Second-order perturbation theory to determine the magnetic state

of finite size aromatic hydrocarbons molecules

A. Valentim1, 2, ⇤ and D. J. Garcı́a1, 2
1
Centro Atómico Bariloche and Instituto Balseiro, CNEA, 8400 Bariloche, Argentina
2
Consejo Nacional de Investigaciones Cientı́ficas y Técnicas (CONICET), Argentina
(Dated: July 4, 2017)
Conjugated system have complex behaviors when increasing the number of monomers, which is
one of the reasons that makes long oligomers hard to be characterized by numerical methods. An ex-
ample of this are fused-azulene, a molecule that has been reported to displays an increasing magnetic
moment with system size. A similar system composed of symmetric fused-benzene rings is reported
to be always no magnetic. Instead of the empiric parametrized Pariser-Parr-Pople (PPP) Hamilto-
nian, a standard model for conjugated molecules, we consider the Hubbard Hamiltonian to explore
a range of low electronic correlation by means of perturbation theory (PT). We show that a simple
second-order perturbation treatment of electronic correlations by means of Rayleigh-Schrödinger PT
allow to accurately infer about the magnetic state of these long complex ⇡-conjugated molecules.
For fused-azulene our results supports the hypothesis that the high-spin ground state on azulene
oligomers comes from the frustrated geometry of these chains. We validate this approach using
Density Matrix Renormalization Group (DMRG) calculations. Our procedure procedure could be
helpful to describe the magnetic ground state of a larger set of conjugated molecules.

I. INTRODUCTION with spin polarization of the oligomer when only a few

The study of carbon based materials has grown to
several direction spanning from engineering of electronic
devices [1–4] to research on biomedical application [5–
7]. Despite of purely organic magnetic compounds be-
ing already a reality [8], the seeking for functional ma-
terials with magnetic properties such as super paramag-
netism and ferromagnetism is still a goal. Once build-
ing blocks of such materials are molecules instead single
atoms, then depending on the number of atoms to be
considered, these systems can be hard to be explored
computationally (for a recent review see Ref.[9]). Reli-
able physical systems that has attracted great deal of
attention are quasi-unidimensional molecules. Exam-
ples are fused-benzene (C4n+2 H2n+4 ) and fuzed-azulene
(C8n+2 H4n+4 ) oligomers built from polycyclic aromatic
hydrocarbons laterally fused. While the first is a one-
dimensional graphene stripe with zigzag edges the second
is a linear chain formed from fused azulene molecules, as
so having conjugated rings with odd number of carbon
atoms.
The fused-benzene series of molecules has already been
synthesized up to nine monomers [10, 11] and is reported
not to be magnetic. Solid state devices of oligoacene (fi-
nite fused-benzene chain) displays a promising increasing
conductivity with the number of aromatic rings [1–4].
Beyond nine monomers, symmetric oligoacenes (benzene
chain with symmetric bond length), has been theoreti-
cally investigated by di↵erent many-body techniques and
has also been reported to not display magnetic polariza-
tion [12–15]. The same kind of numerical approaches pre-
dicts fused-azulene to display a singlet-triplet transition
⇤ alexandravalentim@cpd.ufmt.br
azulene molecules are linearly fused [9, 15, 16]. Fused-
azulene oligomers has also been presented as a candidate
of organic multiferroic material [15], as so displaying fer-
roelectricity and ferromagnetic proprieties.
These planar molecules (schematically shown at
Fig.1(a-b)) conventionally can be described as compose
by unsaturated hydrocarbons linked by alternate dou-
ble and single bonds (which are not represented at fig-
ure). The ladder like representation of these oligomers
( Fig.1(b-c)) only di↵er by a twisted link in the azu-
lene monomer. Within molecular orbital theory [17] hy-
drogen atoms are neglected and the physics of the sys-
tem is described by a extended molecular orbital com-
posed only by a single pz orbital on each carbon atom
(⇡-orbitals). At half filled band the electronic distribu-
tion on ⇡-orbitals allows magnetic frustration on azulene,
due to the rings with odd number of carbon atoms. For
this reason we would expect azulene molecules to have a
lower energy triplet excitation than benzene molecules.
FIG. 1. (color online) Schematic structure for a fused-azulene
(a) and a fused-benzene molecule (b) and its respective ladder
like representations (c) and (d). The square brackets enclosed
areas represents the unit cell of each polymer structure. The
dots at ladder representations denote the positions of the car-
bon atoms.
 2

