Photoelectron spectra of copper oxide

cluster anions from first principles methods

Cite as: J. Chem. Phys. 149, 064306 (2018); https://doi.org/10.1063/1.5038744
Submitted: 04 May 2018 • Accepted: 24 July 2018 • Published Online: 13 August 2018

Bin Shi, Shira Weissman, Fabien Bruneval, et al.

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© 2018 Author(s).
 THE JOURNAL OF CHEMICAL PHYSICS 149, 064306 (2018)

Photoelectron spectra of copper oxide cluster anions from first

principles methods
Bin Shi,1 Shira Weissman,2 Fabien Bruneval,3 Leeor Kronik,2 and Serdar Öğüt1,a)
1 Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607, USA
2 Department of Materials and Interfaces, Weizmann Institute of Science, Rehovoth 76100, Israel
3 DEN, Service de Recherches de Métallurgie Physique, CEA, Université Paris-Saclay,

F-91128 Gif-sur-Yvette, France

(Received 4 May 2018; accepted 24 July 2018; published online 13 August 2018)

We present results and analyses for the photoelectron spectra of small copper oxide cluster anions
(CuO− , CuO−2 , CuO−3 , and Cu2 O− ). The spectra are computed using various techniques, including
density functional theory (DFT) with semi-local, global hybrid, and optimally tuned range-separated
hybrid functionals, as well as many-body perturbation theory within the GW approximation based
on various DFT starting points. The results are compared with each other and with the available
experimental data. We conclude that as in many metal-organic systems, self-interaction errors are a
major issue that is mitigated by hybrid functionals. However, these need to be balanced against a strong
role of non-dynamical correlation—especially in smaller, more symmetric systems—where errors
are alleviated by semi-local functionals. The relative importance of the two phenomena, including
practical ways of balancing the two constraints, is discussed in detail. Published by AIP Publishing.
https://doi.org/10.1063/1.5038744

I. INTRODUCTION resulting from the subtle interplay of their orbital, spin, and
charge degrees of freedom.13 Motivated by these observations,
Gas-phase photoelectron spectroscopy (PES) and its first-
here we examine the performance of various state-of-the-art
principles simulation using various computational approaches
DFT and GW methods in modeling the photoelectron spectra
have proven to be a powerful combination for probing the
of copper oxide anion clusters, by comparing their predic-
electronic structure of atomic and molecular clusters.1,2 In
tions with each other and with the available experimental
gas-phase PES, electrons are emitted upon absorption of
data.
(typically ultraviolet) light, allowing for the exploration of
We focus on four small clusters, Cu2 O− , CuO− , CuO−2 ,
electron removal energies. Computational methods based on
and CuO−3 , which span a relatively wide range of Cu con-
density functional theory (DFT) within the (generalized)
tent and exhibit strong electronic correlations. Photoelectron
Kohn-Sham scheme2–4 or many-body perturbation theory
spectra for these clusters have been available up to pho-
within the GW approximation4–9 are some of the most com-
ton energies of ∼5-6 eV since the pioneering studies of
monly used approaches to determine the energetics of such
Polak et al.14 and Wang et al.15,16 Among them, copper
charged excitations. The degree of accuracy with which var-
monoxide has been extensively studied both experimen-
ious computational methods can predict these excitations
tally14,16,17 and theoretically.10,18–31 Electronic and optical
depends not only on the fundamental limitations and practi-
properties of CuO2 in various charge states have also been
cal implementations of the underlying theoretical framework
of significant interest, especially with regards to its lowest
but also on the nature (e.g., chemical composition, size) of
energy structure (bent versus linear) in various experimen-
the system being studied. From this perspective, transition
tal16,32–36 and theoretical studies.37–43 There have been fewer
metal oxide clusters are stringent test cases for state-of-the-art
investigations on the electronic structures of CuO3 16,44,45 and
computational methods, owing to enhanced electron corre-
Cu2 O.10,15,46,47 The first-principles methods explored here
lations inherent in them, as well as their open-shell charac-
include DFT with semilocal and global hybrid exchange-
ter,10 which require a balanced and accurate description of
correlation functionals (based on shifted eigenvalue spectra),
dynamical and non-dynamical electron correlation. In addi-
DFT with optimally tuned range-separated hybrid (OT-RSH)
tion to the computational challenges in modeling their excited
functionals, and many-body perturbation theory techniques
states,5,11,12 bulk and nanostructured transition metal oxides
within the GW approximation using semilocal or global hybrid
have traditionally been systems of great technological and sci-
functional starting points.
entific interest, as they possess a wide range of complex, and
This article is arranged as follows. We begin with an
often desirable, structural, electronic, and optical properties
overview of the computational methods and their correspond-
ing parameters, given in Sec. II. This is followed in Sec. III
by a brief discussion on the relaxed structures of the copper
a)Electronic mail: ogut@uic.edu oxide clusters considered in this study and detailed analyses

0021-9606/2018/149(6)/064306/12/$30.00 149, 064306-1 Published by AIP Publishing.

