AM05) functional.[4]
Figure 4 shows results for the explosive PETN, and we see that
the experimental points are confined to the nonexploding
region in the lower left corner. We also see that depending on
which group of experimental data is used in the extrapolation
toward the upper right corner (the relevant region is around a
Us of 8 km/s) or how the extrapolation is done, a large varia-
tion of curves can be obtained. For more details and defini-
Figure 1. The engineering tradition illustrated as from a log over a creek to tions see Ref. [5].
the Tacoma Narrows 1940 bridge (University of Washington Libraries, Special
Collections, UW21413, with permission).
The second case we discuss where simulations could be crit-
ical in replacing experiments has to do with radioactive mate-
rials. Due to the risk of radioactive contamination, experiments
more complicated materials models since one single scientist on these materials are dangerous, and thus hard to perform,
seldom can be proficient in more than one or two areas. which also leads to high costs. Being able to replace some of
Highly skilled researchers can be active in both the DFT and these experiments with calculations and, in addition, fine-tune
the MD areas, and can singlehandedly perform upscaling the settings of the remaining experiments to optimize the
between these two areas (creating force fields or potentials for amount of information about the material, would be
MD using DFT, e.g.), but this is a rather rare situation. Instead, invaluable.
the upscaling and bridging are normally heavily dependent on Interestingly, the two groups of materials here discussed,
teamwork and active collaboration between scientists in two explosives/molecular crystals and radioactive materials, are
governed by van der Waals’ forces and strong correlation,
or more areas. In Figure 3, the Equation of State (EoS) field is
respectively, two areas that pose unusually large challenges to
depicted as both a box and a bridge, since this picture was
computational methods.
created in the context of a Sandia effort to formalize the crea-
Having established the need for simulation of at least some
tion of EoS models for use in engineering codes, transitioning
types of materials, where experiments are hard, or even impos-
the bridge into a box.
sible, and expensive to perform, we will now further examine
As seen in Figure 3, the EoS models for an engineering
the case of f-electron materials, to which category most radio-
code such as the Sandia ALEGRA code,[2] can be based on
active materials belong. Because of the similarities in the
experimental data, and they usually are. However, there are
physics governing these materials we will also include d-elec-
cases where we would like or even need, to rely on theory.
tron materials in the following discussion.
The first case we will discuss is the case where experiments
are unavailable. This can happen when information for the EoS
is needed in a part of phase space that is inaccessible to
experiments. Good examples are the location in phase space
of triple points (vapor, solid, and liquid coexistence) and critical
points (where there is no distinction between liquid and
vapor). These points are very important information in the EoS
creation process but they are quite hard to determine experi-
mentally. At Sandia we often calculate the location in phase
space of these points using DFT-MD (MD simulations where
the forces between the ions are determined by a DFT
calculation).
Another example in this category is the unreacted Hugoniot
curve, the set of possible states just prior to detonation in an
exploding material. A Hugoniot curve is the collection of all
final states that can be reached from a specific initial state,
usually the ambient pressure, room temperature state, by a
shock wave (see e.g., Ref. [3]). In contrast to experiments
Figure 2. The transition from real wind tunnels (left, courtesy of NASA) to
determining a usual thermodynamic path, such as an isotherm,
virtual wind tunnels (right, courtesy of MicroCFD) made possible by
each shock experiment can only determine one point on the improved computational fluid dynamics software and increasing computer
Hugoniot. Since the explosive material detonates before any power.

International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097 835

 TUTORIAL REVIEWS WWW.Q-CHEM.ORG

Figure 3. CFD, and other engineering, codes need materials models. To construct such models, information from several length and time scales needs to
be combined. The lower path depicts the Equation of State construction while the upper path depicts other necessary constitutive models such as
strength and fracture.

Density Functional Theory functional derivative of the exchange-correlation energy

functional:
As the founder of DFT, Walter Kohn got the Nobel Prize in
chemistry in 1998. DFT is the preferred tool for calculating dExc ½nðrÞ
properties of more standard materials and it is the foundation Vxc ðrÞ5 (2)
dnðrÞ
of the computational materials science field.
The fundamental theorem of DFT is the Hohenberg–Kohn (or the equivalent for the Dirac-based KS equations which
(HK) theorem[6] which states that the electron charge density we will discuss later). We thus do not consider any scheme
contains all information needed to determine the ground state
properties of a system.
From the HK theorem, one can derive the Kohn–Sham (KS)
equations[7] for an N electron system:
!
1 2
2 r 1Veff ðrÞ wt ðrÞ 5 et wt ðrÞ t51; 2; 3; . . . ; N
2

XN
nðrÞ 5 jwt ðrÞj2 (1)
t51
ð
nðrÞ 0
Veff ðrÞ5VðrÞ1 dr 1Vxc ðrÞ
jr-r0 j
where n(r) is the electron charge density, V(r) denotes the exter-
nal potential, in our case stemming from the ions, and wt(r) is
the wave function of fictitious KS particles that are fermions but
Figure 4. Computed and experimental Us2up (shock wave velocity vs. particle
not electrons. These equations need to be solved self- velocity) Hugoniot data for single-crystal PETN. The red circles represent MD
consistently so that the density and the effective potential are results based on DFT using the AM05 functional. The blue, brown, and green
compatible. The form of Eq. (1) should thus be taken as some- symbols are experimental data. Dashed lines are linear fits to the correspond-
ing data, and solid purple lines are linear and quadratic fits to all experimental
what schematic. In this article, we use Hartree atomic units.
data. For more details, references, and definitions see Ref. [5]. The figure is
We use the term DFT to refer to a KS scheme where the adapted and enhanced from one first published in 2010 in Ref. [5], an article
exchange-correlation potential, Vxc(r), is defined via a produced under a U.S. Government contract and in the public domain.