Low electronic excitations, understood as arising II. MODEL AND METHOD

from delocalized electrons in the molecular orbital (⇡-
electrons), have been appropriately described by the We used the Hubbard model [4] to describe the elec-
empiric Pariser-Parr-Pople Hamiltonian [18, 19] for un- tronic interactions in conjugated systems shown at Fig.1.
saturated ⇡-conjugated organic molecules. For sym- The model Hamiltonian contains a non-interacting part
metric fused-azulene molecules the ground state of Ĥ0 and a term that incorporates the on-site electron-
the PPP model with inter-site Coulomb interaction electron interaction Ĥ1 :
parametrized by the Ohno [20] formula and fixed on-site
Hubbard interaction 4.69 (in units of transfer integral Ĥ = Ĥ0 + Ĥ1 . (1)
between bonded sites) is singlet up to 5-azulene. Be- The non-interacting part is a tight-binding Hamilto-
yond this number of monomers and up to 11-azulene the nian,
oligomers have a triplet state [15]. The fuzed-azulene
geometry has been also explored, in the strong corre-
N
X ⇣ ⌘
lated regime, by using the spin-1/2 antiferromagnetic Ĥ0 = t ĉ†i ĉj + ĉ†j ĉi , (2)
<i,j>;
model Heisenberg model [21]. The magnetic ground state
moment is also observed to increase with the monomer where the first term describe the kinetic energy with a
length. constant hopping t between nearest neighbors atoms of
In order to explore this singlet-triplet transition, at carbon (we take t as the energy unit). In the framework
low correlated regime, by means of an analytic tech- of ⇡ electron theories, the operator ĉ†i ( ĉi ) creates
nique, here we use the Hubbard model to investigate the (annihilate) a electron of spin localized in a ⇡ orbital
ground state of these conjugated systems as a function at site i.
of oligomer size and electron-electron interaction. This The interacting part of Ĥ can be written in the form,
choice is motivated by the flexibility to change arbitrarily N ✓ ◆✓ ◆
X 1 1
the parameters, then small values of electron-correlation Ĥ1 = U n̂i" n̂i# , (3)
can be treated as a perturbation to the system. The Hub- i
2 2
bard Hamiltonian neglect the Coulomb repulsion between
electrons of di↵erent atoms and takes into account just where U is the on-site Coulomb interaction and N de-
the interaction between electrons in the same site (on-site note the number of sites, which is equal to the number of
Coulomb repulsion). This model simplify the complex- electrons in the system. The total electron density com-
ity of the problem while it retains electronic correlations ported by an orbital ⇡ is n̂i = n̂i" + n̂i# and n̂i = ĉ†i ĉi
and is successfully used to elicit information on corre- is the local particle number operator for electrons of spin
lated systems, including conjugated molecules [22–24]. at site i. At half-filling band, the factor 1/2 fixes the
We employ finite density matrix renormalization group chemical potential for occupation hn̂i i = 1 on each site.
(DMRG) and perturbation theory, up to second-order,
to investigate the magnetic GS of oligoacene and fused-
A. First- and second-order perturbation theory
azulene molecules as a function of electronic correlations.
The first is a powerful and complex numerical variational
technique for calculating the ground state of interacting In the limit of weakly correlated electrons we can treat
quantum systems and the second is a well established and the interaction as a small perturbation in the total en-
analytical approach. ergy. The energy for the unperturbed system is simply
the energy of a tight-binding model
Although there exist more sophisticated PT to explore
the ground-state of molecules perturbatively (as Møller- E (0) = hn(0) |Ĥ0 |n(0) i, (4)
Plesset [25]), here we use a simple Rayleigh-Schrödinger (0)
where |n i is the ground state of the unperturbed sys-
PT to investigate transitions that take place at weak cor-
related regime. In agreement with recent works [26–28] tem, which can easily be obtained once Ĥ0 is exactly
we show that second-order PT captures the e↵ect of elec- diagonalizable.
tronic correlation on the magnetic state of these complex Using the Rayleigh-Schrödinger perturbation theory
⇡ conjugated molecules. We empathize that first-order [2] up to second-order, we can write the energy of the
PT fails to reproduce the DMRG results for the magnetic perturbed system as the expansion up to second-order:
state of these oligomers however second-order PT is able E = E (0) + ↵ + 2
+ O( 3
), (5)
to qualitative (for small oligomers) and quantitative (for
larger oligomers) reproduce the numerical DMRG results. where = U/t, ↵ = hn(0) |Ĥ1 |n(0) i and
Our results points to the frustration, arising from a com- X |hn(0) |Ĥ1 |k (0) i|2
2
bination between the geometry of azulene and correlated = (0) (0)
, (6)
⇡-electrons, as the source of the magnetic polarization. k6=n En Ek
At next section we briefly describe the model and nu-
merical approaches used, in section III the results are being |k (0) i a state of the unperturbed system. Notice
presented and our final remarks are given in section IV. that Ĥ1 is not diagonal at the base of states of |k (0) i.
 3

Details on perturbation theory for the Hubbard model
at low correlated regime are presented in [31]. Values of
E (0) , ↵ and to di↵erent oligoacene and fused-azulene
oligomers can be find at Table I.
B. Density Matrix Renormalization Group
Although the DMRG algorithm was first presented
to treat an unidimensional problem [32], di↵erent low-
dimensional systems can also be accurately treated with
this approach [33, 34]. For the ladder like representa-
tions of oligoacene and fused-azulene in Fig.1 (c-d), we
can map the Hubbard Hamiltonian with first-neighbors
interactions, into a unidimensional Hamiltonian with up
to second-neighbors interactions, easily implemented on
a DMRG algorithm.
Oligomers described by Hamiltonian Eq.7 have SU(2)
symmetry so we can take advantage of the degeneracy
of spin projections MS , for a total spin S, and compute
the low-lying energy of the system in a chosen subspace.
The ground state energy in MS subspace is find when
state while fused-azulene presents a increasing ground
state with the chain length. DMRG calculations vali-
dates this analysis, with the agreement between di↵erent
approaches increasing with the size of the system. We
take U/t . 2 as the upper limit of validity for the results
obtain from perturbation theory, as for larger U/t values
H1 becomes the most relevant term in the Hamiltonian
[1, 38].
To estimate Uc we calculate the singlet-triplet spin gap
defined as E(MS ) = E(MS = 1) E(MS = 0) and de-
fine Uc as the value where this gap closes E(MS ) = 0.
This analysis is illustrated in Fig.2(a-b) for two linearly
fused 2-azulene molecule ( 18 atoms). Panel (a) shows
FOPT MS=0
-25 FOPT MS=1
SOPT MS=0
SOPT MS=1
DMRG MS=0
-30 DMRG MS=1

