Molecular Physics

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Use of Löwdin orthogonalised Fermi orbitals for

self-interaction corrections in an iron porphyrin

Der-you Kao & Mark R. Pederson

To cite this article: Der-you Kao & Mark R. Pederson (2016): Use of Löwdin orthogonalised
Fermi orbitals for self-interaction corrections in an iron porphyrin, Molecular Physics, DOI:
10.1080/00268976.2016.1225992

To link to this article: http://dx.doi.org/10.1080/00268976.2016.1225992

Published online: 08 Sep 2016.

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Download by: [University of California, San Diego] Date: 12 December 2016, At: 04:52
MOLECULAR PHYSICS, 
http://dx.doi.org/./..

56TH SANIBEL SYMPOSIUM - SPECIAL ISSUE

Use of Löwdin orthogonalised Fermi orbitals for self-interaction corrections in an

iron porphyrin
Der-you Kaoa and Mark R. Pederson b

a
Mechanical and Aerospace Engineering, The George Washington University, Washington, DC, USA; b Department of Chemistry, Johns Hopkins
University, Baltimore, MD, USA

ABSTRACT ARTICLE HISTORY

A new approach for formulating the self-interaction correction, referred to as the Fermi-Löwdin Received  April 
orbital-based self-interaction correction (FLO-SIC), is briefly reviewed and applied to the Fe(II)- Accepted  August 
porphyrin molecule. The Fermi–Löwdin orbitals are localised but due to the fact they are constructed
KEYWORDS
directly from the spin-density matrices, they lead to a set of orbitals that have the property that Fermi–Löwdin orbital;
each and every orbital is explicitly invariant to unitary transformations. These orbitals allow one to self-interaction correction;
constrain the Perdew–Zunger self-interaction correction in a manner that ensures that the energy Fe(II) porphyrin; density
is explicitly invariant to unitary transformations and size-extensive. We review these improvements functional theory
and show how the multiple solutions, intrinsic to the original formulation, are removed through the
constraint offered by the Fermi–Löwdin construction. The locations of descriptors of Fermi–Löwdin
orbital imitate the formation of classical chemical bonds. The very first application of this method to
a system containing a transition metal atom is presented here.

1. Introduction Fermi–Löwdin orbitals (FLOs). Such orbitals depend

on first constructing normalised Fermi orbitals (FOs)
An approach for implementing the self-interaction cor-
which are explicitly dependent on a single-particle
rection (SIC) to density-functional approximations and
density matrix but depend parametrically on a set of
recovering an asymptotically exact effective potential is
quasi-classical electronic positions or descriptors. When
due to Perdew and Zunger and dates back to 1981 [1].
orthogonalised via Löwdin’s method of symmetric
However, the explicit orbital dependence, or alternatively
orthonormalisation, the formalism allows for the deriva-
unitary non-invariance, associated with this formu-
tion of an N × N unitary matrix that depends explicitly
lation leads to large increases in computational costs
on the density matrix and N quasi-classical electronic
due to the need to solve the localisation equations for
positions that we refer to as electronic descriptors. Thus,
SIC and also leads to an energy expression that is not
for any set of Kohn–Sham orbitals, the self-interaction
size-extensive. In a recent work, a size-extensive unitarily
energy is reduced to a function of 3N parameters that
invariant reformulation of the SIC has been introduced
can be minimised using standard gradient methods.
which proceeds through the construction of energy-
Recent work on applications to small molecules [2],
localised orthonormal orbitals that are referred to as

CONTACT Mark R. Pederson mpeder@jhu.edu

©  Informa UK Limited, trading as Taylor & Francis Group
2 D.-Y. KAO AND M. R. PEDERSON

medium-sized molecules [3], and large molecules [4]