836 International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097 WWW.CHEMISTRYVIEWS.ORG

 WWW.Q-CHEM.ORG
Figure 5. The difference between the DFT and the mean field (MF) view. In
this figure we use q(r) for the electron density. See text for discussion.
Reproduced from Ref. [8], published in 2011, a chapter produced under a
U.S. Government contract and in the public domain.
involving the Hartree–Fock (HF) potential as being a DFT
method. Our definition of DFT gives an exact translation from
the Schro€dinger equation to the KS equations via the effective
potential, as depicted in the lower part of Figure 5. As long as
the effective potential in the KS equations is constructed from
the Schro €dinger equation quantities of the external potential
and the exact exchange-correlation potential, the Schro €dinger
equation and the KS equations will give exactly the same
results for the electron density.
While the HK theorem leads to the KS equations, it does not
tell us what the exchange-correlation functional is. We know
that it exists but we do not know the functional form of it.
The hard problem of solving the SE has been transformed into
a simpler problem to solve, the KS equations, but with the
equally hard problem of finding a good approximation for the
exchange-correlation functional.
Modeling and simulation of actinides and other f-electron
materials and also d-electron materials have long been a chal-
lenge because of the very different behavior of these electrons
compared to s- and p-electrons. This is because the available
DFT functionals have not been up to the task of providing
accurate results for these materials. Instead, a zoo of alterna-
tive methods has been developed to handle the problems.
However, the fact that many competing methods exist indi-
cates in itself that no one method is sufficient for all applica-
tions. In our view, new ideas on how to deal with this class of
materials are needed.
Recently we have taken a new look at the problem, starting
from the very beginning, from the fundamental law of nature
applicable to this type of system, namely the Dirac equation.
In particular, we are trying to cash in on the HK theorem that
establishes that it is sufficient to stay within DFT to be able to
describe also these complicated systems. Traditionally, meth-
ods for these materials have been considered to need theory
beyond DFT. That is, some type of extra consideration is put
on top of the DFT framework. In Figure 5, we make an
International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
TUTORIAL REVIEWS
attempt to disentangle the difference in approach between
our “pure” DFT approach and these “beyond DFT” methods.
In the “beyond DFT” point of view, the KS equations are
considered to be a mean field (MF) theory in which additional
components can be built into the theory by the use of the KS
wave functions. These wave functions, when put in a Slater
determinant form, are considered to be a first approximation
for the electron many-body wave function. This many-body
wave-function can, in this view, then be used in any
Schro €dinger or Dirac equation derived property wave-function
functional, G[W], to extract approximate properties of the
material. This is illustrated in Figure 5.
In contrast, in the pure DFT view, the KS orbitals are only
valid for use in determining the electron charge density, q(r)
or n(r), via the formula on the second line of Eq. (1). This den-
sity, in turn, gives properties of the material via electron den-
sity functionals, F[q]. Unfortunately, there are not many
property density functionals derived. We essentially only have
the total energy density functional. As a side note, to our
knowledge, there is no attempt to find the ultimate density
functional, the density functional of the electron many-body
wave-function, W[q] (circled in red in Fig. 5). Even though the
total energy can give many properties, such as equilibrium vol-
umes, bulk moduli, pressures, and more, many desired proper-
ties are hard to extract from a pure DFT framework. This has
given rise to the practice of using the MF approximation view-
point for extracting approximate properties via insertion of KS
orbitals into wave-function functionals. While this practice is
understandable, we nevertheless point out that if we had the
perfect, or “divine,”[9] exchange-correlation functional, the one
which would give the exact same electron charge density as
the Schro €dinger equation would, only properties calculated via
density functionals would be exact, while properties extracted
from use of the KS orbitals other than the electron charge
density, would still only be approximate.
It is important to note that the main reason we have for
staying within a pure DFT framework is the computational
speed made possible by the KS equations. We do not claim
that staying within pure DFT would necessarily provide a more
accurate method than any other possible scheme for solving
the Schro €dinger equation, but by moving the difficulties from
the solution of the Schro €dinger equation, to the construction
of an accurate exchange-correlation functional, we hope to
make the advanced but computationally expensive DFT-based
methods that are available for standard materials available also
for these more complicated materials.
To emphasize this point we mention that none of the meth-
ods currently considered needed for a highly accurate descrip-
tion of f-electron materials, such as DMFT,[10] GW,[11] and
Gutzwiller,[12] can presently be used to calculate forces on the
ions for use in an MD simulation.
As mentioned earlier, we want to start from the beginning
and work our way toward a full DFT scheme with a clear con-
trol over assumptions and approximations made. Since we are
interested in methods for f-electron materials, and f-electrons
only exist in heavy ions where core and semi-core electrons
can reach relativistic velocities, we need to start with the
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 TUTORIAL REVIEWS WWW.Q-CHEM.ORG
relativistic equation that governs the behavior of relativistic
electrons. This is the Dirac equation.
While d-electron materials are generally considered to be
weakly relativistic, the prevalence of magnetic ordering in this
group of materials shows that d-electron materials will benefit
from a view based on the Dirac equation as well. It is well-
known that orbital and spin moments are coupled in the rela-
tivistic Dirac equation, and these moments only get decoupled
€dinger equation.
in the nonrelativistic limit, that is, in the Schro
Since magnetism is closely related to a competition between
orbital and spin degrees of freedom, the Dirac equation will
shed new light on phenomena in these materials. In any case,
treating nonrelativistic materials with a relativistic theory is still
appropriate, while treating relativistic materials with a nonrela-
tivistic theory is not.
Much of what we here present is not our work but we want
to put all considerations into one article to give a coherent
picture of the field.
Relativistic Density Functional Theory Based
on the Dirac Equation
Starting from the Dirac Equation, Kohn–Sham (KS) equations
can be derived.[13] In this relativistic formulation the 4-current
density, Jl, is the fundamental quantity. While the charge den-
sity, n5J0, remains, the 3-component spin-magnetization, M, in
the Schro €dinger equation-based KS equations is replaced by
the l 5 1, 2, and 3, components of the 4-current Jl as funda-
mental variables. The spin-up and spin-down orbitals are
replaced by four component spinors. While the scalar effective
potential, Veff, remains, the effective magnetic field, Beff, is
replaced by an effective vector field, Aeff. Since nonrelativistic
exchange-correlation functionals are given in terms of n and
M, and not Jl, they cannot be used together with the full
Dirac-based KS equations.
However, performing the so-called Gordon decomposition,
and neglecting the orbital current, I, an approximate Dirac for-
mulation in terms of the usual n and M can be recovered. This
formulation can be implemented in ordinary DFT codes and
be used with ordinary exchange-correlation functionals. A
detailed discussion of the approximations in this formulation is
given in Ref. [14], and a review of all equations is given in the
supplemental material there. In the rest of this article, we will
call this approximate formulation the Dirac treatment, and use
full Dirac for the proper Dirac treatment.
In the absence of a magnetic field and in a spherically sym-
metric effective scalar potential, Veff(r), and after separating
angular and radial variables, the radial equations in the Dirac
formulation becomes (see e.g., Ref. [15])
dfj ð12jÞc
2c 2 fj 5ðEn 2Veff ðrÞ2mc2 Þgj
dr r
(3)
dgj ð11jÞc
c 1 gj 5ðEn 2Veff ðrÞ1mc2 Þfj
dr r
where fj and gj are the radial functions of the lower and
upper components of the four component Dirac spinor,
838 International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
respectively, and j is a nonzero, positive or negative, integer
eigenvalue, coupling spin and orbital momenta. (We have
retained the mass m as a quantity, for pedagogical reasons
since mc2 is the well-known expression for the rest mass. In
the Hartree units, we use here m 5 1). Setting e 5 En2mc2 and
M(r) 5 m1(e2Veff(r))/2c2, and eliminating the lower/small com-
ponent fj, we arrive at
 