E/t
|MS |  S and E(S)  E(S + 1), where E(S) is the
lowest energy belonging to a given S value [35, 36].
To establish the accuracy of our DMRG simulations we -35
have compared DMRG results for the energy at U = 0
with the exact solution of the tight-binding Hamiltonian. (a)
We compute the ground state-energy with di↵erent sizes -40
of the Hilbert space, and we kept a typical cuto↵ of m = 0 1 2 3
800 to a maximum of m = 1200 states per block at final U/t
iteration. In these conditions the energy precision is in
the fourth decimal digit. The relative energy error is 0.6
comparable to the DMRG weight lost kept lower than (b)
10 5 in the worst cases.
0.5
∆E(MS)/t

III. RESULTS AND DISCUSSIONS 0.4

We consider DMRG simulations and a conventional

PT up to second-order to compute the energy and
spin gap excitations of fused-azulene and fused-benzene-
molecules with up to 74 ⇡-orbital (9 azulene and 18 ben-
zene monomers). When referring to the number of ⇡-
orbital or number of atoms we are counting only carbon
atoms. We explore the Hubbard’s model phase space
with correlations ranging from the noninteracting limit,
U = 0, to U = 3t and di↵erent systems size. We calcu-
late the unperturbed lowest energy E (0) (MS ), the first-
order ↵(MS ) and second-order (MS ) coefficients of the
Rayleigh-Schrödinger PT for the system with spin pro-
jection MS = 0 and MS = 1. These results, for di↵erent
oligomer sizes, and the value for Uc obtain by first- and
second-order PT and by DMRG are shown at Table I.
We find that by using fist-order PT both systems un-
dergoes a singlet-triplet state transition in a Uc which
depend of the oligomer size. However by means of second-
order PT we qualitatively reproduce the numerical pre-
dictions, that oligoacene always has a singlet ground
0.3
FOPT
SOPT
0.2 DMRG
0 1 2 3
U/t
FIG. 2. (color online) Panel (a) shows low-lying energies
E(MS = 0) and E(MS = 1), and panel (b) shows the singlet-
triplet spin gap E(MS ), both as a function of U for a fused-
azulene molecule with 2 monomers (18 atoms). The DMRG
data has a error bar which is smaller than the symbols size.
the energy computed on the MS = 0 and MS = 1
spaces. We observe that the curve for E(MS = 0) lies
slightly below E(MS = 1) curve, what indicates a sin-
glet state with a finite gap between the ground state en-
ergy, E(MS = 0), and the energy of the first magnetic
 4

(1) (2)
N E (0) (0) ↵(0) (0) E (0) (1) ↵(1) (1) Uc Uc Uc
2-azulene 18 -24.521 -4.449 -0.284 -24.016 -4.557 -0.271 4.709 - -
4-azulene 34 -46.807 -8.414 -0.532 -46.586 -8.507 -0.517 2.362 - -
5-azulene 42 -57.947 -10.396 -0.656 -57.787 -10.485 -0.641 1.796 - 2.6
6-azulene 50 -69.088 -12.378 -0.780 -68.967 -12.464 -0. 765 1.409 2.376 2.0
7-azulene 58 -80.228 -14.360 -0.904 -80.133 -14.443 -0. 889 1.134 1.593 1.8
9-azulene 74 -102.509 -18.324 -1.153 -102.447 -18.404 -1.137 0.779 0.965 1.0
4-acene 18 -24.930 -4.500 -0.294 -24.340 -4.604 -0.275 5.636 - -
10-acene 42 -58.601 -10.500 -0.696 -58.451 -10.559 -0.658 2.518 - -
18-acene 74 -103.492 -18.500 -1.242 -103.439 -18.537 -1.183 1.415 - -

TABLE I. Non-interacting lowest energy E (0) (MS ), first- ↵(MS ) and second-order (MS ) coefficients of perturbation theory
and critical value of electronic correlation Uc obtain by FOPT, SOPT, and DMRG calculations respectively (all in units of t)
for di↵erent number of monomers (N atoms) in oligoacene and fused-azulene molecules.

excited state, E(MS = 1). As expected, DMRG is the

lowest energy and second-order PT (SOPT) data is closer
to DMRG results than first-order PT (FOPT). At panel (a)
(b) we plot the singlet-triplet spin gap as a function of
electronic correlations. A finite gap indicating a singlet
state is found in agreement with Refs.[9, 15, 16]. FOPT
results points out to a transition from singlet to triplet 0.1
ground state for values of Uc above the validity of the
approximation (not displayed at the plot).
In Fig.3, we plot the singlet-triplet spin gap as a func-
tion of electronic correlations for two di↵erent sizes of
∆E(MS)/t