064306-2 Shi et al.
of the computed photoelectron spectra. Trends in the pho-
toelectron spectra of these clusters are analyzed in terms of
various factors, including self-interaction errors (SIEs), spa-
tial extent of the relevant orbitals, amount of exact exchange
in the DFT description, importance of non-dynamical corre-
lation, spin-splitting, and starting-point dependence in GW
calculations. Finally, we summarize our findings and analyses
in Sec. IV.
II. COMPUTATIONAL DETAILS
Computations within DFT were carried out using the
NWChem code,48 Version 6.5, using the aug-cc-pVTZ basis
set. In these calculations, the geometries of the anions were
optimized using both the Perdew-Burke-Ernzerhof (PBE)49
and PBE050 exchange-correlation functionals. The photoelec-
tron spectra were simulated by convoluting the DFT eigenvalue
spectra of the anions with a 0.1-eV-wide Gaussian broadening
function, without taking photoionization cross sections into
account. For the PBE and PBE0 calculations, the eigenvalue
spectra were shifted so as to align the first peak with the vertical
ionization potential of the anion, computed as the total energy
difference between the anionic and the neutral cluster at the
fixed anion geometry.51,52 The amounts of the shifts and the
vertical ionization potentials for each case are provided in the
supplementary material. OT-RSH calculations were based on
the combination of full long-range Fock exchange, a fraction of
short-range Fock exchange, and PBE-based semi-local short-
range and long-range components, along with PBE correlation.
The calculations were performed for two different values of
the short-range Fock exchange fraction (α), 0.0 and 0.2,53 as
in the functionals long-range-corrected (LC)-ωPBE54 and LC-
ωPBE0,55 respectively. In difference to the parent functionals,
the range-separation parameter, γ, was optimally tuned per
system so as to satisfy the ionization potential theorem,56
γ opt
 H = −IPγ , where  H and IP are the highest occupied
opt
molecular orbital (HOMO) energy and (vertical) ionization
potential of the anion, respectively.
GW calculations were performed using molgw57 within
the perturbative “one-shot” G0 W 0 methodology. In this
approximation, a Green’s function, G0 , computed using
Kohn-Sham wavefunctions and eigenvalues, and the screened
Coulomb interaction, W 0 , obtained from a dynamical
J. Chem. Phys. 149, 064306 (2018)
polarizability computed within the random-phase approxi-
mation, are used to compute the self-energy Σ = iG0 W 0 .
The starting electronic structures were obtained from DFT
calculations with PBE and various hybrid functionals per-
formed within the same package. Quasiparticle wavefunc-
tions were represented using atom-centered Gaussian basis
sets ranging from aug-cc-pVDZ to aug-cc-pV5Z58 with effec-
tive core potentials for Cu.59 The Coulomb interaction terms
were evaluated using the resolution-of-the-identity approxi-
mation.60,61 The GW energies in the complete basis set limit
were obtained by fitting the extrapolated energy E ∞ and coef-
ficient c to E(X) = E ∞ + cX −2 , where X = 2–5 for aug-cc-
pVDZ through aug-cc-pV5Z basis sets, as follows: For Cu2 O− ,
CuO− , and CuO−3 , the variation in the computed GW quasi-
particle energies with a PBE starting point was observed to
be non-monotonic as a function of the basis set size when
aug-cc-pVQZ and aug-cc-pV5Z basis sets were included.
Accordingly, for these three cluster anions, the G0 W 0 @PBE
quasiparticle energies were obtained by fitting to X = 2–3 only,
while for CuO−2 and all other starting points, we extrapolated
from X = 3–5.
III. RESULTS AND DISCUSSION
The optimized structures of copper oxide cluster anions
are shown in Fig. 1. With the exception of one of the isomers
of CuO−3 , the computed inter-atomic distances and angles are
found to be mostly insensitive to the choice of the exchange-
correlation functional. Both CuO− and CuO−3 of C 2v symme-
try possess singlet ground states, whereas the linear CuO−2
(D∞h ) and the CuO−3 cluster of C s symmetry possess triplet
ground states. The bent Cu2 O− (C2v symmetry) is found to
have a doublet ground state. Importantly, the slight differences
observed in the bond lengths and angles did not have a signifi-
cant effect on the computed photoelectron spectra. Therefore,
differences in the photoelectron spectra computed at various
levels of theory, reported next, reflect true electronic struc-
ture effects rather than differences inherited from different
geometries.
A. Cu2 O−
We start our analysis of computed photoelectron spectra
with Cu2 O− , which has the largest Cu content of the anions
FIG. 1. Structures and symmetries of
the Cux O−y clusters considered in this
study. O atoms are denoted by smaller
red balls and Cu atoms are denoted
by larger blue balls. Optimized bond
lengths and angles have been computed
with the PBE and PBE0 (in parenthe-
ses) functionals. For CuO−3 , the structure
with C s symmetry on the right is lower
in energy.
064306-3 Shi et al.
considered in this study. Figure 2 shows the experimental pho-
toelectron spectrum of Cu2 O− along with spectra computed at
various levels of theory. The experimental spectrum consists
of a low-energy peak at 1.1 eV (X), followed by a sizeable
gap, and sharp peaks at 2.53 (A), 2.66 (B), 2.85 (C), 2.95
(D), and 3.08 eV (E). Wang et al.15 interpreted the large gap
between the X and A peaks as an indicator of a large high-
est occupied molecular orbital-lowest unoccupied molecular
orbital (HOMO-LUMO) gap for neutral Cu2 O, suggesting that
the neutral cluster has a closed-shell electronic structure. The
similarity in the spectral features and intensity ratios between
the A and C bands, as well as between the B and D bands, led
Wang et al. to suggest that these bands arise from the removal
of either a spin-down or a spin-up electron from orbitals of the
same character.
With both the PBE and PBE0 functionals, the ground state
of Cu2 O− is found to be a doublet and the neutral cluster
is found to be a closed-shell singlet in its ground state. An
overall comparison of the experimental data with the DFT-
computed spectra (Fig. 2) shows that the (shifted) PBE does
not provide quantitatively accurate predictions for the pho-
toelectron peak positions, while various hybrid functionals
(with or without range separation) perform significantly bet-
ter. The most obvious discrepancy between experimental data
and PBE predictions is the separation of the X band from
the A–E bands, which is severely underestimated. The X–A
separation of 0.56 eV computed with PBE is much smaller
FIG. 2. Experimental photoelectron spectrum of Cu2 O− (adapted from
Ref. 15), along with spectra computed with PBE, PBE0, OT-RSH (α = 0,
γ opt = 0.221 a.u.−1 ), OT-RSH (α = 0.2, γ opt = 0.188 a.u.−1 ), G0 W 0 @PBE,
G0 W 0 @PBE0, G0 W 0 @BHLYP, and equation-of-motion coupled-cluster
(EOM-CC) (adapted from Ref. 10). The PBE and PBE0 spectra are shifted to
align the first peak with the IP of the anion cluster. Contour plots of the selected
molecular orbitals (with symmetries), in both majority (↑) and minority (↓)
spin channels, are shown on the right-hand side, with matching color codes
displayed in the spectra (for G0 W 0 @PBE, the eigenvalues are color-coded).
For PBE and G0 W 0 @PBE, the spectra are scaled by half compared with the
others to fit them in the panels.
J. Chem. Phys. 149, 064306 (2018)
than the experimental value of 1.43 eV. Introducing a frac-
tion of Fock exchange, either globally or in range-separated
form (the latter to correct the asymptotic potential), signifi-
cantly improves the agreement with the experiment, with the
OT-RSH approach additionally removing the need for shifting
the spectra.53,56 Specifically, the mean absolute errors (MAEs)
averaged over the six measured (X–E) peaks for shifted PBE,
shifted PBE0, OT-RSH (α = 0), and OT-RSH (α = 0.2) calcu-
lations are 0.60, 0.19, 0.12, and 0.10 eV, respectively. These
trends are qualitatively the same as those observed previously
for a metal-organic Cu-based complex, copper phthalocyanine
(CuPc).53,62,63
The predictions from the G0 W 0 approximation with a PBE
starting point (Fig. 2) are strikingly poor when compared with
the experimental data. For example, the X and A peaks, as
well as their separation, are underestimated severely, by 0.6,
1.44, and 0.59 eV, respectively. In fact, comparison of the spec-
tra displayed in Fig. 2 reveals that the G0 W 0 @PBE performs
even worse than the shifted PBE spectrum, leading to a MAE of
1.36 eV. Starting the G0 W 0 calculation with a DFT calculation
that contains some fraction of exact exchange leads to better
agreement with experiment. For example, the G0 W 0 @PBE0
predictions are considerably better than the G0 W 0 @PBE
results. In spite of this improvement, the G0 W 0 @PBE0 still
leads to underbound quasiparticle levels. Similar to the shifted
PBE case, the shifted PBE0 predictions are more accurate than
the G0 W 0 @PBE0 predictions, for which the MAE over the six
experimentally measured peaks is 0.44 eV. To investigate the
effect of the amount of exact exchange in the G0 W 0 start-
ing point further, we performed G0 W 0 calculations on top of a
BHLYP64 starting point (with 50% exact exchange). As shown
in Fig. 2, the G0 W 0 @BHLYP results are in nearly perfect
agreement with the experimental data, with the largest dif-
ference being 0.07 eV (for the X peak) and an overall MAE
of less than 0.04 eV. While the importance of using hybrid
functional starting points for the ensuing G0 W 0 calculations
has been highlighted in previous studies of sp-bonded molec-
ular systems,7,65–68 of metal-organic complexes,63,69 and of
bulk metal oxides,5,70 the results presented here show just
how poorly the PBE starting point can be and that basing a
GW calculation on it can in fact make things worse rather than
better.
To gain further insight into our computational results,
Fig. 2 additionally compares them with the quantum chemistry
calculations reported in Ref. 10, which were performed within
the equation-of-motion coupled-cluster (EOM-CC) approach,
at the singles and doubles (CCSD) level, as well as from
differences in CCSD with perturbative triples total energies
between the doublet anion and the lowest neutral state (to
determine the X peak). These calculations predict the photo-
electron peaks X–E at energies of 1.00, 2.62, 2.68, 3.09, 3.19,
and 3.33 eV. Overall, these agree well with the experimental
spectrum, with an MAE of 0.16 averaged over the six mea-
sured values. Remarkably, both the GW calculations (with an
appropriately chosen starting point) and the DFT ones (based
on OT-RSH) are overall as accurate as the EOM-CC ones,
establishing that quantitative interpretation of the experimen-
tal data can be obtained for this cluster anion even without
resorting to expensive wavefunction-based approaches.
064306-4 Shi et al. J. Chem. Phys. 149, 064306 (2018)

