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Spin contamination in MP2 and CC2,

a surprising issue
Cite as: J. Chem. Phys. 154, 131101 (2021); doi: 10.1063/5.0044362
Submitted: 15 January 2021 • Accepted: 7 March 2021 •
Published Online: 1 April 2021

Marios-Petros Kitsarasa) and Stella Stopkowiczb)

AFFILIATIONS
Department Chemie, Johannes Gutenberg-Unversität Mainz, D-55128 Mainz, Germany

Note: This paper is part of the JCP Special Collection in Honor of Women in Chemical Physics and Physical Chemistry.
a)
Electronic mail: mkitsara@uni-mainz.de
b)
Author to whom correspondence should be addressed: sstopkow@uni-mainz.de

ABSTRACT
When calculating the spin multiplicity at either the second-order Møller-Plesset (MP2) or the iterative second-order approximate coupled-
cluster singles and doubles (CC2) levels of theory using the same strategy for the calculation of the expectation value as in regular CC theory
together with the usual definitions of the MP2 and CC2 density matrices, artificial spin contamination occurs in closed-shell molecules. Non-
intuitively, for open-shell systems, results at the MP2 or CC2 levels of theory based on this procedure even suggest stronger contamination at
the correlated level than for the Hartree–Fock reference, although treatment of electron correlation should lower spin contamination. In this
Communication, the reasons behind this inconsistency are investigated and a solution is proposed, which removes spin contamination for
closed-shell molecules and leads to physically meaningful results for open-shell cases. Additionally, we show that CC2 significantly outper-
forms MP2 in describing systems with a strongly spin-contaminated reference with a performance similar to that of full coupled-cluster with
singles and doubles substitutions (CCSD).
Published under license by AIP Publishing. https://doi.org/10.1063/5.0044362., s

I. INTRODUCTION For an eigenfunction to Ŝ2 , |S, M S �, the eigenvalue is given in atomic

Coupled-Cluster (CC) theory is one of the most accurate and
widely used methods for ab initio calculations. CCSD(T), i.e., CC
with singles and doubles substitutions together with a perturba-
tive treatment of triple excitations, is used today as a gold stan-
dard.1 In standard CC theory, a Hartree–Fock (HF) determinant
is used as the reference wavefunction. For open-shell systems, a
CC treatment based on either a restricted open-shell HF (ROHF)
or an unrestricted HF (UHF) reference, respectively, leads to spin-
contaminated wavefunctions.2 In order to obtain a sound wavefunc-
tion, spin contamination needs to be monitored using appropri-
ate tools. Usually, the treatment of electron correlation, in partic-
ular when using CC theory, significantly lowers the extent of spin
contamination as compared to the HF reference.3–6
The first tool to be developed to calculate the spin multiplicity
and hence to study the extent of spin contamination in CC wave-
functions was introduced by Purvis, Sekino, and Bartlett.3 In that
work, the Ŝ2 operator was used, with Ŝ being the total spin operator
Ŝ = Ŝx i + Ŝy j + Ŝz k and i, j, and k being the Cartesian unit vectors.
units by
Ŝ2 �S, MS� = S(S + 1)�S, MS�,
with S being the total spin quantum number, M S being the spin
projection quantum number, and 2S + 1 being the spin multiplic-
ity. To investigate the extent of spin contamination, Purvis, Sekino,
and Bartlett suggested, in analogy to the CC energy expression, to
project the action of this operator on the CC wavefunction onto the
reference wavefunction �0�Ŝ2 �ΨCC� = �Ŝ2 �proj .3
It has been pointed out that the projected expression leads only
to an approximation of the spin multiplicity of the CC wavefunc-
tion.3–5 For this reason, Stanton proposed the calculation of the spin
multiplicity using derivative theory.4 In this formalism, first-order
properties are calculated as derivatives of the CC Lagrangian,7 which
is equivalent to the expectation value in bivariational theory.8,9 Based
on results for open-shell systems, Stanton suggested that there is no
significant advantage in using an ROHF reference over a UHF refer-
ence since the respective CCSD energies seem to be rather invariant