have provided very encouraging results. For example,
using the local density approximation [5] of Perdew and
Wang (PW92), it was found that cohesive energies in
small molecules were significantly improved, especially
for systems with π bonds, and that the HOMO/LUMO
gaps are increased relative to their Kohn–Sham counter-
parts which is the trend one needs to shift the eigenvalues
in a manner that allows the energy of the HOMO state
to match the ionisation energy. To date, there have not
been any applications of the method to systems contain-
ing transition-metal atoms or ions which represent the
types of atoms where the need for SICs was originally
noted by Lindgren [6] and Janak et al. [7]. As such, this
work applies this new formulation to a spin unpolarised
metal porphyrin and to a spin-ordered metal porphyrin
both of which have no net spin. While we are primarily
interested in demonstrating the use of FLO-SIC on the
spin-unpolarised system, we include PW92 results from
a second (lower energy) orbitally ordered system, with
no net moment, since this structure has different fillings
of the 3d orbitals.
Porphyrins, which consist of four pyrrole groups Figure . A bent Fe(II)-porphyrin: hydrogens are white, carbons are
linked by methene bridges with a transition-metal centre, grey, nitrogens are black, and iron is larger central atom. The upper
have been selected by nature as the functional pigment of panel is the top view of Fe(II)-porphyrin and the lower panel is the
side view.
biology. Because transition-metal atoms can exist in mul-
tiple spin and charge states and due to their large natu-
rally occurring terrestrial abundance, nature has chosen rather strong relationships between the spin structure of
such systems to form the basis of many life-sustaining and the electrons and distortions of the porphyrins. Demon-
catalytically interesting molecular systems. The redox strating this for systems with no net moment is instruc-
property of irons centred in porphyrins in heme leads tive, since, in addition to interesting physics, it is a factor
to a charge-induced polarisation of nearby closed shell that must be accounted for if comparisons between dif-
molecules (such as O2 ), and hence the Fe-porphyrin (Fig- ferent calculations are to be meaningful.
ure 1), is able to carry oxygen [8–13]. Although approximations based upon the DFT pro-
Several porphyrin complexes exhibit novel magnetic, vide excellent predictive power for many fundamental
electronic, optical, and photoelectrical properties. For properties, an outstanding challenge has been to reliably
instance, in a study of polypyrrole, containing porphyrin predict some properties of transition-metal-containing
moieties, it has been shown that the molecular system molecules, especially when undercoordinated, such as for
experiences an immediate increase in electric resistance the case of Fe(II)-porphyrin. Lower spin states are known
when carbon monoxide gas binds to the iron at the cen- to be favoured by GGA exchange-correlation function-
tre of the porphyrin [14]. In addition, it has been demon- als, while hybrid functionals that include a fraction of
strated that a self-assembled oligomeric porphyrin ladder Hartree–Fock exchange often prefer high-spin states.
can mimic light harvesting [15] that is found in natu- Furthermore, different energy gaps between spin states
rally occurring photosystems. A network of Fe(II) meso- are obtained with different exchange-correlation func-
tetra(4-pyridyl) porphyrin with an effective moment of tionals [17]. One suggested deficiency of DFT in describ-
5.52 B has been reported with high thermal stability at ing transition metals is that relatively localised 3d valence
room temperature [16]. Preliminary understanding of electrons suffer strongly from self-interaction error pre-
this experimental investigation posits that the observed senting in pure density functionals. Self-interaction error
spin-glass-like behaviour could be caused by either local is only approximately corrected in hybrid functionals.
lattice distortions or the existence of vacancies at the While the work discussed here is on a transition-metal
Fe(II) sites. Both of these effects are expected to modify system, it should be noted that such problems are even
the local exchange coupling. An additional result from more severe in the heavier atoms where even stronger
the work discussed here shows that there are, indeed, errors in the Coulomb interaction cause qualitatively