Figure 2 also shows the DFT-computed molecular orbitals

for the highest seven (counting both spin channels) occupied
states of Cu2 O− . Based on the nodal structure along the Cu–O
and Cu–Cu directions, these can be viewed as anti-bonding
orbitals. The HOMO, possessing a1 symmetry, is a relatively
extended orbital with significant Cu content, with appreciable
contributions from 3d and 4s atomic orbitals and some from
4p, and smaller (∼15%) O 2p character. In going from PBE
to PBE0, the shape of the molecular orbital remains virtually
the same, but the Cu 4s content increases at the expense of a
decrease in the Cu 3d content. A similar behavior is observed
for the lower lying states of b2 , b1 , and a1 symmetry, for which
the Cu 3d content decreases at the expense of an increase in the
O 2p content. These observations are in accordance with the
expectation that introduction of exact exchange should push
the localized Cu 3d orbitals down in energy due to mitigation
of self-interaction error (SIE).71 Another difference between
PBE and PBE0 predictions is related to the ordering of the
various orbitals. In particular, the ordering of the first five
occupied orbitals in increasing the binding energy (BE) at the
PBE level is a1 ↑ b2 ↓ b2 ↑ b1 ↓ b1 ↑ , while the ordering at the PBE0
level is a1 ↑ b1 ↓ b2 ↓ b2 ↑ b1 ↑ . While in some cases the relevant
energy differences are small, such rearrangement of orbitals is
generally related to (i) the spatial extent (degree of localiza-
tion) of the relevant orbitals, which determines the amount that
the introduction of exact exchange shifts the orbital eigenval-
ues in going from PBE to PBE0 to partially correct for SIE,2
and (ii) the tendency of exact exchange to segregate (energeti-
cally) orbitals belonging to the same spin channel. In this case, FIG. 3. Experimental photoelectron spectrum of CuO− (Ref. 16), along
with spectra computed with PBE, PBE0, OT-RSH (α = 0, γ opt = 0.225
PBE0 leads to a configuration in which HOMO-1/HOMO- a.u.−1 ), OT-RSH (α = 0.2, γ opt = 0.138 a.u.−1 ), G0 W 0 @PBE, G0 W 0 @PBE0,
3 (and HOMO-2/HOMO-4), associated with A/C (and B/D) G0 W 0 @BHLYP, and EOM-CC (Ref. 10). The PBE and PBE0 spectra are
bands in the experiment, are in opposite spin channels (unlike shifted to align the first peak with the IP of the anion cluster. Contour plots of
molecular orbitals discussed in the text are shown on the right, with matching
PBE). They also have different symmetries (b1 and b2 ), in
color codes displayed in the spectra.
agreement with the experimental suggestion that A/C and B/D
bands correspond to removal of spin-up/spin-down electrons
from orbitals of the same character. When viewed both from state of CuO− was found to be a closed-shell singlet (1 Σ+ )
the perspective of low MAE and the experimentally suggested that could roughly be described as 3d 10 2pσ 2 2pπ 4 . Based on
ordering of the orbitals, the G0 W 0 @BHLYP prediction with these studies and the relative intensity ratios, X and Y states
the a1 ↑ b1 ↓ b2 ↓ b1 ↑ b2 ↑ ordering and the OT-RSH (α = 0, and α were interpreted as arising from the removal of 2pπ and 2pσ
= 0.2 being very close) prediction with the a1 ↑ b2 ↓ b1 ↓ b2 ↑ b1 ↑ electrons, leading to the X2 Π ground state and Y2 Σ+ excited
ordering have the best overall agreement with the state of CuO, respectively. The experiments of Wu et al. also
experiment. revealed a broad and noisy band (labeled Z in Fig. 3) in the
In summary, the photoelectron spectra of Cu2 O− com- 4–6 eV energy range, which was interpreted as being due to
puted with hybrid functionals within DFT, or within the G0 W 0 the detachment of Cu 3d electrons. In addition, weak features
approximation with hybrid functional starting points, are in at 1.27 and 3.18 eV were observed, which were attributed
much better agreement with the experimental data and EOM- to transitions from an electronically excited state of CuO− .
CC results, as compared with the PBE (or G0 W 0 @PBE) In the following discussion, we only focus on the X, Y, and
predictions. This is a somewhat expected finding, because as Z bands, corresponding to transitions from the ground state
discussed above the introduction of Fock exchange mitigates of CuO− .
SIE and binds orbitals of large Cu 3d content more strongly, We first discuss DFT and GW results for the X and Y
while PBE typically underbinds such orbitals. bands. A comparison of the computed spectra with the exper-
imental data surprisingly shows that the PBE provides the
best predictions (within 0.05 eV of experiment) for the posi-
B. CuO−
tions of the first two peaks. The PBE0 and OT-RSH (α = 0.2)
Figure 3 shows the computed and experimental photo- predictions are virtually the same, but they significantly under-
electron spectra of CuO− . In the experiments of Polak et al.14 estimate both the IP and the X–Y separation, by ∼0.5 eV. The
and Wu et al.,16 the first two main peaks (labeled X and Y OT-RSH predictions with α = 0 for the positions of the first
in Fig. 3) were reported at 1.78 and 2.75 eV, respectively. two peaks (both IP and X–Y separation underestimated by
In previous electronic structure calculations,18–21 the ground ∼0.2 eV) lie between those of PBE and those of other hybrid
064306-5 Shi et al.
functionals. Similar to the case of Cu2 O− , the G0 W 0 @PBE
results are poor, with both X and Y peaks underestimated by
∼1.4 eV. The use of a PBE0 starting point for G0 W 0 calcula-
tions significantly improves the quasiparticle energies, but the
X and Y levels are still underestimated by ∼0.4 eV compared
with the experiment. Better agreement with the experiment
can be obtained at the G0 W 0 @BHLYP level, where the X
and Y peaks are predicted to be 0.07 and 0.32 eV below the
experimental values.
As in the discussion of Cu2 O− , we additionally compare
our results with those obtained from the EOM-CC calcula-
tions.10 The best results obtained from such calculations find
transitions at 1.89 and 2.56 eV from the CuO− reference. These
values are within ∼0.1 and ∼0.2 eV of experimental data. The
EOM-CC calculations also provide a convenient point of ref-
erence for the Z-band calculations, where the broad and noisy
nature of the Z band precludes direct comparisons with the
experiment. These higher energy transitions, arising from the
ionization of orbitals with large Cu 3d character, were found to
be 4.83, 5.11, and 5.57 eV.10 These values fall within the range
(4–6 eV) of the Z band observed in the photoemission exper-
iments and therefore indeed provide an adequate benchmark.
Comparing this benchmark with the computational approaches
employed here, we observe that PBE significantly underesti-
mates the BEs of these higher energy states, while the hybrid
functionals do slightly better. The G0 W 0 @PBE predictions are
again poor, while hybrid functional starting points, especially
G0 W 0 @BHLYP, perform much better. Overall, taking all five
peaks (with BEs less than 6 eV) into account, the EOM-CC
performs quite well. The G0 W 0 @BHLYP results are also in
good agreement with the experiment and quantum chemistry
results. The PBE predictions are excellent for the two most
loosely bound states, but they do not perform as well for states
with higher BEs, while the opposite trend is observed for the
case of hybrid functionals.
Figure 3 also provides the orbital characters of the molecu-
lar orbitals involved. The doubly degenerate HOMO/HOMO-1
has π? character: These antibonding states can be described
well as nearly equal mixtures of Cu d xz (d yz ) and O 2px
(2py ) atomic orbitals. The non-degenerate HOMO-2 has
anti-bonding σ? character with significant Cu dz2 and 4s
contribution and O 2pz admixture. The doubly degenerate
HOMO-3/HOMO-4 are non-bonding Cu d xy and dx2 −y2 type
orbitals. HOMO-5/HOMO-6 are also doubly degenerate, cor-
responding to bonding π orbitals, while HOMO-7 is a bonding
σ orbital, both with large contributions from Cu d atomic
orbitals.
The surprising observation that PBE outperforms PBE0
for the position of the first two (X, Y ) peaks can be inter-
preted in terms of the spatial extent of the relevant orbitals and
the compatibility of exact exchange and correlation. Figure 4
shows the unshifted eigenvalue spectra of CuO− , computed for
various values of exact exchange and semilocal (PBE) correla-
tion. More specifically, using an exchange-correlation energy
E xc (α, β) expressed as
Exc (α, β) = αEx,HF + (1 − α)Ex,PBE + βEc,PBE , (1)
where E x ,HF is the Hartree-Fock exchange and E x ,PBE
and E c,PBE are semilocal PBE exchange and correlation,