fused-azulene molecules. FOPT and DMRG calculations FOPT

displays a finite gap in both cases, for small values of
U/t, indicating a singlet state. SOPT estimate Uc be-
low 2t when the chain is larger than 6-azulene. In Ta-
ble I we show that the agreement of the value of Uc be-
tween the di↵erent approaches increases with the num-
ber of monomers. These results on fused-azulenes could
lead to the incorrect assumption that first-order treat-
ment of electronic correlations is enough to describe these
molecules. We show that for fused-benzene FOPT in-
correctly predicts a singlet-triplet transition while SOPT
correctly predicts that the ground state for fused-benzene
is always a singlet.
At Fig.4 we repeat the analysis of the singlet-triplet
spin gap for ten fused monomers of benzene (10-acene
with 42 atoms). DMRG simulations and SOPT cal-
culus exhibit a significant spin gap while using FOPT
the spin gap goes to zero. Second-order PT predicts a
singlet ground state for all values of U/t in agreement
with DMRG. We checked these results up to 18 fused
monomers (see Table I) and we can reproduce the ex-
pected behavior of spin excitations of oligocene chains,
i.e. a finite spin gap which indicates that the ground
state of the system is a singlet independently of the elec-
tronic correlation magnitude and system size [15].
The possibility for ferromagnetism in odd-membered
rings oligomers (fused-azulene geometry) could be related
to flat-band magnetism [39, 40], a ferromagnetic behavior
due to the accumulation of degenerated states at Femi
level. As shown at Fig.5 both n-acene and n-azulene
0 SOPT
DMRG
0.1
(b)
0
0 1 2 3
U/t
FIG. 3. (color online) Singlet-triplet spin gap E(MS ) as a
function of U/t for (a) 5-azulene and (b) 6-azulene oligomers
with 42 and 50 atoms respectively. Arrows points the values
of Uc estimated with each approach. The DMRG data has a
error bar which is smaller than the symbols size.
accumulates states in the Fermi level, but only fused-
azulene shows a transition to a high spin state, ruling
out flat-band as the source for the magnetism on azulene
oligomers. Geometric frustration on n-azulene increases
as the chain length increases (more twisted links as in
Fig.1c) and the Coulomb repulsion needed for a S = 0
to S = 1 transition diminish. These results points to
 5

state for 2-azulene and 3-azulene with a decreasing of

the singlet-triplet spin gap as a function of the chain
length. They argue this would indicate a tendency to
FOPT a magnetic ground state, however simulations on bigger
0.3 SOPT oligomer sizes are need in order to confirm the predic-
DMRG
tion by DMRG [15]. The authors also conjecture the
increasing frustration percentage (number of frustrated
∆E(MS)/t

0.2 links, n, divided by the number of non-frustrated links,

9n + 1) as the origin of a possible higher ground state for
long azulene oligomers [9]. In agreement with Ref.[15]
and our results, density functional theory methods also
0.1
reports a triplet state for 6-azulene [16]. In summary,
second-order PT allowed us to explore the low correla-
tion regime (U/t . 2) and find the same magnetic transi-
0
0 1 2 3 tions shown by more sophisticated and computationally
U/t demanding numerical methods. In the specific case of
fused-azulene our second-order PT results show that a
magnetic transition in this weak interaction regime hap-
FIG. 4. (color online) Singlet-triplet spin gap E(MS ) as a pens for oligomers with more than four monomers.
function of U/t for 10-benzene oligomer with 42 atoms. The
DMRG data has a error bar which is smaller than the symbols
size.
IV. CONCLUSION

frustration (absent on oligoacene) as the source of the

magnetic transition. We employ Rayleigh-Schrödinger perturbation theory
and DMRG technique to study low-lying spin excitations
for two geometrically related conjugated systems. We in-
vestigate the ground state of these conjugated molecules
by using the Hubbard model with weak on-site coulomb
6 interaction, ranging from the non-interacting limit to
Number of states at Fermi level

4 3 U/t = 3, and di↵erent monomer length. We show that

second-order perturbation theory is a reliable tool to
6 characterize magnetic transitions on complex molecules,
3 3 using as a non trivial example fused-benzene and fused-
azulene oligomers. Our results support that for n-azulene
-2 -1 0 1 2 there is a magnetic transition from singlet to triplet as
2 E/t the size the system increases. This transition is not re-
lated to flat-band magnetism, instead, the comparison
fused-azulene with oligoacene suggest that the origin of magnetism in
1 fused-azulene oligomers comes from the frustrated geom-
oligoacene
etry of these chains. For fused-azulene the value of Uc
in which a transition from a singlet to a triplet state
0
10 20 30 40 50 60 70 80 90 take place decrease with the size of the system, being
lower than 2t for oligomers bigger than 4-azulene. The
Number of carbon atoms increasing agreement between SOPT and DMRG simula-
tions, for longer oligomers, makes this approach a useful
FIG. 5. (color online) Accumulation of the number of states tool to the investigation of conjugated organic molecules,
near the Fermi level for oligoacene and azulene molecules as a at weak correlated regime, to system-sizes that would be
function of oligomer size. The number of states is computed
impossible by means of numeric techniques.
within a range of 0.1t around the Fermi level for the tight-
binding model. The inset displays the number of states over
the whole energy spectrum for fused-azulene and oligoacene
chains with 42 atoms. V. SUPPLEMENTARY MATERIAL

DMRG results on antiferromagnetic spin-1/2 Heisen-
berg Hamiltonian for both azulene and benzene oligomers
shows that the magnetic state does not require the ex-
istence of flat energy bands [15]. Configuration inter-
action on PPP model also reports a S = 0 ground
See supplementary material (1) for a detailed deriva-
tion of perturbation theory for the Hubbard model at low
correlated regime and supplementary material (2) for a
Maxima [5] script to compute the fist- and second-order
quantities presented in Table I.