incorrect fillings in the f-electron series. A discussion of
this problem can be found in [18].
The need for the use of SICs for systems containing
transition-metal ions was first suggested by Lindgren [6]
in applications to the Cu atoms. The formulation pro-
posed by Lindgren introduced the self-interaction at the
level of the single-electron Hamiltonian and proposed
correcting the error in the interelectronic exchange func-
tional, derived from the free-electron-gas model, in a
local-density approximation. In 1981, Perdew and Zunger
proposed the SIC at the level of the total energy expres-
sion, so it could be applied to functionals designed to
include correlation and exchange effects [1] and also serve
as an ab initio alternative to the LSDA+U method for the
description of strongly correlated systems.
Perdew and Zunger posited that the orbital densi-
ties, ρ i (r) = |φ iσ (r)|2 , could be constructed from a set
of localised orbitals that are similar to the Edmiston–
Ruedenberg [19] energy-localised orbitals in the Hartree
approximation. Later, Pederson et al. [20–22] suggested
the use of localisation equations as a variational means
for addressing the unitary non-invariance that existed
in the original PZ formulation. This approach has been
the primary means for variational SICs as discussed
in recent reviews [23–30]. While the original version
of SIC [20–22] only considered real orbitals, several
researchers [27,31,32] have noted that there is no a pri-
ori reason to expect that complex orbitals could not lead
to lower SIC energies in the original PZ formulation and
have subsequently derived additional formula for finding
stationary solutions. Pederson and Perdew noted in [33]
that real localised orbitals which minimise the SIC energy
are stationary with respect to complex unitary transfor-
mations but again did not guarantee that the real solu-
tions could not be a saddle point or local maximum. More
recently, a modification of the functional has been made
through the use of FLOs for the SIC.
While we have stressed the fact that this new version of
SIC has the same functional form as the original Perdew–
Zunger (PZ) SIC but offers formal improvements by con-
straining the functional to be an explicit density func-
tional, it is appropriate to reconsider some past discus-
sions on one of the simplest atoms where the original
formulation leads to multiple stationary solutions for a
given set of Kohn–Sham orbitals. Except for cases that
explicitly violate size-extensivity, the existence of multi-
ple stationary solutions is not a formal problem since it
is only the lowest energy configuration of these multiple
solutions that should be compared to experiment. How-
ever, the fact that they exist in the simplest isolated atoms
creates intrinsic uncertainties in applications, since, for
energy landscapes with multiple stationary points, it is
always difficult to guarantee that the ground-state has
MOLECULAR PHYSICS 3
been determined. Consider, for example, the neon atom
which is a closed shell with a 2s2p3 valence. Within this
shell, one can construct at least three sets of localised
orbitals that automatically satisfy the localisation equa-
tions due to symmetry considerations. These sets are the
cartesian set given by {|2s 〉, |2px 〉, |2py 〉,
|2pz 〉}, an explicitly complex spherical harmonic set
|2p +i|2p  |2p −i|2p 
that is given by {|2s, x√(2) y , x√(2) y , |2pz }, and
the standard sp3 hybrids. It was demonstrated in 1988
by Pederson and Lin [20] that the hybrids minimise the
total energy for the Kohn–Sham exchange only func-
tional. It has been further discussed that this is the only
choice that automatically leads to three-fold degenera-
cies for the canonical 2p orbitals and it is now recog-
nised that this set is the minimising set determined from
the FLO-SIC formulation [34]. Here, we argue further
that since the choice of the nodal features of the min-
imising set of localised orbitals, in the original PZ func-
tional, will also depend on the features of the functional
itself (GGA, LDA, SCAN [35], etc.), the FLO-SIC formu-
lation would remove this seemingly undesirable trait of
the original formulation. Based on the considerations of
this paragraph, we argue strongly for the hypothesis that
the FLO-SIC formulation must be further considered and
that arguments for further modification of the PZ for-
mulation, presented in [34] based on considerations of
results from many authors, may be a better way to further
achieve the nearly nodeless orbital densities discussed in
[33].
In Section 2, the FLO-SIC [34] is reviewed. The results
from a calculation on a spin-unpolarised porphyrin are
reported in Section 3, with additional remarks about this
study in Section 4.
2. Fermi–Löwdin orbital-based self-interaction
correction
In PZ self-interaction-corrected expression for a spin-
polarised system, the localised orbital density can be
represented with both localised {φ i,σ (r)} and canonical
{ψ i,σ (r)} orbitals [20–22]:
   
ρσ (r) = φi,σ (r)2 = ψi,σ (r)2 . (1)
i i
The orbitals used for constructing the SIC energy must
satisfy O(N2 ) localisation equations given by