J. Chem. Phys. 149, 064306 (2018)
FIG. 4. Unshifted eigenvalue spectra of CuO− computed for various values
of exact exchange and PBE correlation, defined by Eq. (1). Orbitals of π ? ,
σ ? , non-bonding d, π, and σ character (same as in Fig. 3) are color-coded to
highlight changes in their energies as a function of α and β. See text for more
details.
respectively, we performed a series of computations by vary-
ing α and β from 0 to 1. As discussed above, in general, one
excepts stronger effects of adding Fock exchange to PBE cal-
culations for more localized orbitals, as the SIE is more severe
in spatially localized orbitals compared with the more extended
ones. This is indeed what we observe in CuO− too. While all
orbitals become more bound (DFT eigenvalues decreasing),
the magnitude of eigenvalue decrease correlates directly with
the spatial extent of the molecular orbital involved. In particu-
lar, the spatial extent of the σ? orbital is larger than that of the
π? orbital. As a result, as more Fock exchange is introduced,
the eigenvalue of the π? orbital decreases more significantly
(by ∼5 eV) than that of the σ? orbital (by ∼3.2 eV) in going
from α = 0 to 1 (at β = 1). For the more localized lower
lying orbitals with large d character, the eigenvalue shifts to
lower energies upon increasing Fock exchange are consider-
ably larger than those of σ? and π? orbitals. Among them,
the bonding σ orbital (HOMO-7 at the PBE level) is the least
localized one, and this orbital has the smallest eigenvalue shift
in going from α = 0 to α = 1, at which point this σ orbital
becomes the least bound one among orbitals of large d char-
acter, similar to what is observed for the case of σ? and π?
orbitals.
Of particular importance in Fig. 4 is the ordering of the
orbitals at the HF level (equivalent to α = 1, β = 0), where
the HOMO is incorrectly predicted to be of σ? character and
the doubly degenerate HOMO-1/HOMO-2 has π? character.
Adding more semilocal correlation to HF decreases the mag-
nitude of the π? − σ? separation slightly, but the HOMO still
has σ? character even at β = 1. Upon removing some of the
exact exchange, however, the π? − σ? ordering gets reversed,
and for α . 0.5, HOMO has π? character, in agreement with
the experimental data. Therefore, the small π? − σ? separation
predicted by PBE0 (α = 0.25, β = 1) can be traced to the incor-
rect description of the ordering at the HF level, with PBE0 still
having “too much” exact exchange or “not enough” semilocal
exchange. Since semilocal exchange is known to partially rep-
resent non-dynamical correlation,72–76 we attribute the appar-
ent success of the PBE predictions (for the first two peaks) to
064306-6 Shi et al.
a more accurate accounting of non-dynamical correlation in
PBE compared with PBE0.
In order to investigate the effect of the degree of orbital
localization on the difference between semilocal and hybrid
functional predictions, we have also performed PBE and PBE0
calculations for diatomic molecules CuS− and AgO− and com-
pared with CuO− . Substituting Cu and O with isovalent ele-
ments in the next row should result in more extended d− and
p−like orbitals, respectively. Figure 5 shows the predicted pho-
toelectron spectra of CuS− , AgO− , and CuO− at the PBE and
PBE0 levels. For CuS− , the agreement between PBE and PBE0
for the first two peaks (π? and σ?) is very good, much bet-
ter than the case for CuO− , both in terms of the position of
the first peak (doubly degenerate HOMO and HOMO-1) and
the π? − σ? separation. Since these three orbitals making up
the first two peaks have large S 3p character, they are signifi-
cantly more spatially extended than the corresponding orbitals
in CuO− with large O 2p character. Indeed, we have observed
no π? − σ? crossing as a function of α for CuS− , which has
a doubly degenerate HOMO even at the HF level of theory.
Lower lying orbitals of large Cu 3d character, on the other
hand, are still significantly underbound at the PBE level com-
pared with the PBE0, similar to what is observed in CuO− .
For AgO− , on the other hand, the first two peaks have very
similar behavior to that observed in CuO− , with significant
differences between PBE and PBE0 predictions. Also similar
to CuO− , the HOMO of AgO− at HF level is found to be the
singly degenerate orbital of σ? character. For the lower lying
orbitals of largely d character, on the other hand, the agree-
ment between PBE and PBE0 predictions is quite good, as
these molecular orbitals primarily derived from Ag 4d atomic
orbitals are significantly more extended than their counterparts
in CuO− and undergo less severe self-interaction corrections
when a fraction of Fock exchange is mixed in at the PBE0
level.
In summary, as in the case of Cu2 O− , the photoelectron
spectrum of CuO− is well captured by the G0 W 0 @BHLYP
and the hybrid functionals do well in predicting the excita-
tion energies of lower lying states of predominantly Cu 3d
FIG. 5. Eigenvalue spectra of CuS− , AgO− , and CuO− computed with PBE
and PBE0 functionals. The spectra are shifted to align the first peak with the
IP of the anion cluster. Orbitals of π ? , σ ? , non-bonding d, π, and σ character
are same as in Figs. 3 and 4.
J. Chem. Phys. 149, 064306 (2018)
character. However, for the first two peaks, the semi-local
PBE functional provides a much better prediction. This some-
what surprising finding is interpreted in terms of a stronger
SIE effect for the lower lying states, as compared with a
larger role of non-dynamical correlation for the higher lying
states.
C. CuO−2
For the linear CuO−2 structure shown in Fig. 1, DFT cal-
culations at both the PBE and the PBE0 level show that the
molecule does not possess a closed-shell singlet configuration
as originally assumed,16,34 but rather it has a triplet ground
state. At the PBE level, the (3 Σg− ) triplet state of CuO−2 is
energetically favorable than the 1 Σg+ singlet configuration by
0.71 eV, in good agreement with the value of 0.68 eV obtained
previously by Deng et al.39 At the PBE0 level, the triplet
state is energetically favorable by a larger energy difference
of 1.22 eV.
Removing an electron from the triplet CuO−2 to find its IP
requires more careful considerations, as the electron removal
can lead to either a doublet or a quartet configuration of the
neutral cluster. With PBE, the quartet state (4 Π u ) is lower
in energy than the doublet state (2 Π g ), by a relatively small
0.09 eV. However, we find that the quartet configuration pos-
sesses unstable vibrational modes, again in agreement with
the results of Deng et al.39 Furthermore, the doubly degener-
ate HOMO of CuO−2 is in the majority spin channel, and the
charge density difference between the triplet state of CuO−2
and the doublet state of neutral CuO2 indeed corresponds to
the charge density distribution associated with the HOMO of
CuO−2 . PBE0 also predicts the quartet state of the neutral to be
lower in energy than the doublet state but with a much larger
energy difference of 1.36 eV. Furthermore, PBE0 calculations
do not reveal any unstable vibrational modes, and because the
doubly degenerate HOMO of CuO−2 is in the minority spin
channel, the charge density difference between the triplet state
of CuO−2 and the quartet state of neutral CuO2 does correspond
to the charge density distribution associated with the HOMO
of CuO−2 .
Figure 6 shows the computed and experimental photo-
electron spectra of CuO−2 . In the experiments of Wu et al.,16
sharp photoelectron peaks were observed at 3.47 (X), 3.79 (A),
4.10 (B), 4.28 (C), 4.67 (D), and 5.16 eV (E). In light of the
above discussion, the PBE and PBE0 spectra have been shifted
according to the total energy difference between the triplet
3 Σ − state of CuO− and the doublet or quartet state of CuO ,
g 2 2
respectively. As explained above, for the OT-RSH results, no
shift of eigenvalues is needed. Nevertheless, the neutral energy
still comes into play as part of the optimal tuning process.
As in PBE0, the OT-RSH calculations also found the quartet
to be lower in energy and with a charge density difference
compatible with the HOMO of the anion.
Comparison of the computed peaks with the measured
photoelectron spectrum reveals interesting trends. With PBE,
the onset energy of 4.01 eV is much too high in comparison
with the measured value at 3.47 eV. However, the overall line
shape of the spectrum appears to correspond to the experiment
fairly well. Indeed, Fig. 6 also reveals that if the PBE data are
064306-7 Shi et al. J. Chem. Phys. 149, 064306 (2018)