1 2 lðl11Þ
2 g00j 1 g0j 2 2 gj
2MðrÞ r r
  (4)
ð11jÞ d 1
2 g0j 1 gj 1Veff ðrÞgj 5egj ;
r dr 2MðrÞ
where we have also used that j(j11)5l(l11) for both signs of j.
In Eq. (4), spin and orbital momenta are not independent
constants of motion but coupled, a coupling represented by j,
the eigenvalue of the operator
!
r  L11 0
K^5 (5)
0 2ðr  L11Þ
where r are the Pauli matrices and L is the ordinary orbital
momentum operator that squared gives eigenvalues l(l 1 1).
If the j-dependent term in Eq. (4) is dropped, as suggested
by Harmon and Koelling,[16] the spin and orbital momenta are
decoupled and only l is needed for the description of the
resulting solution:
 
1 2 lðl11Þ
2 g00l 1 g0l 2 2 gl
2MðrÞ r r
(6)
d 1
2g0l 1Veff ðrÞgl 5egl
dr 2MðrÞ
This is the scalar relativistic (SR) treatment. The term
neglected in the SR treatment (as compared to the Dirac treat-
ment in Eq. (4)) is the spin-orbit (SO) coupling.
The SO term can be included in a SR calculation as a pertur-
bation in various ways. It can, of course, always be included
into the energy after self-consistency is reached in a SR KS
loop, but in all-electron codes based on the muffin tin geome-
try (linear muffin tin orbital (LMTO) and linear augmented
plane wave (LAPW) codes) it is customary to include the SO
term inside the muffin tins (MTs) also in the self-consistent
loop, the so called variational inclusion. In this scheme, the
basis functions inside the MTs are calculated with the SR equa-
tions but the subsequent diagonalization performed to obtain
the KS orbitals is performed with the SO term included. If the
basis had been complete, and derived with appropriate
boundary conditions, this would yield the exact Dirac solution
inside the MTs. The differences in results from this approach
compared to the full use of the Dirac equation are stemming
from the incompleteness of the basis in the MTs, inappropriate
boundary conditions, and from the neglect of the SO term in
the interstitial region.
Historically, the different emphasis on the MT versus the
interstitial regions in LMTO versus LAPW codes, in constructing
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Figure 6. Energy versus volume curves for Thorium calculated with several
different types of basis sets and with several different relativistic treat-
ments. See text for details.
its basis functions, gave rise to some controversy. Because an
LAPW code has its best basis in the interstitial region, accuracy
requires making the MTs as small as possible. In contrast, an
LMTO basis is most accurate inside the MTs, and thus one
tends to make the MTs as large as possible. In a calculation of
several volumes, to obtain an energy versus volume curve for
determining the equilibrium volume, an LAPW code would use
a MT with a fixed radius reasonable for the smallest supercell
volume, while an LMTO code would keep a fixed volume frac-
tion (MT volume/supercell volume) to maximize the MT region
for all volumes. It is understandable that in the SR1SO treat-
ment, a standard use of LMTO and LAPW codes would thus
yield different results. Although LAPW calculations usually give
reasonable results using SR1SO, we demonstrate below that
this is the result of a fortuitous cancellation of errors.
In Figure 6, we show energy versus volume curves for Tho-
rium calculated with an LMTO code, RSPt,[17] using the Dirac,
SR1SO, and SR treatments. Two different types of basis sets
are used, double and triple/full, and the calculations are done
using both the constant MT volume/radius and constant MT
volume fraction schemes. We can draw several conclusions
from this figure.
If we first focus on the differences in the SR calculations
using the fixed volume fraction and fixed radius schemes (the
upper 4, blue, curves), we see that those two calculations dif-
fer when using a double basis but not when using a triple/full
basis. This means that the exact division of space into MT and
interstitial regions is unimportant when using a triple/full
basis; the calculations are converged with respect to basis set.
In fact, using this type of basis it has been shown that the
RSPt LMTO code gives results as accurate as any other good
DFT code.[18,19] The ability to perform the same calculation in
two different ways, fixed radius versus fixed volume fraction,
and get near identical results, can serve as a good conver-
gence criteria, on a par with convergence with respect to
cut-off energy in a plane wave code. For a single volume
calculation, a variation of the MT radius would serve the same
purpose.
International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
TUTORIAL REVIEWS
Next, we focus on the Dirac calculations (next 4, red, curves)
and we see the same trend between double and triple/full
basis, but also that the equilibrium volume only changes very
slightly compared to the SR calculation.
Last we focus on the SR1SO curves (the lower 4 black
curves) and we see that also for the full basis the fixed radius
versus fixed volume fraction schemes give very different
results. It would be reasonable to argue that the fixed volume
fraction curve should give the best result since more of the
SO coupling is included in each volume, but it is also evident
that the fixed radius curve gives an equilibrium volume much
closer to the experimental value of 220.0 bohr3, thus the con-
troversy on how to perform SR1SO calculations.
It was later discovered[20] that the underlying reason causing
these widely different and unexpected results using the
SR1SO treatment was the difference between the behavior at
the origin of the SR p-orbital and the Dirac p1/2-orbital; a SR
basis can simply never describe a Dirac p1/2-orbital. This is dis-
cussed in more detail in Ref. [14].
There have been several attempts to cure the underlying
deficiency of the SR p-orbital in the SO treatment. One is to
simply omit the faulty p-orbital in the SO coupling,[21] another
to add a Dirac p1/2-orbital to the basis inside the MT.[22]
From Figure 6 it is tempting to conclude that a simple SR
treatment would be good enough for most calculations, but
that is not a correct conclusion. In Figure 7, we show the Den-
sity of States (DoS) at experimental equilibrium volume using
SR, SR1SO, and Dirac treatments. While SR1SO and Dirac
both correctly give the well-known consequence of relativistic
spin-orbit coupling, a splitting of the p-orbital peak into p1/2
and p3/2 (see e.g., Ref. [15]), this splitting is not present in a SR
treatment. Note that if SO coupling of p-orbitals is omitted,
the splitting of the 6p DoS peak will not be present, losing, as
we have just seen, one of the most striking effects of the spin-
orbit interaction, which in general would seem to be an unde-
sirable approach to relativistic treatment.
Figure 7. Density of States for Thorium at the experimental equilibrium vol-
ume, with SR (black), SR1SO (blue), and Dirac (red) treatment, aligned at
their Fermi energies. While both Dirac and SR1SO are splitting the 6p
peak into a 6p1/2 and a 6p3/2 peak, the SR treatment gives only one peak.
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 TUTORIAL REVIEWS WWW.Q-CHEM.ORG