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(Springer Berlin Heidelberg, Berlin, Heidelberg, 2004) pp.
135–137.
[36] E. Lieb and D. Mattis, Journal of Mathematical Physics
3, 749 (1962), http://dx.doi.org/10.1063/1.1724276.
[1] D. Khomskii, Basic Aspects of the Quantum Theory of
Solids: Order and Elementary Excitations (Cambridge
University Press, 2010).
[38] F. Essler, H. Frahm, F. Göhmann, A. Klümper, and
V. Korepin, The One-Dimensional Hubbard Model (Cam-
bridge University Press, 2005).
[39] Z. Gulácsi, A. Kampf, and D. Vollhardt, Phys. Rev. Lett.
105, 266403 (2010).
[40] Y. Suwa, R. Arita, K. Kuroki, and H. Aoki, Phys. Rev.
B 68, 174419 (2003).
[5] Maxima Open-source Computer Algebra Systems Max-
ima; software available at http://maxima.sourceforge.net.
 7

SUPPLEMENTARY MATERIAL (1) FOR The first-order Rayleigh-Schrödinger perturbation

“SECOND ORDER PERTURBATION THEORY teory correction for the energy is
TO DETERMINE THE MAGNETIC STATE OF
FINITE SIZE AROMATIC HYDROCARBONS ↵ = hn(0) |Ĥ1 |n(0) i. (13)
MOLECULES”
The Rayleigh-Schrödinger second-order perturbation
Usually first- and second-order Rayleigh-Schrödinger term at non-degenerate state |n(0) i is
perturbation theory is used in condensed matter starting
from the large interaction limit where the kinetic energy X |hn(0) |Ĥ1 |k (0) i|2
2
is used as a perturbation[1]. In this appendix we show = (0) (0)
, (14)
k6=n En Ek
how to treat the electronic repulsion as a weak pertur-
bation (the general formalism is exposed in refs. 2 and
3). where |k (0) i =
6 |n(0) i is a state of the unperturbed system.
On the main text we use the Hubbard model[4] to de- The diagonal part of Ĥ1 , proportional to the constant
scribe the electronic interactions in conjugated systems. term U/2N , does not introduce any contribution to the
The model Hamiltonian contains a non-interacting part second-order correction for the energy. In this expression
Ĥ0 and a term that incorporates the on-site electron- only the correlation term U n̂i" n̂i# , not diagonal in the
electron interaction Ĥ1 : k basis, contributes to the energy correction at second-
order.
Ĥ = Ĥ0 + Ĥ1 . (7) We write the non-interacting state |n(0) i or |k (0) i as
the direct product of up and down states
The non-interacting part is a tight-binding Hamiltonian,
(0) (0)
X⇣ † ⌘ |n(0) i = |n" i|n# i, (15)
Ĥ0 = t ĉi ĉj + ĉ†j ĉi , (8) (0) (0)
i,j; |k (0) i = |k" i|k# i. (16)

that describe the kinetic energy with a constant hopping For the second-order correction Eq. (14) we need to
t between sites i and j. The interacting part of Ĥ is compute
N
X N
X
Ĥ1 = U (n̂i" 1/2)(n̂i# 1/2), (9) hk (0) |Ĥ1 |n(0) i = hk (0) |U n̂i" n̂i# |n(0) i (17)
i=1 i=1
N
X
where U is the on-site Coulomb interaction and N denote
the number of sites. Ne, is the number of electrons with =U hk (0) |n̂i" n̂i# |n(0) i
spin in the system. i=1

Let us call ĉp the operators that diagonalize Ĥ0 . The

original annihilation site operators are written as a linear
combination of these operators as Using Eqs. (15) and (16)
X N
ĉi = p0 ,i ĉp0 . (10) X (0) (0) (0) (0)
p0
hk (0) |Ĥ1 |n(0) i = U hk# |hk" |n̂i" n̂i# |n" i|n# i (18)
i=1
In the limit of weakly correlated electrons we treat N
X (0) (0) (0) (0)
the interaction as a small perturbation in the total en- =U hk" |n̂i" |n" ihk# |n̂i# |n# i
ergy. The energy of a state can be written as E = i=1
E (0) + ↵ + 2 + O( 3 ) where = U/t. The energy
for the unperturbed system is simply the energy of a Evaluating one of these mean values for the generic spin
tight-binding model variable we have
Y Y †
E (0) = hn(0) |Ĥ0 |n(0) i, (11) hk (0) |n̂ |n(0) i = (h0| ĉq )ĉ†i ĉi ( ĉq0 |0i).
q2Sk, q 0 2Sn,
where
Y Using Eq. (10) we write this expression as
|n(0) i = ĉ†p# ĉ†p" |0i (12)
Y X Y
p" 2Sn," ,p# 2Sn,# hk (0) |n̂|n(0) i = h0| ĉq ⇤ †
p0 i p i ĉp ĉp0 ĉ†q0 |0i
q2Sk, pp0 q 0 2Sn,
is a state of the unperturbed system, which can easily be
obtained once Ĥ0 is exactly diagonalizable. Sn, is a set (19)
X Y Y
of eigenstates of Ĥ0 labelled by p ( =", #) with energy = p0
⇤
i p i h0| ĉq ĉ†p ĉp0 ĉ†q0 |0i.
"p . pp0 q2Sk, q 0 2S n,
 8