the G0 W 0 @BHLYP, which was shown earlier to lead to very

FIG. 6. Experimental photoelectron spectrum of CuO−2 (Ref. 16) along with
spectra computed with PBE, PBE0, OT-RSH (α = 0, γ opt = 0.314 a.u.−1 ),
OT-RSH (α = 0.2, γ opt = 0.230 a.u.−1 ), G0 W 0 @PBE, G0 W 0 @PBE0, and
G0 W 0 @BHLYP. The PBE and PBE0 spectra are shifted to align the first peak
with the IP of the anion cluster. Also shown is the PBE spectrum shifted by
the IP of the quartet configuration. See the text for details. Contour plots of the
molecular orbitals discussed in the text, with matching color codes displayed
in the spectra, are shown on the right.
good agreement with the experiment for Cu2 O− (Fig. 2) and
CuO− (Fig. 3), does not perform well for CuO−2 : The sepa-
ration of 1.53 eV between the first two peaks computed with
G0 W 0 @BHLYP is much too large compared with the exper-
imental X − A separation, resulting in a spectrum where all
(A–E) but the lowest energy (X) transitions are predicted above
4.75 eV, approximately 1 eV higher than the experimental
spectrum.
As the differences between the PBE and PBE0 predic-
tions are striking, it is instructive to examine them in more
detail. At the PBE level, the HOMO of CuO−2 occurs in the
majority spin channel and is a doubly degenerate orbital of
eg symmetry that is a nearly equal mixture of O 2p and Cu
3d states. The LUMO in this case corresponds to the same
(spin-split) eg orbital in the minority spin channel. At the
PBE0 level, on the other hand, while LUMO is still the eg ↓
orbital, HOMO occurs in the minority spin channel and has
eu symmetry, which is almost purely composed of O 2p states
(in a slightly π bonding configuration). In Fig. 7, we plot the
(unshifted) eigenvalue spectra of CuO−2 at the PBE, PBE0, and
HF levels. As observed in the figure, this switch in the orbital
character of HOMO occurs as the eg ↑ orbital gets pushed down
by as much as 1.98 eV, while the eu ↓ orbital is pushed down
by only 0.6 eV in going from PBE to PBE0. At first sight, it
is tempting to interpret this large difference in the downward
shift of the eigenvalues in terms of the character of the relevant
orbitals, namely, since the eg orbital has approximately 50%
Cu 3d character, while the eu orbital has practically no con-
tribution from the Cu 3d states, the SIE is expected to affect