ities in the charge density due to implicit or explicit surfaces,

Table 1. Thorium equilibrium volumes in cubic bohr and bulk moduli in
GPa, calculated using the SR, SR1SO, and Dirac methods, with three dif- it still does not account for the electron localization present in
ferent exchange-correlation functionals, AM05,[4] PBE,[24] and LDA in the many d- and f-electron materials. In the next section we will
PW[25] version. discuss our approach for correcting for this failure in the con-
struction of functionals, a scheme that should render a func-
V (bohr3) B (GPa)
tional adequate for d- and f-electron materials.
Method AM05 PBE LDA AM05 PBE LDA
SR 204.55 217.36 199.89 58.9 54.5 65.5 Exchange-Correlation Functionals
SR1SO 189.62 201.21 186.45 74.1 68.6 80.4
Dirac 205.98 217.98 201.54 62.4 58.3 68.0 With the help of Figure 8, it is straightforward to understand
These should be compared with the experimental volume extrapolated how differently electrons with different angular momenta can
to zero temperature with zero point motion subtracted: 220.00 behave in a material. While s-electrons can move freely
bohr3.[26] Experimental bulk moduli vary but Ref. [27] gives a best value through the ion lattice, f-electrons can still be tightly bound.
at room temperature of 58 GPa, and the zero-temperature extrapolated
value must be larger than the room temperature value. The s-electrons are delocalized while the f-electrons are local-
ized at the ion sites. There are other situations as well where
localized and delocalized electrons cohabit the same material.
All in all, we conclude that the only reliable route to accu-
This cohabitation often gives rise to interesting and valuable
rate DFT calculations for relativistic materials is the use of the
properties of the material, in particular in materials that consist
Dirac equation-based KS equations. At the very least, such a
of ions that in their atomic state have partially occupied d- or
method should be available and used for benchmarking and
f-orbitals. The competition between localization and delocaliza-
evaluation of more approximate schemes. In particular, we dis-
tion in these materials can give rise to a rich phase diagram
courage the use of the SR1SO scheme, in particular, when p-
with many competing arrangements of ions driven by the pos-
electrons are involved. Simply put, if the SO coupling is large
sibility of large changes in electronic structure with tempera-
enough to make a difference in the calculations, it is also too
ture and/or volume.
large to be treated as a perturbation. However, additional
This can be understood from Figure 9, where a schematic
inquiry into the Dirac scheme is needed to assess the influ-
density of states for the material in Figure 8 is shown. Depend-
ence of the approximation of neglecting the orbital current. It
ing on whether the chemical potential is in the broad s-band
has been shown that orbital polarization makes a non-
or in the narrow f-band, large variations in properties can be
negligible contribution in some materials,[21,23] and this would
obtained.
indicate that the full Dirac scheme might be needed. However,
As an important side note we point out that in the SR calcu-
the number of patches applied to SR calculations for these
lations discussed in the previous section, the radial part of the
materials to mimic the full Dirac treatment (spin polarization,
of the p-electrons orbitals is forced to go to zero near the
orbital polarization, partial SO coupling etc.), could obscure
nucleus because of the angular momentum barrier shown in
the correct contribution from each term. Careful evaluation is
Figure 8. In a Dirac treatment, however, the inclusion of the
required to decide when the full Dirac scheme is needed and
SO term cancels the angular momentum term for l51 and
when the approximate Dirac scheme is sufficient.
j51, that is, for the p1/2 orbital (use that M(r) ! 1/r as r ! 0
In Table 1, we show the equilibrium volume and bulk modu-
lus calculated with the different relativistic treatments here dis-
cussed, and with three different exchange-correlation
functionals. All calculations are done with the usual LMTO
fixed volume fraction scheme, and it is clear that without cor-
rections the straightforward SR1SO scheme is not valid. As we
noted before, SR and Dirac treatments give almost identical
equilibrium properties, regardless of functional, but the
absence of splitting of the 6p DoS peak (see Fig. 7) in the SR
calculations leaves us with the conclusion that the Dirac
scheme is the only reasonable approach for true predictability.
Comparing the equilibrium results with respect to which
exchange-correlation functional was used, it is clear that PBE
gives the best results for Thorium. However, it is well-known
that PBE generally predicts values for the lattice constants of
Figure 8. In a material consisting of a periodic array of ions, electrons with
solids that are too large (for example, the equilibrium volume different angular momenta will move in different effective potentials, as
predicted for gold is 7% larger than experiment.[26]) In general, seen from the included formula (compare with Eq. (4)). Even though the s-
the functional trend for solids is for PBE to be underbinding electrons, with l50, can move freely in the material as depicted by the
orange free electron band, f-electrons, with l53, can be tightly bound to
(giving too large volumes), LDA to be overbinding (giving too
the ions and only form narrow bands (blue). The “angular momentum
small volumes), and for AM05 to be somewhere in barrier” near the center of the ion in the f-electron effective potential is
between.[18,26] Although AM05 correctly handles inhomogene- further discussed in the text.