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to the choice of reference and also the calculated spin contamina-
tion based on an ROHF vs a UHF reference is similar. Additionally,
even for systems with a strongly spin-contaminated reference, the
powerful treatment of correlation and effective orbital relaxation at
the CCSD level brings the CC spin-expectation value very close to
the exact eigenvalue Se.v. .4 Note, however, that CCSD(T) or excited-
state wavefunctions at the Equation of Motion (EOM)-CCSD level
are rather sensitive to the spin contamination of the reference.10,11
For large systems, CCSD with its N 6 scaling, where N is the
number of electrons, is often computationally very expensive and
second-order Møller–Plesset perturbation (MP2) theory or the iter-
ative second-order approximate coupled-cluster singles and doubles
(CC2) method may be used instead.12–16
Because of the intrinsic relation between Many-Body Peturba-
tion Theory (MBPT) and CC theory, CC models can be viewed as an
infinite-order summation of selected excitations of the MBPT the-
ory.17 Hence, the projection approach for the calculation of the Ŝ2
expectation value �Ŝ2 �proj has already been introduced in the work of
Purvis, Sekino, and Bartlett and is also used in the work of Chen and
Schlegel for MP2.3,5 An extension to CC2 theory is readily available.
However, applying the expectation-value approach to MP2 and
CC2 requires caution. In this Communication, we show that the
results obtained using this formulation together with the usual def-
initions of the one- and, in particular, the two-particle reduced
density matrices (RDMs) introduce artificial spin contamination to
closed-shell systems, which is obviously not meaningful. In addition,
at the MP2 and CC2 levels of theory, the �Ŝ2 � results obtained in
this manner give unexpectedly strong contamination for open-shell
systems. After discussing the origin of this inconsistency, we pro-
pose a modification to this approach in Sec. II. We then describe the
implementation in Sec. III, apply the modified approach to our test
systems, and present the findings in Sec. IV.
II. THEORY
The total spin-squared operator Ŝ2 can be expressed (in atomic
units) as the following sum:
Ŝ2 = Ŝ− Ŝ+ + Ŝ2z + Ŝz ,
where Ŝ± are the spin ladder operators and Ŝz is the spin projector
operator onto the z axis. In second quantization, these operators are
given as
Ŝ+ = � S+pq̄ p† q̄,
pq̄
Ŝ− = � S−p̄q p̄† q,
p̄q
1 1 1 1 1
Ŝz = � p p − � p̄ p̄ = n̂α − n̂β = �n̂.
† †
2 p 2 p̄ 2 2 2 < |�Sproj | since higher-order correlation contributions are present
The creation (p† ) and annihilation operators (p) refer to α electrons
and β electrons when carrying overbars, respectively. The letters p,
q, r, s are used for the combined hole and particle space; a, b, c, d
for the particle space; and i, j, k, l for the hole space. The symbols
n̂σ , with σ = α, β, are the electron number operators for α and β
electrons, respectively, and �n̂ = n̂α − n̂β . The S± elements of the
ladder operators correspond to orbital-overlap integrals between α
and β orbitals with
J. Chem. Phys. 154, 131101 (2021); doi: 10.1063/5.0044362
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S∗+qp̄ = �q�p̄�∗ = �p̄�q� = S−p̄q .
The norm of these elements is given as
�Sqp̄ �2 = S+qp̄ S−p̄q .
The Ŝ2 expectation value for the reference determinant can then be
expressed by
1 1
�Ŝ2 �ref = �n� �n + 1� + � �Saī �2 .
2 2 īa
In the UHF and ROHF approaches, the reference wavefunction
is a spin eigenfunction to Ŝz as it preserves the number of α and β
electrons,
Ŝz ΦUHF/ROHF = MS ΦUHF/ROHF ,
but only the ROHF wavefunction is an eigenfunction to Ŝ2 . For this