shifted by the IP (3.92 eV) of the “incompatible” quartet con-

figuration anyway, improvement with the experiment improves
drastically. We note that in this scenario the PBE spectrum is
shifted so as to align the doubly degenerate HOMO-1/HOMO-
2 in the minority spin channel with the IP of the quartet
configuration, so that the removal of one of the electrons in
HOMO-1/HOMO-2 of CuO−2 would lead to the 4 Π u configu-
ration of CuO2 . However, this comes at the cost of predictive
power, as strict validity of the theoretical procedure demands
that the doublet be used. With PBE0 or OT-RSH, while the
onset energy is close to the measured value [especially with
OT-RSH (α = 0) for which the onset is 3.50 eV], separations
between the first two computed peaks, which are 0.85, 1.03,
and 1.27 eV for PBE0, OT-RSH (α = 0), and OT-RSH (α = 0.2),
respectively, are much too large compared with the experimen-
tal X − A separation of 0.32 eV and, in fact, are in much worse
agreement with the experiment than the prediction of PBE.
Turning to the GW results, as before the G0 W 0 @PBE quasi-
particle energies with an onset energy of 2.81 eV are signif-
icantly underestimated with respect to the experimental data.
However, unlike the case for Cu2 O− and CuO− , G0 W 0 @PBE0 FIG. 7. (Unshifted) Eigenvalue spectra of CuO−2 (along with symmetries of
the associated orbitals) in the majority (↑) and minority (↓) spin channels
provides very good agreement with the experimental data: The
at the PBE, PBE0, and HF level of theory. Contour plots of the molecular
onset energy is only 0.09 eV higher than the X peak, and the orbitals discussed in the text, with color codes matching the levels shown in
MAE over the six measured peaks is 0.17 eV. Interestingly, the spectra, are shown on the left.
064306-8 Shi et al.
the eg orbital more than the eu orbital, leading to the observed
change in the HOMO orbital character. However, SIE cannot
be the sole explanation, as the orbital of eu symmetry in the
majority spin channel (eu ↑ ), which has the same nearly pure O
2p composition as eu ↓ , is observed to shift down by the large
amount of 1.87 eV, unlike its eu ↓ counterpart, in going from
PBE to PBE0. Note that this difference in the amount by which
spin-split orbitals get pushed down in energy becomes most
obvious in the extreme case of HF level of theory; e.g., the
eu ↑ and eu ↓ orbitals shift down by the significantly different
amounts of 7.88 and 1.93 eV, respectively, in going from PBE
to HF.
In addition to SIE, another factor that contributes to the
different ordering of orbitals at the PBE and PBE0 level is
the amount of spin-splitting. In general, introduction of exact
exchange is expected to increase spin-splitting. This is indeed
what we observe in CuO−2 , especially for doubly degenerate
orbitals for which the increase in spin-splitting as a func-
tion of the amount of exact exchange is particularly large.
For example, the 1.22 eV spin-splitting of the eu orbitals (of
predominantly O 2p character) at the PBE level increases
to 2.50 and 7.20 at the PBE0 and HF levels, respectively.
Similarly, the 1.38 eV spin-splitting of the eg orbital men-
tioned earlier (HOMO and LUMO at PBE) increases to 4.53
and 15.35 eV at PBE0 and HF, respectively. Accordingly, as
more exact exchange is introduced, the eigenvalue spectrum
becomes more segregated with respect to the spin channel;
namely, the spectrum consists of clusters of several states in
the majority/minority spin channels before switching to the
other spin channel. For example, as shown in Fig. 7, the six
highest energy-occupied orbitals at the HF level all occur in the
minority spin channel, followed by six orbitals in the majority
spin channel, and so on. This is significantly different from the
much more homogeneous ordering of orbitals (with respect to
spin channel) at the PBE level. This observation can be qual-
itatively understood as follows: Removing an electron from
the minority (as opposed to majority) spin channel of a given
orbital in the anion cluster would result in a neutral cluster
configuration with a larger spin imbalance and hence be ener-
getically more favorable due to the increased magnitude of
the exchange energy. Because the HF eigenvalues are related
to (unrelaxed) electron removal energies, it makes sense that
in all the occupied spin-split orbitals, those in the minority
channel appear at higher energies (less negative eigenvalues)
than those in the majority spin channel, as observed in Fig. 7.
However, one should notice that this exchange interaction has
a profound effect, at the HF level, not just on spin-split orbitals
but also on orbitals of significantly different shape and atomic
orbital content. For example, Fig. 7 shows that at the HF level
the six highest eigenvalues all occur in the minority spin chan-
nel. In particular, the doubly degenerate HOMO-2/HOMO-3
of eg symmetry in the minority spin channel, where the Cu
atom is in a pdπ bonding configuration with the O atoms, is
located ∼3.30 eV higher than the eu orbitals in the majority
spin channel, in spite of the fact that eg ↓ orbitals have ∼85%
Cu 3d character, while the eu ↑ orbitals have almost purely O
2p content.
Because the amount by which spin-split levels are
pushed down in energy with more exact exchange is
J. Chem. Phys. 149, 064306 (2018)
FIG. 8. DFT eigenvalue centers (average of majority and minority spin chan-
nel eigenvalues) of CuO−2 orbitals mentioned in the text computed with
differing amounts of exact exchange [α in Eq. (1) varying from 0 to 1, with
β = 1]. The orbitals have the same color code as in Figs. 6 and 7. The eigenvalue
centers for HF calculations (α = 1, β = 0) are also shown.
spin-channel-dependent, we focus on how the centers of spin-
split states change as a function of exact exchange (α), as
shown in Fig. 8. This averaging over spin-splitting provides a
clearer effect of SIE. Indeed, the trends observed in Fig. 8 are
consistent with the orbital characters of the states. The states
with symmetries of a1g (σ bonding), b1g , b2g (non-bonding
Cu d xy and dx2 −y2 orbitals), and eg (π bonding), which have
pure or very large Cu 3d content, fall into one category, which
are affected the most by exact exchange. Above them are three
states with symmetries of a2u , a1g (σ anti-bonding), and eu
(π bonding of O 2p orbitals), which have very little or (practi-
cally) no Cu 3d content. Finally, although the center of the eg
state (nearly equal mixture of O 2p and Cu 3d orbitals in an
anti-bonding π configuration) does not show a significant vari-
ation as a function of α, the reason for this is that the unoccu-
pied eg ↓ orbital (LUMO at PBE and PBE0 levels and LUMO+5
at HF) is pushed up in energy to maintain the symmetry of
spin-splitting. As shown in Fig. 7, the occupied eg ↑ orbital
does experience significant SIE, as the level moves down
by ∼8.3 eV.
The above analysis shows that on the one hand, there
is a significant role played by SIE, indicating a preference
for hybrid functionals. But on the other hand, the disagree-
ment between the eigenvalue spectra produced by the hybrid
functionals and experiment, along with the good agreement
(up to a shift) between the PBE data and the experiment,
suggests a strong role of non-dynamical correlation. This sug-