840 International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097 WWW.CHEMISTRYVIEWS.ORG

 WWW.Q-CHEM.ORG
Figure 9. A schematic density of states for a solid material with both s-
and p-electrons, which form a broad free-electron like band, and d- or f-
electrons, which form a narrow band.
in Eq. (4)). This leads the orbital to be non-zero at the origin,
the same as for an s-orbital in either treatment, which is the
fundamental cause that SR1SO calculations generally fails. An
SR basis cannot describe a SR1SO p1/2 orbital and only a fully
variational approach to SR1SO or the Dirac treatment will be
able to give accurate results.
The ability to describe these materials computationally is
fundamentally related to the ability of the exchange-
correlation functional to describe localized and delocalized
electrons equally well, as not to bias the calculation toward
one phase or the other. While the understanding of materials
with a competition between localized and delocalized elec-
trons is well understood in DoS space, exchange-correlation
functionals live in real space. The question is then how we can
translate the knowledge we have about localization and deloc-
alization in DoS space, to real space.
The paradigm system for a broad free-electron-band is the
uniform electron gas, while atomic orbitals can be taken as a
paradigm system for the narrow f-band, noting that this nar-
row band is formed from electrons hopping or tunneling
between of a collection of discrete atomic levels.
The local density approximation (LDA) functional is based
on results for the uniform electron gas, and this functional
also works well in systems where broad free-electron-like
bands govern the properties. From Table 1, however, we see
that LDA does not give good equilibrium properties for tho-
rium, which is consistent with LDA failing in many other d-
and f-electron systems.
However, we note that the Perdew–Burke–Ernzerhof (PBE)
functional[24] gives good equilibrium properties and we note
that when PBE gives good equilibrium volumes for solids it is
often taken to mean that an exact exchange or a hybrid
exchange-correlation functional is needed for a good descrip-
tion of all properties of those solids. This is because PBE is
constructed to work well for atoms and molecules, which are
systems well described by hybrids. The fact that PBE gives bet-
ter results than AM05 for thorium’s equilibrium volume is thus
a sign that the physics encoded in the exchange energy
expression, which is the same as the Hartree-Fock energy
expression that is included in a hybrid functional, might be
needed for the description of d- and f-electron materials.
International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
TUTORIAL REVIEWS
The crucial ingredient that is included in the exact exchange
and Hartree–Fock treatments is the Pauli principle, which in
turn describes the fermionic nature of electrons. We thus con-
clude that the fermionic nature of electrons, or more adequately
stated, the Kohn–Sham particles, which are also fermions, needs
to guide us when we seek to construct a functional that better
describes the mixture of broad and narrow bands, delocalized
and localized electrons, of the d- and f-electron materials.
Let us now focus on what distinguishes a fermion from a
boson. One of the main consequences of the Pauli principle is
that fermions cannot be in the same point in space unless they
have different spin quantum number, for example spin up and
spin down. In more general terms this means that every fermion
needs to have its own set of quantum numbers. We can for
example put one electron with spin up and one with spin down
in each quantized energy level of a quantum mechanical system
(for simplicity we assume zero temperature), since each such
level is described by a unique set of quantum numbers. If this
same quantum mechanical system’s energy levels were popu-
lated with bosons, all bosons would go into the lowest quantum
level since bosons can be in the same point in space and can all
have the same quantum numbers (bose condensates). For a
boson, all wavefunctions can be the same and in this case
rffiffiffiffiffiffiffiffiffi
nðrÞ
wb ðrÞ5 : (7)
N
It is useful for our present discussion to understand fer-
mions and bosons in the context of potential and kinetic
energy as the quantum numbers are giving the total eigen-
value energy of quantum particles. Let us first examine the
“uniform electron gas,” which in our context is defined as fer-
mions moving in a constant potential. In a uniform electron
gas all fermions have the same potential energy, and to differ-
entiate among themselves, all with the same spin need to
have different kinetic energy. Bosons in a constant potential,
however, can all have the same kinetic energy, and from Eq.
(7) and the positive definite definition of the kinetic energy
density term (obtained by a partial derivative of the total
kinetic energy obtained from the very first term in the KS
equations (Eq. (1)), it is straightforward to obtain
jrwb ðrÞj2 1 jrnðrÞj2
sb ðrÞ5N ¼ : (8)
2 8 nðrÞ
In fact, this formula is always valid for bosons, regardless of
system. Note that for a “uniform electron gas” the kinetic
energy density of a Bose condensate is 0 since the density has
no gradients. In a uniform electron gas it is fairly straightfor-
ward to derive the kinetic energy density for fermions as well,
and the result is
3  2 2=3
su ðrÞ5 3p nðrÞ5=3 : (9)
10
The kinetic energy density of a uniform fermion gas is indeed
larger than a uniform boson system with the same density.
841
 TUTORIAL REVIEWS WWW.Q-CHEM.ORG
Let us now consider an isolated atomic potential with non-
interacting (other than with statistics) quantum particles.
Boson and fermions would have the same atomic energy lev-
els/states to populate. While the bosons could all populate the
lowest energy state, only two spin half fermions would be
able to go into each level, one spin-up and one spin-down. In
this case each same spin fermion, however, already has differ-
ent average potential energy, and they do not need to adjust
their kinetic energies because of other fermions nearby. How-
ever, the density of a boson system with all particles in the
lowest level would not be the same as the density of the fer-
mion system. To have the same density in both the boson and
the fermion systems, we would need to put two bosons in
each level as well. But in this case, bosons and fermions would
have exactly the same kinetic energy density. In summary,
when a fermion is completely localized it has the same kinetic
energy as a similarly localized boson.
The last case we consider is the classically forbidden region.
Far outside of a surface we will only find quantum particles
with very large kinetic energy. It is tempting to assume that
bosons and fermions would have the same very large kinetic
energy, but that is not the case. This can be understood from
how bosons and fermions behave at very low density. At very
low density fermions arrange in a Wigner crystal because of
the exchange interaction, while bosons do not have any incen-
tive to arrange themselves in any pattern since they can share
the same point in space without penalty. This is a sign that,
even at very low density, fermions will have to adapt their
kinetic energy though bosons do not.
This view is in contrast with the view that electrons far out-
side of a molecule have kinetic energy density in form of the
von Weizs€acker kinetic energy, which is the kinetic energy den-
sity of a pure one-electron system or a spin-up/spin-down pair
of electrons, so called single-orbital system. The kinetic energy
of a single orbital system is of course the same as the boson
kinetic energy since no other electrons with same spin are
around that this single electron needs to adjust to, and of
course the von Weizs€acker kinetic energy density formula is
identical to the boson condensate kinetic energy density in
Eq. (8). This difference in views might be only academic, at
least in more extended systems such as solid state systems,
since in those systems the single orbital scenario will never be
valid. However, it is a large conceptual difference in these two