    σ
Hoσ + ViσSIC  φiσ = λ  φ jσ (2)
ij
j

φiσ | ViσSIC − V jσ
SIC
| φ jσ = 0. (3)
4 D.-Y. KAO AND M. R. PEDERSON

Based on the complexity associated with the above Table . For the two-orbital case, there are two ways to use Gram–
equations, a new version based upon FLOs [34] which Schmidt to reorthogonalise orbitals but only one way to deter-
mine new orbitals with the Löwdin’s method. The generalisation
satisfies many desirable properties for self-interaction-
to N orbitals is that there would be N! different ways to construct
corrected functionals has been developed. This advan- orthonormal orbitals if Gram–Schmidt is employed.
tageous new formulation [34] of the self-interaction-
Gram–Schmidt  Gram–Schmidt  Löwdin
corrected density-functional expression, that evades the
requirement for solving the computational demanding φ F F F1 − 21  F1 |F2 F2
localisation equation (Equation (3)), is now discussed. φ F −  F |F 〉F F −  F |F 〉F F2 − 21  F1 |F2 F1
This expression is explicitly unitarily invariant and size-
extensive [2] because it is based on the FO [36,37], con-
structed from the spin-density matrix, which is explicitly The intermediate Löwdin orbitals (ILO), which struc-
invariant under unitary transformations. Given a trial set turally are similar to molecular orbitals and Bloch
of Kohn–Sham orbitals, a normalised FO can be defined Functions, are eigenstates of the overlap matrix and are
at any point in space aiσ according to therefore constructed from a unitary transformation
on the FOs according to

∗
μ ψμσ (aiσ )ψμσ (r) ρσ (aiσ , r) 
Fiσ (r) = 
=√ . (4) |Tα  = Tα j |Fj  (7)
|ψ (a )|2 ρσ (aiσ ))
μ iσ j

The eigenvalues of the FO-overlap matrix, Qα , determine

The positions used for construction of the FOs, now
the total amount of charge each ILO captures. From Equa-
referred to as descriptors (aiσ ), provide a semiclassical
tions (5)–(7), the FLOs, designated by φ k , are constructed
picture of an electron as they look like electronic posi-
with the ILO transformation matrix and associated eigen-
tions [2,34]. For plane waves enclosed in a cubic Bril-
values according to
louin zone, ψkσ = √1V eik·r , Equation (4) reduces to Wan-

nier function, √1V k e−ik·aiσ eik·r . When an FO is val-  1 

|φk  = √ Tkα Tα j |Fj  ≡ φkFj |Fj . (8)
ued at aiσ , the FO captures all the spin density at the Qα
αj j
point in space. The FO is reduced to a delta function if
it is constructed with a full orbital set and therefore fully
Because the overlap matrix is real and symmetric, the
recovers the classical ideal of an electronic position. For
inverse transformation between FLOs and FOs is
special sets of points, the FOs can be immediately orthog-
onal (e.g. Wannier functions), but in general, they are not.
In order to derive an orthonormalised orbital set of
localised orbitals from the initial FOs, Löwdin’s method
of symmetric orthonormalisation is applied. The Löwdin
symmetric reorthonormalisation procedure guarantees
that each localised orbital {φ iσ } is spatially similar to its
parent FO in a least-squares sense [38] but each localised
orbital now depends parametrically on all the FO descrip-
tors and on the spin-density matrix, or equivalently, on
the Kohn–Sham orbitals (Equation (4)). According to
Löwdin’s method of symmetric orthonormalisation, an
overlap matrix is constructed with FOs according to
Si j =  Fi |Fj , (5)
which is Hermitian and positive definite (eigenvalues are
positive) since FOs are generally expected to be linearly
independent. Therefore, the overlap matrix can be diag-
onalised by a unitary matrix, Tjα :
 Gram-Schmidt orbitals are chosen, there are always some
Tαi∗ Si j T jα = Qα . (6)
ij