gests that a useful compromise between these two constraints
may be sought by using a Fock exchange fraction α that is
lower than the default 25% in PBE0. This idea has prece-
dence in the context of energy differences between high-spin
and low-spin energy splittings in spin-crossover molecules,
such as Fe(ii)–S complexes, where an exact exchange admix-
ture of 10%-15% was recommended.77–79 Figure 9 shows the
shifted spectra computed with α values ranging from 0 (PBE)
to 0.25 (PBE0). We observe that it is indeed possible to get
very good agreement with the experimental data if one uses
a Fock exchange fraction of 15%. In this case, the largest
064306-9 Shi et al.
FIG. 9. The experimental photoelectron spectrum of CuO−2 along with DFT
eigenvalue spectra computed with Fock exchange fractions α varying from 0
(PBE) to 0.25 (PBE0). In each case, the spectrum is shifted to align the first
peak with the IP of the anion cluster.
discrepancy of 0.25 eV is in the predicted position of the A
peak and the MAE averaged over the six experimental peaks
is 0.09 eV.
In summary, unlike in the previous cases, the photo-
electron spectrum of CuO−2 is not well captured by PBE, or
PBE0/OT-RSH, or even by GW based on a BHLYP starting
point. This is likely owing to a large role of both non-dynamical
correlation and SIE considerations, with the former benefiting
from lack of Fock exchange and the latter suffering from it.
However, using a smaller fraction of exact exchange (15%
for PBE0 and 25% as the starting point for GW ) results in a
quantitatively useful compromise between the two conflicting
requirements.
D. CuO−3
For CuO−3 , the two lowest energy isomers we have found,
shown in Fig. 1, have C s (Iso1) and C2v (Iso2) symmetries. Iso1
possesses a triplet ground state, while the ground state of Iso2
is a singlet. Within both PBE and PBE0, Iso1 is lower in energy
than Iso2, by 0.05 and 0.43 eV, respectively. Both Iso1 and Iso2
feature an O2 unit bonded to a CuO unit. This bonding scenario
is consistent with the work of Wu et al.,16 who suggested it
based on photodissociation events observed at a 355 nm photon
energy for both CuO−3 and Cu(O2 )− complex.
Figures 10 and 11 show the experimental photoelectron
spectrum for the CuO−3 cluster, as compared with the theoret-
ical spectra computed for Iso1 (Fig. 10) and Iso2 (Fig. 11).
In the experiments of Wu et al.,16 sharp photoelectron peaks
were recorded at 3.39 (A) and 4.34 eV (D), as well as weaker
ones at 3.19 (X), 3.51 (B), 4.02 (C), and ∼5.8 eV (E), with the
J. Chem. Phys. 149, 064306 (2018)
FIG. 10. Experimental photoelectron spectrum of CuO−3 (Ref. 16), along with
spectra computed using PBE, PBE0, OT-RSH (α = 0, γ opt = 0.349 a.u.−1 ),
OT-RSH (α = 0.2, γ opt = 0.284 a.u.−1 ), G0 W 0 @PBE, and G0 W 0 @PBE0 for
the lower energy (Iso1) C s structure of CuO−3 . The PBE and PBE0 spectra are
shifted to align the first peak with the IP of the anion cluster.
possibility of feature B (separated from A by 0.12 eV) being
a vibrational replica of A. The spectrum of CuO−3 is basically
divided into two main groups, with features X, A, and B form-
ing the first group and features C and D forming the second.
These two groups are followed by the broader and weaker fea-
ture E. The observed separation between the two main groups
of peaks is roughly the same as the X–Y separation in CuO− .
Accordingly, Wu et al. suggested that these two groups could
be interpreted as derived from the X–Y states of CuO− per-
turbed by an O2 molecule and assigned features X through D
to O 2p orbitals and the E feature at high BE due to Cu 3d
orbitals.
Comparison of the spectra computed with PBE, PBE0,
OT-RSH, G0 W 0 @PBE, and G0 W 0 @PBE0 for Iso1 (Fig. 10)
with the experimental data shows that none of the DFT or GW
methods results in satisfactory agreement with the experiment.
For example, the onset energy with PBE (2.67 eV) is much
smaller than the position of the X peak. While it may be possi-
ble to assign some of the peak positions predicted with hybrid
functionals and G0 W 0 @PBE0 to photoelectron data (e.g., the
first two peaks of PBE0 and G0 W 0 @PBE0 are within ∼0.15
and ∼0.04 eV of the experimental X and A bands, respectively),
the overall shapes of the predicted spectra do not resemble the
experimental spectrum that has two broad peaks centered at
064306-10 Shi et al.
FIG. 11. Experimental photoelectron spectrum of CuO−3 (Ref. 16), along with
spectra computed with PBE, PBE0, OT-RSH (α = 0, γ opt = 0.246 a.u.−1 ),
OT-RSH (α = 0.2, γ opt = 0.165 a.u.−1 ), G0 W 0 @PBE, G0 W 0 @PBE0, and
G0 W 0 @BHLYP for the Y-shaped Iso2 structure of CuO−3 (with C2v symme-
try). The PBE and PBE0 spectra are shifted to align the first peak with the IP
of the anion cluster. Contour plots of the molecular orbitals (with associated
symmetries) discussed in the text are shown on the right, with matching color
codes displayed in the computed spectra.
3.39 and 4.34 eV and no appreciable signals between 4.34 and
5.80 eV.
Agreement between theory obtained for Iso2 and experi-
ment, though not perfect, is much more satisfactory. Assuming
that the experimental feature B is indeed a vibrational level
of feature A, we can compare the first four computed peaks
at each level of theory with features X, A, C, and D in the
experiment. The MAEs for PBE, PBE0, OT-RSH (α = 0), and
OT-RSH (α = 0.2) are then found to be 0.17, 0.15, 0.24, and
0.34 eV, respectively. We therefore focus on Iso2, although
we comment further on the isomer issue below. We also note
that using a Fock exchange fraction α between PBE and PBE0
values leads to only slightly better agreement with the experi-
ment. The MAEs for α = 0.05, 0.10, 0.15 are found to be 0.085,
0.12, and 0.10 eV, respectively. The computed binding ener-
gies are reported in the supplementary material. Therefore, for
the analysis and discussion to follow, we focus on PBE, PBE0,
OT-RSH, and G0 W 0 levels of theory.
For Iso2, the first peak is predicted quite well (within ±0.1
eV) with both PBE and hybrid functionals. While PBE and
PBE0 predictions for the first two peaks are very close to each
other and agree well with the experiment, the positions of the
next two peaks are overestimated and underestimated by PBE
and PBE0, respectively, by 0.2-0.3 eV. Surprisingly, the exper-
imental peak at ∼5.8 eV is best predicted with PBE, while the
predictions from PBE0 and range-separated hybrid functionals
are not as good, even though the relevant orbitals in this energy
range indeed have large (>90%) Cu 3d character. Similar to
the other clusters considered, the G0 W 0 @PBE predictions are
J. Chem. Phys. 149, 064306 (2018)
poor, with the first two peaks underestimated by 0.8-1.0 eV
and an averaged MAE of 0.73 eV. The G0 W 0 @PBE0, on the
other hand, provides excellent agreement with the experimen-
tal data for the first four peaks with an MAE of 0.07 eV. The
fifth peak, however, lies too low in the G0 W 0 @PBE0 cal-
culation. Similar to the case of CuO−2 , the G0 W 0 @BHLYP
results, while better than the G0 W 0 @PBE, are not good; the
predicted quasiparticle levels are found to be much more
bound compared with the experiment, and the averaged MAE
is 0.51 eV.
Analysis of the different orbital characters for Iso2, also
shown in Fig. 11 at various levels of theory, additionally lends
support to the assumption of a CuO− unit perturbed by an O2