views and for functional development, it might be important.
At this point, we will briefly describe the electron localiza-
tion function that codifies this information in a compact
formula.
The Electron Localization Function and the
Fermionic Nature of Electrons and Kohn–Sham
Particles
The electron localization function (ELF), was formulated by
Becke and Edgecomb in 1990.[28] It includes quantities we
have already mentioned in this article, such as the positive
definite definition of kinetic energy density, boson kinetic
842 International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
energy density (Eq. (8)), and the uniform electron gas fermion
kinetic energy density (Eq. (9)):
1
ELF5
11ðD=Dh Þ2
1 jrnðrÞj2 (10)
D5s2
8 nðrÞ
3  2 2=3
Dh 5 3p nðrÞ5=3
10
In the Becke and Edgecomb article, however, the elements
of ELF are associated with a statistical interpretation. Instead
we have developed[29] a new interpretation of ELF, in terms of
the fermionic nature of the KS particles, based on an article by
Silvi and Savin in 1994.[30]
We see that for a localized system, where the kinetic energy
density of the KS particles is boson like, the ELF 5 1. In a uni-
form electron gas, ELF 5 1=2, and far outside of a surface ELF !
0. By examining ELF in a real system, we can identify the
nature of the physics governing different regions in space.
It is important to note that while the kinetic energy density
is only defined in terms of the total kinetic energy, and thus is
not unique, the ELF is unique. As long as the same definition
of kinetic energy density is used for the calculation of all
ingredients in D and Dh, the ELF is independent of definition.
This translate to that the ELF is uniquely identifying the nature
of the physics in regions in space. We also note that since a
boson system always has the smaller kinetic energy density, D
will always be positive, regardless of the definition of the
kinetic energy density itself. A last note is that despite that the
name of ELF includes “electron” this index is valid for all fer-
mions. This is important in this context, as the KS particles are
fermions but not necessarily have anything to do with
electrons.
In recent work by John Perdew and collaborators,[31] the
quantity aP 5 D/Dh has been used extensively, and we will
show the limits of this parameter in addition to the ELF to
emphasis the equivalence of the two indices. Our interpreta-
tion of ELF in terms of the fermionic nature of the particles is,
however, not shared between our group and the Perdew
group.
The subsystem functional scheme
The subsystem functional scheme was proposed by Walter
Kohn and Ann E. Mattsson in 1998,[32] and has been further
developed and generalized together with Rickard
Armiento.[33–35] It is extensively described in Ref. [35] and we
will here only give the key ingredients of this scheme. The
exchange-correlation energy density, exc[n(r)], the “functional,”
is defined via the total exchange-correlation energy by
ð
Exc ½nðrÞ5 nðrÞexc ½nðrÞ: (11)
V
The subsystem functional scheme is based on the fact that
any integral over a space V can be divided into integrations
WWW.CHEMISTRYVIEWS.ORG
 WWW.Q-CHEM.ORG
Figure 10. The ELF (green, dash-dotted) and scaled exchange energy density calculated exactly (black, solid) via the conventional definition and with the
parameterizations based on the uniform electron gas (red, dashed) and the Airy gas (blue, dotted), of two harmonic oscillator systems. a) a highly confined
system with a 5 0.06, and b) a less confined system with a 5 5.40. For more details see Ref. [29]. The figures are reproduced from Ref. [29], published in
2014, an article produced under a U.S. Government contract and in the public domain.
over subsystems. The main idea is to divide the system into
parts and to use a distinct functional in each part that gives
an adequate description of the governing physics in that
specific part. The subsystem functional scheme thus needs
two types of ingredients: (1) a function, or index, that can
identify the governing physics in each part of space, and (2)
one functional for each type of physics that needs to be
described.
In the Armiento-Mattsson 2005 (AM05) functional,[4] the first
subsystem functional, the scaled/dimensionless density
gradient,
jrnj
s5 ; (12)
2ð3p2 Þ1=3 n4=3
is used to identify either of two subsystems; the uniform elec-
tron gas (when s 5 0) or an electronic surface (s ! 1). In the
uniform electron gas limit, the local density approximation is
used while in a region with an electronic edge a functional
derived from the Airy gas and the jellium surface model sys-
tems, is used. In practice, the user never needs to divide the
system but an interpolation index is used to interpolate
between the two limits, so that when s has a non-zero value,
the global functional provides predetermined (from the con-
struction process) proportions of the two subsystem
functionals.
We note that, as with the kinetic energy density, the defini-
tion in Eq. (11) is not unique but any function that integrates
to zero can be added. The consequence, as in the case of the
kinetic energy density, is that the same definition of exchange-
correlation energy density needs to be used in each subsys-
tem. If this is not done, surface terms would arise from the
boundaries of the subsystems and those would be unac-
counted for in a general functional.
In particular, this means that the exchange part of each sub-
system functional needs to be based on the same definition of
exchange energy density. This precludes the use of the
constraint-based functional forms of exchange, such as the
PBE[24] and PBEsol[36,37] exchange functionals used in recent
work by the Perdew group,[31] since the underlying exact defi-
nitions of these functionals are unknown. Instead we use the
well-defined conventional exchange energy,
International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
TUTORIAL REVIEWS
ðX
wt ðrÞwt ðr0 Þwg ðrÞwg ðr0 Þ 0
ex ðrÞ52 dr (13)
t;g
jr2r0 j
In the context of the subsystem functional scheme this was
first discussed in 2002 in Ref. [34].
The correlation energy in DFT is defined as “the rest,” that
is, the remaining energy when all known energies in DFT are
subtracted from the true SE or Dirac equation energy for the
same system. The correlation part of the functional thus exhib-
its the same ambiguity as the exchange part but it is much
harder to pinpoint because of the lack of explicit definition.
However, if a total energy density can be calculated with the
SE/Dirac equation, the correlation energy density would be
the energy density remaining when all well-defined contribu-
tions are subtracted. One example is the uniform electron gas
where the SE total energy corresponds to the total energy
density because of the uniformity and the infinite dimensions
of the system.
The AM05 functional includes the physics of surfaces,[4]
which is distinctly different from the physics of a uniform elec-
tron gas, and gives very good results for a large group of
materials and properties.[18,26,38–40] In fact, when published in
2005, it outperformed every existing functional of the same
type (based on the dimensionless gradient) and opened up for
a new examination of a field that was considered closed. How-
ever, the additional distinctly different physics of localization is
not taken into account in AM05, and our goal is to include
this physics in addition to the uniform electron gas, and the
electronic edges, into a new functional.
Since the ELF can distinguish between regions in space
where either of the three types of physics we are considering
exists, we want to trade the dimensionless gradient-based
index used in AM05 for ELF. The remaining ingredients needed
in a subsystem functional scheme are one specialized func-
tional for each of the three types of physics we are
considering.
Uniform Electron Gas. The natural functional to use for the
uniform electron gas (ELF51=2, aP51) is the LDA. LDA exchange
is based on the conventional exchange energy and thus a
valid functional for the subsystem functional scheme. In addi-
tion, an LDA correlation based on the Ceperley and Alder
843
 TUTORIAL REVIEWS WWW.Q-CHEM.ORG