(0) (0)
For this mean value to be di↵erent from zero in any case |k# i =
6 |n# i
p0 must belong to Sn and there are two possibilities for
p: X X ⇤ ⇤ ⇤ ⇤
p0 ",j p",j p0 #,j p#,j p0 ",i p",i p0 #,i p#,i
(0) (0) 0 =
• p = p0 implying that Sk, = Sn, so hk | = hn |. "p" + "p# "p 0 " "p 0 #
i,j p0" 2Sn" ,p0# 2Sn#
The Eq. (20) then resumes to
p" 2S
/ n" ,p# 2S
/ n#
X (23)
| p i |2 = hn(0) |n̂i |n(0) i = hn̂i i (20) hP i2
p=p0 2Sn, ⇤ ⇤
X j p0 j" pj" p0 j# pj#
= .
(0) (0) (0) "p" + "p# "p 0 " "p 0 #
and the energy of the state |k i is Ek = En = p0" 2Sn" ,p0# 2Sn#
(0) (0) p" 2S
/ n" ,p# 2S
/ n#
hn |Ĥ0 |n i.
(0) (0)
• If p 6= p0 , then p must not belong to Sn . Then Eq. " is the term obtained when |k" i 6= |n" i and
(20) becomes (0)
|k# i
(0)
= |n# i
⇤
hk (0) |n̂ |n(0) i = p0 i p i (21)
X X ⇤ ⇤
p0 ",j p",j p0 ",i p",i hn̂j# ihn̂i# i
and Sk, must contains all the elements of Sn, that " = (24)
"p" "p 0 "
include p and exclude p0 . The energy of the state i,j p0" 2Sn"
(0) (0) (0) p" 2S
/ n"
|k i is Ek = En + "p "p 0 . P
X [ ⇤ 2
j p0 ",j p",j hn̂j# i]
The condition |k i = 6(0) (0)
|n i can be written as =
"p" "p 0 "
(0) (0) (0) (0) p0" 2Sn"
|k" i|k# i = 6 |n" i|n# i. This last condition can be sat-
p" 2S
/ n"
isfied in three cases
# is completely analogous to ".
(0) (0) (0) (0)
I . |k" i =
6 |n" i ^ |k# i =
6 |n# i
P ⇤
(0) (0) (0) (0) X [ j p0 #,j p#,j hn̂j# i]
2
II . |k" i 6
= |n" i ^ |k# i = |n# i # = (25)
"p# "p 0 #
p0# 2Sn#
(0) (0) (0) (0)
III . |k" i = |n" i ^ |k# i =
6 |n# i p# 2S
/ n#

Taking into considerations these possibilities Eq. (14) The last fourth equations give the second-order pertur-
becomes bation correction to the energy of the state |n(0) i due to
Ĥ1 .
2
= U 2( 0 + " + #) (22) A Maxima [5] script to perform these calculations
is found in supplementary material (2), the executable
(0) (0)
where 0 is the term obtained when |k" i 6= |n" i and script is made available on requesting to the authors.

[1] D. Khomskii, Basic Aspects of the Quantum Theory of
Solids: Order and Elementary Excitations (Cambridge
University Press, 2010).
[2] J. Sakurai and J. Napolitano, Modern Quantum Mechan-
ics, 2nd ed. (Addison-Wesley, 2011).
[3] tagkey1981169, in Second Quantization-Based Methods in
Quantum Chemistry, edited by P. Jørgensen and J. Simons
(Academic Press, 1981) pp. 169 – 172.
[4] J. Hubbard, in Proceedings of the Royal Society of London
A: Mathematical, Physical and Engineering Sciences, Vol.
276 (The Royal Society, 1963) pp. 238–257.
[5] Maxima Open-source Computer Algebra Systems Max-
ima; software available at http://maxima.sourceforge.net.
SUPPLEMENTARY MATERIAL (2) FOR
‘SECOND ORDER PERTURBATION THEORY
TO DETERMINE THE MAGNETIC STATE OF
FINITE SIZE AROMATIC HYDROCARBONS MOLECULES’

1 to set the number of azulene oligomers at the

system
Nsit defines the number of atoms at the system

–> NumberOfOligomers: 2 $ Nsit : 10 + ( NumberOfOligomers - 1)*8; t: 1.$

18

2 to create a matrix, OliMatrix, for the non in-

teracting Hamiltonian

–> modulo( a, b ) :=a - b*floor( a/b )$

–> OliMatrix:zeromatrix(Nsit, Nsit) $
–> for i: 1 thru Nsit do for j: 1 thru Nsit do if i-j = 1 and modulo(i,8)=7 then
OliMatrix[i,j]:-t else if i-j = -1 and modulo(i,8) = 1 then OliMatrix[i,j]:-t else if
i-j = 2 then OliMatrix[i,j]:-t;
–> auxMat:OliMatrix + transpose(OliMatrix)$ OliMatrix:auxMat$

3 compute the eiguenvalues and eigenvectors of

the unperturbed system

–> load (lapack)$

–> eigenSys: dgeev ( OliMatrix ,True)$
–> eigenvalues: eigenSys[1]$
–> eigenvectors: transpose ( eigenSys[2] ) $

1
4 Tight-binding calculation for the electronic den-
sity of the non-perturbated system

–> orderedeigenvalues : sort (eigenvalues) $

FermiGround defines the Fermi level, FermiP1 and FeermiM1 set the eletronic
filling for first excited state

–> FermiGround : orderedeigenvalues[Nsit/2]; FermiP1 : orderedeigenval-

ues[Nsit/2 + 1]$ FermiM1 : orderedeigenvalues[Nsit/2 - 1]$
–> sitedensity (i, FermiLevel) := sum ( if eigenvalues[j] <= FermiLevel then eigen-
vectors[j][i]ˆ2 else 0, j, 1, Nsit)$
–> density : makelist ( [ i , 2. * sitedensity(i,FermiGround)] , i, Nsit)$
densDn and densUp compute respectively the density of electrons with spin up
and down

–> densDn : makelist ([ i , sitedensity(i,FermiM1)], i, Nsit)$ densUp : makelist ([

i , sitedensity(i,FermiP1)], i, Nsit)$
densUpDnMs0 is density of electrons with spin up and down compputed on Ms
= 0 spin projections sub - spaces

–> densUpDnMs0 : makelist ( sitedensity(i,FermiGround)*sitedensity(i,FermiGround),

i, Nsit)$
densUpDnMs1 is density of electrons with spin up and down compputed on Ms
= 1 spin projections sub - spaces