|Fl  = Qβ Tlβ Tβn |φn . (9)
βn
The set of FLOs is guaranteed to be an orthonormal set
and therefore a unitary transformation of Kohn–Sham
orbitals. To illustrate the uniqueness of the Löwdin proce-
dure, we consider another popular systematic method for
orthonormalising a set of orbitals known as the Gram–
Schmidt orthonormalisation. Gram–Schmidt orthonor-
malisation does not construct the new set of orbitals
in a symmetric manner. Considering a two-dimensional
example, there are two sets of ‘new’ orbitals that can be
constructed using the Gram–Schmidt procedure but only
one set that can be determined from the Löwdin’s method.
These sets of orbitals are listed in Table 1. Löwdin’s
method treats every orbital in the same pattern and there
is only one outcome regardless of the number of FOs.
On the other hand, if the Gram–Schmidt orthonormali-
sation is adopted, there are N! different ways to construct
orthonormalised orbitals. Regardless of what set of the
orbitals that are very delocalised.
 MOLECULAR PHYSICS 5

Once the FLOs are determined for a given set of Table . Structural and energetic data of flat Dd Fe(II)-porphyrin
descriptors, the energy is minimised by varying these without constraining spin-up and spin-down electrons in the
descriptors. A set of Kohn–Sham orbitals is obtained same orbitals. This is the lowest energy of Ms =  electronic con-
figuration, so the relative energy is  eV (the first row). The super-
through standard DFT self-consistent field procedure and script on the left of symmetry label is the occupation number and
the positions of descriptors can be determined with the on the right is spin index of occupied electron. The Fe atom is at
methods for optimising molecular geometries. Minimisa- the centre.
tion of the energy in molecules by brute force adjustment E = . eV
of the FO descriptors leads to improved atomisation ener-
gies [2–4,30,34]. However, it was noted that with deriva- Coordinates of atoms (Å)
tives it would be possible to use methods such as conju- N (., ., .)
gate gradients to variationally determine the positions of C (., ., .)
C (., ., .)
FO descriptors. In order to do this, the derivatives of SIC C (., ., .)
energy with respect to the position of FO descriptors is H (., ., .)
H (., ., .)
needed:
Configurations of iron d orbitals (eV)
    
dE SIC dφk  SIC    dφk
= Vk φk + φk VkSIC  . d↓
z2
.
dam dam dam . d↑ /. d↑ .
k xz yz
       . d↓ − .
dφk  dφl  xy
. d↑ |
=
klk  φl − φk , (10) − . |
dam 
xy
dam . d↓ /. d↓
xz yz − .
kl
. d↑ − .
z2

with
klk =  φl |VkSIC |φk . Due to the fact that the localised
orbitals are constrained to lie in the space of the Kohn–
Sham orbitals, this is a generally correct formula and
there is no requirement that Kohn–Sham orbitals need to
be self-consistent solutions of a Hamiltonian. A complete
derivation of the FO derivatives may be found in [30,34].
The calculations reported here were performed with the
NRLMOL suite of codes [39].
Table . Structural and energetic data of flat Dd Fe(II)-porphyrin
with constraining spin-up and spin-down electrons in the same
orbitals. The relative energy is . eV (the first row). The super-
script on the left of symmetry label is occupation number and on
the right is spin index of occupied electron.
E = . eV
Coordinates of atoms (Å)

N (., ., .)