reason, for UHF based calculations, one often calculates the devia-
tion of the expectation value �Ŝ2 � from the eigenvalue Se.v. evaluated
with the exact spin quantum number S, i.e., S(S + 1), as a diagnostic
tool,5,6
�S = �Sˆ2 � − Se.v. .
A. Expressions using projection techniques
According to the derivation of Purvis, Sekino, and Bartlett, the
CC correlation contribution for the projected expression �Ŝ2N �proj is
given by3
�Ŝ2N �proj = �Ŝ2 �proj − �Ŝ2 �ref
= + � S−j̄a S+ab̄ tj̄b̄ − � S−j̄a S+ij̄ tia
j̄b̄a j̄ai
− � S−j̄a S+ib̄ (tiaj̄b̄ + tia tj̄b̄ ),
j̄aib̄
with tia being the CC single amplitudes and tijab being the CC double
amplitudes.
Note that the projected expression yields no spin contamina-
tion with an ROHF reference |ΦROHF � due to
�ΦROHF �Ŝ2 �ΨCC� = �Ŝ2 ΦROHF �ΨCC � = S(S + 1)�ΦROHF �ΨCC �
= S(S + 1)
even though the correlated wavefunction is indeed spin contami-
nated.4 As discussed by Stanton and Purvis, Sekino, and Bartlett,3,4
�Ŝ2N �proj can be considered an approximation since �0| is not the
left-side CC eigenstate and it does not take the response of the CC
amplitudes into account. Chen and Schlegel showed with their first-
order approximation to the expectation-value approach that |�SCC |
in �Ŝ2N �CC .5 On practical consideration, �Ŝ2N �proj is readily available
after a CC energy calculation, while �Ŝ2N �CC requires the additional
calculation of the λ amplitudes as usual for properties within CC the-
ory. Furthermore, it has been pointed out by Stanton that, since in
the expectation-value approach for CC theory the ket wavefunction
�ΨCC� = eT̂ �0� is not the Hermitian conjugate of the bra wavefunc-
tion �Ψ ̃ CC � = �0�(1 + Λ̂)e−T̂ , there is no lower bound for �Ŝ2 �CC and
spin contamination may even be negative �SCC < 0.4
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Applying the projected variant to MP2 and CC2 theory is with the curly bracket notation {�} signifying normal-ordered prod-
straightforward. For the MP2 case, the tijab amplitudes are replaced by ucts of quasi-particle operators with respect to the Fermi vacuum.
�ab�ij�−�ab� ji�
=−
ab(1) Essentially, the RDMs are defined by all parts of the expectation
the first-order response of the wavefunction tij ,
εab
ij value apart from the integral itself.
ij = εa + εb − εi − εj as the difference of the orbital ener-
with εab In many cases, a first-order property A, depending on a param-
gies �p , while the ti
a(1)
are zero. This is included in the work of eter κ, can be calculated via
Purvis, Sekino, and Bartlett, which contains a detailed description @Lcorr
Acorr = = �(γN )pq + � (ΓN )pqrs
@fpq @Wpqrs
of �Ŝ2N �proj for the MBPT series.3 For the CC2 case, and generally @κ @κ pqrs @κ
, (4)
pq
for the CCn series, the CC amplitudes are replaced by the respective
CCn solutions. which also reflects the equivalence of generalized derivative theory
and linear response apart from orbital relaxation.14,18,19 MP2 proper-
B. Expressions based on the (bivariational) ties and CC2 properties are reported in Refs. 18 and 14 using deriva-
expectation value tive theory and response theory,19 respectively. Within a Lagrangian
A description improving upon the projected—and hence only formulation, we may define
(1) (1)
LMP2 = �0�Ĥ + [Ĥ, T̂2 ]�0� + � λab �Φab
ij �Ĥ + [F̂, T̂2 ]�0�,
approximate—expressions discussed before was given by Stanton ij(1)
via the CC expectation value of Ŝ2 .4 In this formulation, the CC abij
Lagrangian is defined as17
̃ + � λai �Φai �Ĥ1 + [Ĥ1 , T̂2 ]�0�
LCC2 = �0�H�0�
LCC = �0�(1 + Λ̂)e−T̂ ĤeT̂ �0� = ECC ,
ai
with Λ̂ being the de-excitation operator containing the λ amplitudes + � λab �Φab
ij �Ĥ1 + [F̂, T̂2 ]�0�
ij