Figure 11. The exchange energy density for a harmonic oscillator system with a 5 0.23 obtained with, a) the uniform electron gas and different parameter-
izations of the conventional definition of the Airy gas exchange energy density (LAA,[4] LAG,[43] and ARPA[44]), and b) with four different exchange function-
als. Only the Airy gas parameterizations and the functional based on the conventional definition of the Airy gas exchange, AM05x, give sensible results in
the surface region. For details and definitions, see Ref. [42]. The figures are reproduced from Ref. [42], published in 2010, an article produced under a U.S.
Government contract and in the public domain.

Quantum Monte Carlo calculations for the uniform electron To contrast this work to the work of the Perdew group we
gas[41] gives a well-defined correlation energy density. show, in Figure 11, the exchange energy density for a confined
HO gas system as calculated with a few additional exchange
The Airy Gas. The Airy gas[32] and jellium surface systems
functionals not based on the conventional definition, namely
have already proven to be adequate model systems for the
PBEx and PBEsolx. It is clear that only the Airy gas-based
physics of electronic edges (ELF ! 0, aP ! 1). Both the Airy
AM05 exchange functional gives a good description in the sur-
gas exchange and the jellium surface exchange are calculated
face region. For more information see Ref. [42].
from the conventional definition of exchange. The correlation
part of the AM05 functional is obtained from the total surface Summary. To obtain a computationally efficient exchange-
energy of the jellium surfaces and is not completely unambig- correlation functional that can give accurate results for d- and
uous even though it is clearly confined to the edge region of f-electron materials and compounds, we suggest using the
a system. This should minimize the magnitude of possible sur- subsystem functional scheme. We want to use the electron
face terms. In the new global functional proposed here, we localization function, ELF, to determine what specialized func-
will continue to use the jellium surface energy, making adjust- tional to use in what region of space. As specialized function-
ments for the new subsystem functional included to appropri- als we suggest using: (1) The local density approximation,
ately describe localization regions. LDA, which is based on the uniform electron gas model sys-
The Harmonic Oscillator Gas. For regions in space with local- tem, in the regions where ELF  1=2, indicating that the fer-
ized fermions (ELF51, aP50) we have suggested using the mionic Kohn–Sham particles behave as if they were in a
Harmonic oscillator (HO) gas[42] model system, a three dimen- uniform electron gas; (2) A functional based on the Airy gas
sional system with a confining harmonic potential in one
direction and constant potentials in the other two. It can be
seen as a metal slab and in the limit of strong confinement
the fermion gas becomes two-dimensional. In recent work by
Perdew et al.,[31] a functional based on an atomic system is
used in this region, but we prefer a more open system that
will better describe the coexistence of, and transition between,
localization and delocalization.
In Figure 10, we show the conventional exchange energy
density in two different HO systems with degrees of confine-
ment described by the chemical potential parameter a: a low
value gives a strongly confined system close to two-
dimensional, and a large value gives a less confined system
tending toward a three-dimensional electron gas. For exact
definitions and a complete description, see Refs. [29,42].
We note that neither the Airy gas nor the uniform electron
gas, can describe the exchange energy density where ELF is
Figure 12. A summary of our subsystem functional strategy for creating a
large, while both give good descriptions when ELF  1=2 (uni-
global functional appropriate for d- and f-electron systems by including
form electron gas limit). When we are in the surface region the physics of the uniform electron gas, the Airy gas, and the HO gas in
(1=2 > ELF ! 0) only the Airy gas gives a good description. proportions determined by an index based on the ELF.