C (., ., .)
3. Results and discussion C (., ., .)
C (., ., .)
Fe(II)-porphyrin plays the key role for carrying oxygen in H (., ., .)
mammals and its geometry and energy differ as a function H (., ., .)
of spin states of the iron. The difficulty in determining Configurations of iron d orbitals (eV)
the geometries is due to the small difference in energy . d↑↓ .
and the detail of d-orbital filling. Here, only the MS x 2 −y2
. LUMO .
= 0 geometries and spin configurations are discussed, . d↑↓ /. d↑↓ .
xz yz
because the primary effort here is to demonstrate that this . d↑↓ − .
z2
version of SIC maybe be used on systems containing d . d↑↓ − .
xy
electrons.
In this work, the D4d symmetric flat geometry is cal-
culated within PBE-GGA to serve as the reference. Once spin-up and three spin-down d electrons associated with
the geometry is optimised, the symmetry is removed iron. Comparing the filling of d orbitals in Tables 2 and 3,
while the FLO-SIC calculations are performed. The full it is energetically less favoured when the electrons carry-
symmetry of the flat porphyrin can be generated by (x, y, ing both spins are constrained to be in the same d orbitals.
z) → (y, x, z), (x, y, z) → (x, y, −z), and (x, y, z) → (x, The energy of geometry in Table 3 is 0.54 eV higher than
−y, z). The inequivalent atomic positions for the relaxed the energy of the geometry in Table 2, which allows spin-
geometry and electron configuration for the low-energy up and spin-down electrons in different orbitals, because
structure is reported in Table 2 and the higher energy the Coulomb energy dominates the electron filling in d
structure is reported in Table 3. The major difference orbitals. The Kohn–Sham orbital density in one of the
between these two geometries is the filling of d orbitals. spin channels is shown in Figure 2, which corresponds
In the spin-unpolarised Fe(II)-porphyrin, there are three to the calculation in Table 3. The dxy orbital has the
6 D.-Y. KAO AND M. R. PEDERSON
Figure . Kohn–Sham orbital density of iron d-orbitals and occu-
pation numbers of spin-unpolarised calculation within PBE-GGA.
lowest energy among all the iron d-orbitals, because the
electronic lobes of dxy avoid the lobes of the nitrogens. A
0.01 eV gap between dz2 and dxz /dyz is found. The frac-
tional occupation numbers are observed for degenerate
orbitals dxz and dyz at Fermi level [7]. This is generally
an indicator of self-interaction error. dx2 −y2 is the orbital
with the highest energy since the electronic lobes of iron
collide with nitrogens and form anti-bonding orbitals.
Since the positions of FO descriptors are transfer-
able, the initial positions of the electrons associated
with the atoms on the ring are adopted from Mg(II)-
porphyrins [4]. Since many initial sets of FO descrip-
tors are possible, identification of good guesses for the
initial positions of FO descriptors are screened through
consideration of the lowest eigenvalue of the intermedi-
ate Löwdin orbitals, the summation of the magnitude of
the square of force, and the SIC energy. Generally speak-
ing, several initial positions are chosen to compete for
the geometry with the lowest energy, which is minimised
with respect to the positions of FO descriptors. The geo-
metric mean of the intermediate Löwdin orbitals, the nat-
ural log of the norm of FO derivatives, and the difference
of the SIC energy relative to the minimum are introduced
to determine the stages of the evolution of the positions
of FO descriptors [34].
The FLO-SIC calculation is performed within the
PW92-LDA approximation. The fractional occupied
solutions are removed once the SIC is applied. The posi-
tions of FO descriptors are the red circles in Figure 3.
The FO descriptors near the plane imitate the classi-
cal chemical bonds, and the symmetry of the electronic
Figure . Positions of FLO descriptors in the spin-unpolarised
Fe(II)-porphyrin are shown in as the smallest spheres. These are
the descriptors of spin-up channel while those of the spin-down
channel are identical. Iron is at the centre, nitrogens are light grey,
carbons are dark grey, and hydrogens are in white.
configuration appears to be broken [3,30]. The carbon–
carbon and carbon–hydrogen σ bonds and π bonds
are reproduced by FO descriptors. From the side
view, we observe that some of the FO descriptors can
hover above/below the porphyrin plane. The hovering
behaviour indicates that those descriptors are flexible
to move with very small changes in the total energy.
This appears to be a classical means for understanding
the concept of aromaticity [4,30]. The resonance struc-
tures observed in typical Kekule’ structures involve nine
delocalised π bonds (five carbon–carbon, two carbon–
nitrogen, and two nitrogen–iron bonds). As discussed
in [40], our lowest energy geometry is in accord with
this understanding. This paper shows that there are nine
descriptors, referred to as ‘hovering descriptors’ [4,30],
that are displaced far above the plane of the molecule.
Four of the hovering descriptors are on top of the vertices
of the tetrahedral coordination of nitrogens and they are
similar to the ammonium ion (NH4+ ) tetrahedral config-
uration. In addition, there are always 24 FO descriptors
in close proximity to the iron centre with the other two