unit: In particular, at the PBE level, HOMO-1 of b1 symmetry
and HOMO-2 of a1 symmetry have very similar shapes and
orbital content as those of X (π?) and Y (σ?) states of CuO−
(see Fig. 3), respectively, as they contain very little (less than
3%) contribution from the O2 unit. We note, however, that
these b1 and a1 states of CuO−3 do have appreciable (∼40 and
∼70%, respectively) Cu 3d content, similar to π? and σ? states
of CuO− . Orbitals of large O 2p character at the PBE level are
HOMO (a2 symmetry) and HOMO-3 (b2 symmetry) with very
little (less than 10%) Cu 3d contribution.
One of the significant changes in the ordering of the
orbitals in going from PBE to PBE0 for Iso2 of CuO−3 is the
switching of a1 and b2 orbitals. This behavior can again be
understood in terms of the degree of spatial localization of the
relevant orbitals. In going from PBE to PBE0, orbitals of a2 ,
b1 , and a1 symmetry are pushed down in energy by the sim-
ilar amounts of 1.67, 1.60, and 1.45 eV, respectively, while
the b2 orbital becomes more bound by only 0.76 eV (keep in
mind that the spectra plotted in Fig. 11 are shifted eigenvalue
spectra). From the shapes and spatial extents of the molecular
orbitals plotted in Fig. 11, one can easily observe that the b2
is the least localized orbital, which accordingly gets affected
the least by SIE, consistent with the difference in the shifts of
the corresponding eigenvalues.
Another important observation about the PBE and PBE0
spectra of CuO−3 is related to the separation of the b1 and a1
orbitals, which correspond to the π? and σ? orbitals of CuO− ,
as mentioned above. With PBE, the b1 − a1 separation in CuO−3
has exactly the same value of 0.88 eV as the π? − σ? separation
of CuO− . However, with PBE0, while the π? − σ? separation
of CuO− drops significantly to 0.46 eV, the b1 − a1 separation
in CuO−3 is only reduced to 0.73 eV and remains close to the
PBE value. Earlier, we attributed the large change in the π?
− σ? separation of CuO− upon addition of exact exchange
to a more accurate accounting of non-dynamical correlation
in PBE compared with PBE0. Our finding of similar b1 − a1
separation in CuO−3 with PBE and PBE0 is then in accordance
with the expectation that non-dynamical correlation should
play a less significant role in larger and less symmetric molec-
ular systems. Accordingly, both the PBE and the PBE0 do a
reasonably good job of describing the first two main (broad)
experimental peaks, while PBE is clearly much better for the
CuO− molecule.
The results additionally show that while starting points
that involve some fraction of exact exchange are defi-
nitely needed for satisfactory agreement of one-shot G0 W 0
064306-11 Shi et al.
predictions with experiment, the amount of that fraction is
highly dependent on the cluster composition: Clusters with
larger Cu content (Cu2 O− and CuO− ) appear to need DFT
starting points with a larger exact exchange fraction, such
as BHLYP, than clusters with a smaller Cu content (CuO−2
and CuO−3 ) for which the PBE0 starting point works quite
well.
Finally, we note that because Iso1 is slightly lower in
energy than Iso2, one could have expected it to be the exper-
imentally pertinent isomer. Here, we note that generally pho-
toemission measurements of clusters are not necessarily taken
at thermal equilibrium and that higher energy clusters may
dominate the experimental spectrum owing to kinetic con-
siderations.51 Still, the remaining differences between theory
for Iso2 and experiment may indicate some presence of Iso1
under the experimental setup. Furthermore, the Iso1 structure
is inherently floppy and its orbital arrangement may depend
on the exact geometry, and therefore change with temperature.
The overall observed spectrum may then reflect contributions
from both the isomers.80 Exploring this scenario, however,
would require extensive molecular dynamics simulations that
are outside the scope of this article.
IV. SUMMARY
In summary, we provided a systematic comparison of
DFT- and GW -computed eigenvalue spectra to experimen-
tal photoelectron spectra of four small copper oxide cluster
anions–Cu2 O− , CuO− , CuO−2 , and CuO−3 —with a focus on
comparison between semi-local and hybrid functional (within
DFT and as a starting point for a G0 W 0 calculation). A main
theme found in the comparison between theory and experiment
is that the theoretical success hinges on a number of constraints
that are difficult to fulfill simultaneously. On the one hand,
hybrid functionals have a clear advantage in mitigating self-
interaction errors. On the other hand, removal of some semi-
local exchange, which is necessary for creating a hybrid func-
tional, results in a less successful treatment of non-dynamical
correlation. Generally, we found non-dynamical correlation to
increase for smaller, more symmetric clusters but to bear some
importance also for the larger ones. As a consequence, for
some clusters (notably Cu2 O− ), conventional hybrid function-
als were very successful, for others (notably CuO−2 ), a semi-
local hybrid (with some rigid shift) was quite accurate. For
others yet, a hybrid functional with a reduced amount of Fock
exchange turned out to be a successful compromise. These
trends reflected themselves in the GW calculations as well:
Whereas Cu-rich clusters, where SIE is a major issue, required
more (50%) exact exchange in the hybrid functional starting
point, Cu-poor clusters required less exact exchange (25%).
These results obtained with the one-shot G0 W 0 method suggest
that it would be interesting future work to examine the effects
of various levels of GW self-consistency as well as the effects
of beyond-GW corrections. Generally, the importance of non-
dynamical correlation is expected to decrease with the sys-
tem size, explaining the well-documented success of DFT for
larger clusters. However, larger clusters can and very often do
encounter a significant problem of multiple isomers, which has
also been reflected here in the case of CuO−3 . Taken together,
J. Chem. Phys. 149, 064306 (2018)
these findings call for careful assessment of the opposing roles
of non-dynamical correlation and self-interaction errors in
functional choice for small transition metal oxide and metal-
organic clusters. They also call for further development of DFT
and GW approaches that can balance the two issues in a natural
way.
SUPPLEMENTARY MATERIAL
See supplementary material for tabulated PBE and PBE0
atomic coordinates, and experimental, DFT (PBE, PBE0, OT-
RSH), and G0 W 0 (with PBE, PBE0, and BHLYP starting
points) binding energies for all copper oxide cluster anions
considered.
ACKNOWLEDGMENTS
B.S. and S.Ö. would like to acknowledge support from the
U.S. Department of Energy Grant No. DE-SC0017824, as well
as the National Energy Research Scientific Computing Cen-
ter, a DOE Office of Science User Facility supported by the
Office of Science of the U.S. Department of Energy under Con-
tract No. DE-AC02-05CH11231, for computational resources.
F.B. acknowledges High Performance Computing resources
from GENCI-CCRT-TGCC (Grant No. 2017-096018). Work
in Rehovoth was supported by the European Research Council.
We also would like to thank Natalie Orms and Anna I. Krylov
for useful discussions.
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