844 International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097 WWW.CHEMISTRYVIEWS.ORG

 WWW.Q-CHEM.ORG
and jellium surface model systems when ELF ! 0, indicating
that the fermionic Kohn–Sham particles have high kinetic
energy and behaves as they are outside of a surface; (3) A
functional based on the Harmonic oscillator gas model system
in regions where ELF  1, indicating that the Kohn–Sham par-
ticles are localized and behave like bosons. This strategy is
summarized in Figure 12.
As a last note we point out that since ELF depends on the
kinetic energy density, the resulting global functional will at a
minimum be a meta-generalized gradient approximation
(meta-GGA). However, simultaneous efforts are underway[45] of
finding good density-based approximations for the kinetic
energy density. While the accuracy of such approximations
needs to be very high for use in the orbital-free DFT method,
where such an approximation is replacing the full kinetic
energy term in the KS equations (see Eq. (1)), we suggest that
the same high accuracy might not be needed for an interpola-
tion index in the subsystem functional scheme. In addition,
there are efforts at replacing the ELF directly with a purely
density-based alternative.[46] However, our use of ELF is based
on its interpretation as a measure of the fermionic nature of a
system, an interpretation that is unique for ELF and not con-
sistent with available alternatives.
Conclusions and summary
In this article, we have examined many aspects of the method
development needed to provide highly accurate DFT calcula-
tions for d- and f-electron materials and compounds. Since our
ultimate goal is to provide a computationally effective method
able to perform, for example, the DFT-based MD calculations
needed for examining properties at non-zero temperatures, we
have focused on the “pure” DFT scheme that lies well within
the Hohenberg–Kohn theory.
We have discussed the necessity for basing a treatment of
heavier ions on the relativistic Dirac equation instead of using
the ordinary treatment based on the Schro €dinger equation,
even if it is amended with a variational treatment of spin-orbit
coupling.
However, to be able to use DFT exchange-correlation func-
tionals in standard form, that is, in terms of electron charge
density and spin magnetization, Exc[n(r),M(r)], an approxima-
tion in the Dirac equation-based Kohn–Sham equations is
needed. This approximation, of not including the orbital cur-
rent, is well-defined and the neglected term should be eval-
uated in a post-processing manner. If, in the future, it turns
out that the neglected term is too large to be neglected, the
only alternative is to construct exchange-correlation function-
als in terms of the four current, Exc[Jm(r)]. Most of the con-
straints used in the constraint-based functional development
€dinger
approach of the Perdew group are based on the Schro
equation, and not automatically valid for the Dirac equation. If
we need to develop this new type of functional, several ingre-
dients, such as, the definition of exchange and correlation,
need to be revisited, and new challenges, such as choice of
gauge, are expected to arise. We will need either a new set of
constraints derived from the Dirac equation or new, alterna-
International Journal of Quantum Chemistry 2016, DOI: 10.1002/qua.25097
TUTORIAL REVIEWS
tive, approaches to functional development. As such, the sub-
system functional scheme, which is based on exact
(Schro€dinger or Dirac equation) calculations of exchange and
correlation in model systems, should still work.
By realizing the ability of the electron localization function,
ELF, to distinguish regions in space where confinement, sur-
face, and uniform electron gas behavior of the Kohn–Sham
particles dominates the physics, we propose a scheme for con-
structing a global exchange-correlation functional that accu-
rately describes systems where these three types of competing
behavior exist. The global functional will use ELF in an interpo-
lation index that interpolates between three specialized func-
tionals each designed to accurately describe one particular
situation. While the ELF probably cannot be used in a 4-
current functional directly, the interpretation of it as identify-
ing the fermionic character of the KS particles could probably
guide us toward an appropriate interpolation index for this
type of exchange-correlation functional.
Acknowledgments
Sandia National Laboratories is a multi-program laboratory man-
aged and operated by Sandia Corporation, a wholly owned subsidi-
ary of Lockheed Martin Corporation, for the U.S. Department of
Energy’s National Nuclear Security Administration under contract
DEAC04-94AL85000. Los Alamos National Laboratory, an affirma-
tive action/equal opportunity employer, is operated by Los Alamos
National Security, LLC, for the National Nuclear Security Administra-
tion of the US Department of Energy under contract DE-AC52-
06NA25396.
Keywords: density functional theory  dirac equation  relativis-
tic treatment  exchange-correlation functional  subsystem
functional scheme
How to cite this article: A. E. Mattsson, J. M. Wills. Int. J. Quan-
tum Chem. 2016, , 834–846. DOI: 10.1002/qua.25097
[1] For a video of the construction and collapse of the Tacoma Narrows
1940 bridge from the Stillman Fires Collection, visit https://archive.org/
details/Pa2096Tacoma. Another account of the collapse, with many
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ment of Transportation at: http://www.wsdot.wa.gov/TNBhistory/Con-
nections/connections3.htm
[2] For information about the ALEGRA family of multi-physics codes,
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