relocated to somewhere on the ring. This implies that
the centred iron atom is +2 charged. These observations
imply that the behaviour of FO descriptors coincide with
chemical intuition.
4. Summary
In this paper, the FLO-based SIC is applied to the Ms =
0 Fe(II)-porphyrin to demonstrate that this new theoret-
ical method is viable for large molecules containing tran-
sition metal systems. FOs depend explicitly on the den-
sity matrix and are therefore unitarily invariant highly
localised orbitals. Use of Löwdin symmetric orthonor-
malisation preserves size-extensivity and the transferabil-
ity of descriptors. In this study, we show that the SIC is
able to lower the energy and resolve the fractional occu-
pation. The similarity between FLO descriptors and the
classical chemical bonds is explored. In addition, aro-
maticity of Fe(II)-porphyrin ring is interpreted by the
hovering FLO descriptors.
Acknowledgments
Mark R. Pederson acknowledges the long-standing support
from NRL which allowed development of NRLMOL. Der-you
Kao was supported by a fellowship at The George Washing-
ton University Institute of Nanotechnology. The authors thank
Drs Torsten Hahn, Jens Kortus, Tunna Baruah, Koblar Jackson,
and Mr Simon Liebing for many interesting discussions.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported in part by Office of Naval Research
(ONR) [N00014-16-1-2464]; and The George Washington Uni-
versity Institute of Nanotechnology.
ORCID
Mark R. Pederson http://orcid.org/0000-0003-2489-4849
References
[1] J.P. Perdew and A. Zunger, Phys. Rev. B 23(10), 5048–
5079 (1981).
[2] M.R. Pederson, A. Ruzsinszky, and J.P. Perdew, J. Chem.
Phys. 140(12), 121103 1–4 (2014).
[3] T. Hahn, S. Liebing, J. Kortus, and M.R. Pederson,
J. Chem. Phys. 143(22), 224104 1–7 (2015).
[4] M.R. Pederson, T. Baruah, D. Kao, and L. Basurto,
J. Chem. Phys. 144(16), 164117 1–8 (2016).
[5] J.P. Perdew and Y. Wang, Phys. Rev. B 45, 13244–13249
(1992).
MOLECULAR PHYSICS 7
[6] I. Lindgren, Int. J. Quant. Chem. 5(S5), 411–420 (1971).
[7] J.F. Janak, Phys. Rev. B 18(12), 7165–7168 (1978).
[8] J.P. Collman, J.L. Hoard, N. Kim, G. Lang, and C.A. Reed,
J. Am. Chem. Soc. 97, 2676–2681 (1975).
[9] H. Goff, G.N. La Mar, and C.A. Reed, J. Am. Chem. Soc.
99, 3641–3646 (1977).
[10] M.S. Liao and S. Scheiner, J. Chem. Phys. 117, 205–219
(2002).
[11] H. Nakashima, J.-Y. Hasegawa, and H. Nakatsuji, J. Com-
put. Chem. 27(4), 426–433 (2006).
[12] C.A. Reed, T. Mashiko, W.R. Scheidt, K. Spartalian, and
G. Lang, J. Am. Chem. Soc. 102, 2302–2306 (1980).
[13] E. Sigfridsson and U. Ryde, J. Inorg. Biochem. 91, 101–
115 (2002).
[14] S. Paul, F. Amalraj, and S. Radhakrishnan, Synth. Met.
159(11), 1019–1023 (2009).
[15] C. She, S.J. Lee, J.E. McGarrah, J. Vura-Weis, M.R.
Wasielewski, H. Chen, G.C. Schatz, M.A. Ratner, and J.T.
Hupp, Chem. Commun. 46(4), 547–549 (2010).
[16] D. Danilovic, C.L. Lin, T. Yuen, L. Pan, and J. Li, J. Appl.
Phys. 101(9), 09E103 1–2 (2007).
[17] E.I. Ioannidis and H.J. Kulik, J. Chem. Phys. 143(3),
034104 1–11 (2015).