–> densUpDnMs1 : makelist ( sitedensity(i,FermiP1)*sitedensity(i,FermiM1), i,

Nsit)$

5 energies of the unperturbated system on Ms

= 0 and Ms=1 spin projections sub - spaces

–> energyMs0 : 2. * sum ( if eigenvalues[j] <= FermiGround then eigenvalues[j]

else 0, j, 1, Nsit);
24.52188174203637

–> energyMs1 : energyMs0 + FermiP1 -FermiGround;

24.01615315026958

2
6 First-Order Perturbation Theory for the Hub-
bard model on Ms=0 and Ms=1 spin projec-
tions sub-spaces
Eq.(7) at SUPPLEMENTARY MATERIAL (1) compputed on Ms=0 spin pro-
jections sub-spaces

–> alfaMs0 : sum ( densUpDnMs0[i], i, 1, Nsit) - Nsit/2.;

4.449986242244303

Eq.(7) at SUPPLEMENTARY MATERIAL (1) compputed on Ms=1 spin pro-

jections sub-spaces

–> alfaMs1 : sum ( densUpDnMs1[i], i, 1, Nsit) - Nsit/2.;

4.557368647201192

Uc is the critical value of the electronic correlation for First-Order Perturbation

Theory

–> float ( solve ( [ Uc * ( alfaMs1 - alfaMs0 ) - ( energyMs1 - energyMs0)], [Uc]) ) ;

[Uc = 4.709603886873415]

7 Second-Order Perturbation Theory for the Hub-

bard model on Ms=0 spin projections sub-
space
SumBB is the numerator in Eq.(17) at supplementary material (1)

–> SumBB (ppu,pu,ppd,pd) := if eigenvalues[ppu] <= FermiGround

and eigenvalues[pu] > FermiGround and eigenvalues[ppd] <= Fer-
miGround and eigenvalues[pd] > FermiGround then sum ( eigenvec-
tors[ppu][j]*eigenvectors[pu][j]*eigenvectors[ppd][j]*eigenvectors[pd][j] , j,
1, Nsit) else 0$

3
SumBB is the denominator in Eq.(17) at supplementary material (1)

–> DeltaE (ppu, pu, ppd, pd) := if eigenvalues[ppu] <= FermiGround and eigen-
values[pu] > FermiGround and eigenvalues[ppd] <= FermiGround and eigen-
values[pd] > FermiGround then eigenvalues[pu] + eigenvalues[pd] - eigenval-
ues[ppu] - eigenvalues[ppd] else 10000$
To build a table, TableBBEner, for the fraction at Eq.(17 )

–> array (TableBBEner, flonum, Nsit, Nsit, Nsit, Nsit,2);

–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do for ppd: 1 thru Nsit do for pd:
1 thru Nsit do TableBBEner[ppu,pu,ppd,pd,1]:SumBB(ppu, pu, ppd, pd)ˆ2$
–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do for ppd: 1 thru Nsit do for pd:
1 thru Nsit do TableBBEner[ppu,pu,ppd,pd,2]:DeltaE(ppu, pu, ppd, pd)$
Eq.(17) at supplementary material (1)

–> beta0 : sum ( sum ( sum ( sum ( TableBBEner[ppu,pu,ppd,pd,1]/

TableBBEner[ppu,pu,ppd,pd,2], pd,1,Nsit) , ppd,1,Nsit), pu,1,Nsit) ,
ppu,1,Nsit)$
DeltaEUp is the denominator in Eq.(18) at supplementary material (1)

–> DeltaEUp (ppu, pu) := if eigenvalues[ppu] <= FermiGround and eigenvalues[pu]

> FermiGround then eigenvalues[pu] - eigenvalues[ppu] else 10000$
SumBBNd is the numerator in Eq.(18) at supplementary material (1)

–> SumBBNd (ppu,pu) := if eigenvalues[ppu] <= FermiGround and eigenval-

ues[pu] > FermiGround then sum ( eigenvectors[ppu][j]*eigenvectors[pu][j]*
1./2. * density[j][2] , j, 1, Nsit) else 0$
To build a table, TableBUNdEner, for the fraction at Eq.(18)

–> array (TableBUNdEner, flonum, Nsit, Nsit,2)$

–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do TableBUN-
dEner[ppu,pu,1]:SumBBNd(ppu,pu)ˆ2;
–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do TableBUN-
dEner[ppu,pu,2]:DeltaEUp(ppu, pu);
Eq.(18) at supplementary material (1)

–> betaUp : sum ( sum ( TableBUNdEner[ppu,pu,1]/ TableBUNdEner[ppu,pu,2],

pu,1,Nsit) , ppu,1,Nsit)$

4
Eq.(8) at SUPPLEMENTARY MATERIAL (1) compputed on Ms=0 spin pro-
jections sub-spaces

–> betaMs0 : (beta0+2*betaUp);

0.28447881854422

EnergyU2Ms0 is the energy of the system computet at Ms = 0 spin projections

sub - spaces by using second-order perturbation theory

–> U : 1.0$
–> energyU2Ms0 : energyMs0+ alfaMs0*U-(betaMs0)*Uˆ2;
29.25634680282489

8 Second-Order Perturbation Theory for the Hub-

bard model on Ms=1 spin projections sub-
space
SumBB is the numerator in Eq.(17) at supplementary material (1)

–> SumBB (ppu,pu,ppd,pd) := if eigenvalues[ppu] <= FermiP1

and eigenvalues[pu] > FermiP1 and eigenvalues[ppd] < Fermi-
Ground and eigenvalues[pd] >= FermiGround then sum ( eigenvec-
tors[ppu][j]*eigenvectors[pu][j]*eigenvectors[ppd][j]*eigenvectors[pd][j] , j,
1, Nsit) else 0$
SumBB is the denominator in Eq.(17) at supplementary material (1)