[18] A. Svane, L. Petit, Z. Szotek, and W.M. Temmerman, Phys.
Rev. B 76(11), 115116 (2007).
[19] C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35,
457–465 (1963).
[20] M.R. Pederson and C.C. Lin, J. Chem. Phys. 88(3), 1807–
1817 (1988).
[21] M.R. Pederson, R.A. Heaton, and C.C. Lin, J. Chem. Phys.
80(5), 1972–1975 (1984).
[22] M.R. Pederson, R.A. Heaton, and C.C. Lin, J. Chem. Phys.
82(6), 2688–2699 (1985).
[23] J.P. Perdew, A. Ruzsinszky, J. Sun, and M.R. Pederson, in
Advances in Atomic, Molecular, and Optical Physics, edited
by E. Arimondo C.C. Lin S.F. Yelin (Burlington Academic
Press, 2015), Vol. 64, Chap. 1, pp. 1–14.
[24] K.A. Jackson, in Advances in Atomic, Molecular, and Opti-
cal Physics, edited by E. Arimondo C.C. Lin S.F. Yelin
(Burlington Academic Press, 2015), Vol. 64, Chap. 2,
pp. 15–27.
[25] A. Pertsova, C.M. Canali, M.R. Pederson, I. Rungger, and
S. Sanvito, in Advances in Atomic, Molecular, and Opti-
cal Physics, edited by E. Arimondo C.C. Lin S.F. Yelin
(Burlington Academic Press, 2015), Vol. 64, Chap. 3,
pp. 29–86.
[26] P.M. Dinh, P. Reinhard, E. Suraud, and M. Vincendon, in
Advances in Atomic, Molecular, and Optical Physics, edited
by E. Arimondo C.C. Lin S.F. Yelin (Burlington Academic
Press, 2015), Vol. 64, Chap. 4, pp. 87–103.
[27] N. Poilvert, G. Borghi, N.L. Nguyen, N.D. Keilbart,K.
Wang, and I. Dabo, in Advances in Atomic, Molecular,
and Optical Physics, edited by E. Arimondo C.C. Lin S.F.
Yelin (Burlington Academic Press, 2015), Vol. 64, Chap.
5, pp. 105–127.
[28] N. Gidopoulos and N.N. Lathiotakis, in Advances in
Atomic, Molecular, and Optical Physics, edited by E. Ari-
mondo C.C. Lin S.F. Yelin (Burlington Academic Press,
2015), Vol. 64, Chap. 6, pp. 129–142.
[29] S. Kümmel, in Advances in Atomic, Molecular, and Opti-
cal Physics, edited by E. Arimondo C.C. Lin S.F. Yelin
(Burlington Academic Press, 2015), Vol. 64, Chap. 7,
pp. 143–151.
8 D.-Y. KAO AND M. R. PEDERSON
[30] M.R. Pederson and T. Baruah, in Advances in Atomic,
Molecular, and Optical Physics, edited by E. Arimondo
C.C. Lin S.F. Yelin (Burlington Academic Press, 2015),
Vol. 64, Chap. 8, pp. 153–180.
[31] S. Klüpfel, P. Klüpfel, and H. Jónsson, Phys. Rev. A. 84(5),
050501R 1–4 (2011).
[32] S. Lehtola and H. Jónsson, J. Chem. Theory Comput.
10(12), 5324–5337 (2014).
[33] M.R. Pederson and J.P. Perdew,  K Newsletter Scientific
Highlight of the Month (February, 2012). <http://www.
psi-k.org/newsletters/News_109/Highlight_109.pdf >.
[34] M.R. Pederson, J. Chem. Phys. 142(6), 064112 1–7 (2015).
[35] J. Sun, A. Ruzsinszky, and J.P. Perdew, Phys. Rev. Lett. 115,
036402 1–6 (2015).
[36] W. Luken and D.N. Beratan, Theor. Chim. Acta 61(3),
265–281 (1982).
[37] W. Luken and J.C. Culberson, Theor. Chim. Acta 66(5),
279–283 (1984).
[38] B.C. Carlson and J.M. Keller, Phys. Rev. 105(1), 102–106
(1957).
[39] M.R. Pederson, D.V. Porezag, J. Kortus, and D.C. Patton,
Phys. Stat. Solidi B 217, 197–218 (2000).
[40] D. Kao, M.R. Pederson, T. Baruah, T. Hahn, S. Liebing,
and J. Kortus (submitted).