–> DeltaE (ppu, pu, ppd, pd) := if eigenvalues[ppu] <= FermiP1 and eigenval-
ues[pu] > FermiP1 and eigenvalues[ppd] < FermiGround and eigenvalues[pd]
>= FermiGround then eigenvalues[pu] + eigenvalues[pd] - eigenvalues[ppu] -
eigenvalues[ppd] else 10000$
To build a table, TableBBEner, for the fraction at Eq.(17 )

–> array (TableBBEner, flonum, Nsit, Nsit, Nsit, Nsit,2)$

–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do for ppd: 1 thru Nsit do for pd:
1 thru Nsit do TableBBEner[ppu,pu,ppd,pd,1]:SumBB(ppu, pu, ppd, pd)ˆ2;
–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do for ppd: 1 thru Nsit do for pd:
1 thru Nsit do TableBBEner[ppu,pu,ppd,pd,2]:DeltaE(ppu, pu, ppd, pd);

5
Eq.(17) at supplementary material (1)

–> beta0 : sum ( sum ( sum ( sum ( TableBBEner[ppu,pu,ppd,pd,1]/

TableBBEner[ppu,pu,ppd,pd,2], pd,1,Nsit) , ppd,1,Nsit), pu,1,Nsit) ,
ppu,1,Nsit);
SumBB is the denominator in Eq.(18) at supplementary material (1)

–> DeltaEUp (ppu, pu) := if eigenvalues[ppu] <= FermiP1 and eigenvalues[pu] >
FermiP1 then eigenvalues[pu] - eigenvalues[ppu] else 10000$
SumBB is the numerator in Eq.(18) at supplementary material (1)

–> SumBBNd (ppu,pu) := if eigenvalues[ppu] <= FermiP1 and eigenvalues[pu] >

FermiP1 then sum ( eigenvectors[ppu][j]*eigenvectors[pu][j]*densDn[j][2] , j, 1,
Nsit) else 0$
To build a table, TableBUNdEner, for the fraction at Eq.(18 )

–> array (TableBUNdEner, flonum, Nsit, Nsit,2);

–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do TableBUN-
dEner[ppu,pu,1]:SumBBNd(ppu,pu)ˆ2;
–> for ppu: 1 thru Nsit do for pu: 1 thru Nsit do TableBUN-
dEner[ppu,pu,2]:DeltaEUp(ppu, pu);
Eq.(18) at supplementary material (1)

–> betaUp : sum ( sum ( TableBUNdEner[ppu,pu,1]/ TableBUNdEner[ppu,pu,2],

pu,1,Nsit) , ppu,1,Nsit);
SumBB is the denominator in Eq.(19) at supplementary material (1)

–> DeltaEdown (ppd, pd) := if eigenvalues[ppd] < FermiGround and eigenval-

ues[pd] >= FermiGround then eigenvalues[pd] - eigenvalues[ppd] else 10000$
SumBB is the numerator in Eq.(19) at supplementary material (1)

–> SumBBNu (ppd,pd) := if eigenvalues[ppd] < FermiGround

and eigenvalues[pd] >= FermiGround then sum ( eigenvec-
tors[ppd][j]*eigenvectors[pd][j]*densUp[j][2] , j, 1, Nsit) else 0$
To build a table, TableBUNuEner, for the fraction at Eq.(19)

–> array (TableBUNuEner, flonum, Nsit, Nsit,2)$

–> for ppd: 1 thru Nsit do for pd: 1 thru Nsit do TableBUNu-
Ener[ppd,pd,1]:SumBBNu(ppd,pd)ˆ2;
–> for ppd: 1 thru Nsit do for pd: 1 thru Nsit do TableBUNu-
Ener[ppd,pd,2]:DeltaEdown(ppd, pd);

6
Eq.(19) at supplementary material (1)

–> betaDn : sum ( sum ( TableBUNuEner[ppd,pd,1]/ TableBUNuEner[ppd,pd,2],

pd,1,Nsit) , ppd,1,Nsit)$
Eq.(8) at SUPPLEMENTARY MATERIAL (1) compputed on Ms=1 spin pro-
jections sub-spaces

–> betaMs1 : (beta0+betaUp+betaDn);

0.27116767746926

EnergyU2Ms1 is the energy of the system computet at Ms = 1 spin projections

sub - spaces by using second-order perturbation theory

–> U : 1.0$
–> energyU2Ms1 : energyMs1+ alfaMs1*U-(betaMs1)*U*U;
28.84468947494004

9 Uc calculations for second-order Perturbation

theory
Uc is the ritical value of the electronic correlation U obtained with Second-Order
Perturbation Theory

–> float ( solve ( [ -(betaMs1-betaMs0)*Uc2ˆ2+( alfaMs1 - alfaMs0 )*Uc2 + (

energyMs1 - energyMs0)], [Uc2]) ) ;

23
[Uc2 = 5.15148293230098610 9.0475477503885631022 %i 7.8298885269561681022

23
Uc2 = 5.15148293230098610 9.0475477503885631022 %i + 7.8298885269561671022 ]

–> wxplot2d([-(betaMs1-betaMs0)*xˆ2+( alfaMs1 - alfaMs0 )*x + ( energyMs1 -

energyMs0)], [x,0,5], [y,0,0.5], [box, false], [label, [”x”, 5.2, 0.],[”Spin Gap”, -1.6,
.3]])$

7
plot2d: some values were clipped.