Λ̂ = λia i† a+ 14 λab i† aj† b+�, T̂ being the excitation operator containing

ij
abij

the CC amplitudes T̂ = tia a† i+ 14 tijab a† ib† j+�, and Ĥ being the Hamil- ̃
and take the corresponding derivative with respect to κ. Here, H
tonian. The Ŝ2 expectation value is calculated as a first derivative of
= e Ĥe and Ĥ1 = e Ĥe . In MP2 theory, the λ amplitudes are
−T̂ T̂ −T̂1 T̂1
the Lagrangian using the modified Hamiltonian
simply given by the complex conjugate of the first-order response
�ij�ab�−�ij�ba�
Ĥ → Ĥ0 + �Ŝ2 , amplitudes λab = (tij )∗ = −
ij(1) ab(1)
(1) εab
. In CC2 theory, the λ
ij

where Ĥ0 is the electronic Hamiltonian and � is a scalar prefactor
that can be varied. The latter is formally set to 0 for the calculation of
the energy, and its mere purpose is to introduce a perturbative linear
dependency of the Lagrangian on the Ŝ2 operator. The derivative is
then given as
= �Ŝ2 �CC = �0�(1 + Λ̂)e−T̂ Ŝ2 eT̂ �0�,
@LCC
@�
which is identical to the definition of the expectation value in bivari-
ational theory.8,9 To obtain the correlation contribution Lcorr
CC , the HF
energy is subtracted from Eq. (2).
C. Derivatives and density matrices in MPn and CCn
In the general case, and also here for � = 0, the Lagrangian for
the correlation contribution can be brought to the form7,8,17
L corr
= �(γN )pq fpq + � (ΓN )pqrs Wpqrs ,
pq pqrs
where f pq are the elements of the Fock matrix and W pqrs = �pq|rs�
− �pq|sr� are the elements of the two-electron interaction part of
the Hamiltonian, i.e., the antisymmetrized two-electron integrals.
This means that the normal-ordered one- and two-particle RDMs
are defined such that they reproduce the correlation energy when
inserted into Eq. (3). In the case of CC theory, they are given as17
amplitudes are obtained iteratively.14 For perturbative methods such
as MPn and CCn that rely on the MP partitioning of the Hamilto-
nian, the Fock operator F̂ is part of the unperturbed system, while
the two-electron part Ŵ is the perturbation. Hence, in Eq. (3), the
elements f pq are zeroth-order contributions and are therefore com-
bined with elements (γN )pq of order n. Conversely, the elements
W pqrs comprise the perturbation and are of first order. Hence, they
(2)
are combined with elements (ΓN )pqrs of order n − 1. Many proper-
ties, such as geometrical gradients, can be expressed as in Eq. (4).
Since they contain the derivatives of f pq and W pqrs , the order in
perturbation theory of the RDMs is the same as for the energy.
However, as seen in Sec. IV, MP2 and CC2 results based on
Eq. (2) together with RDMs that fulfill Eq. (3) lead to artificial spin
contamination, which is discussed in the following paragraph.
D. Expectation-value expressions in MPn and CCn
(3) The derivation of the �Ŝ2 � expectation value in CC theory is
summarized in Sec. II B. Since the derivative of the Lagrangian [see
Eq. (2)] is taken with respect to � after modification of the Hamilto-
nian according to Eq. (1), it does actually not lead to perturbed Fock
matrices and two-electron integrals. Instead, as discussed in Ref. 4,
it is found that
�Ŝ2N � = � S−p̄a S+as̄ (γN )p̄s̄ − � S−īq S+rī (γN )rq
p̄s̄a īqr

−T̂ − � S−p̄q S+rs̄ (ΓN )p̄rs̄q .

�0�(1 + Λ̂)e {p q}e �0� = (γN )pq ,
† T̂ (5)
p̄qrs̄

Note here that the two-particle RDM is contracted with combi-

�0�(1 + Λ̂)e−T̂ {p† q† sr}eT̂ �0� = (ΓN )pqrs , nations of overlap integrals instead of (differentiated) two-electron

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FIG. 1. Contributions to the one-body RDM for CC2. For MP2, only the terms inside
the square brackets contribute.
integrals. Since the perturbation Ŵ is not part of the equation, to
calculate �Ŝ2N � within MPn or CCn theory, both the one- and the
two-particle RDMs must be of order n. In the case of CC2 and
MP2, they should hence both be of second order. The issue stems
from the fact that the additional term �Ŝ2 in Eq. (1) is neither part
of the unperturbed system nor does it belong to the perturbation
Ŵ. In other words, the two-body RDM that would reproduce the
MPn or CCn energy is of the wrong order in perturbation theory
when calculating �Ŝ2N �. The inconsistency that two-particle RDMs of
different order are required for reproducing the energy vs for cal-
culating the �Ŝ2N � expectation value is solely an issue for perturbative
methods such as MPn and CCn and poses no problem for regular CC
methods.
To fix the problem and in order to obtain physically meaning-
ful results in the evaluation of Eq. (5), the two-body RDM hence
needs additional contributions of order n. For the specific cases of
MP2 and CC2, the unmodified one- and two-body RDMs for MP2
and CC2 are given in Figs. 1 and 2. Compared to CCSD, the second-
or higher-order contributions λ2 t2k , with k ≥ 1, where λ2 and t 2 are
the sets of λ and t double amplitudes, respectively, are missing in
J. Chem. Phys. 154, 131101 (2021); doi: 10.1063/5.0044362
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CC2. To construct the modified two-particle RDM for the calcula-
tion of �Ŝ2 �mod
CC2 , all second-order contributions need to be added to
the usual definition of the CC2 two-body RDM. These modifications
are denoted as (ΓN )mod pqrs in Fig. 3 and include all λ2 t 2 terms. (ΓN )pqrs
mod
for CC2 is identical to the CCSD two-particle RDM, except for the
ijab block, which in CCSD contains additional λ2 t22 contributions.
(ΓN )mod
(CC2)ijab can thus be written more compactly as
1
(ΓN )mod
(CC2)ijab = (ΓN )(CCSD)ijab − � λ tmn tij
mn ab ef
4 efmn ef
− P(ij) � λmn ea bf
ef tmi tjn .
efmn
Because of the additional second-order terms, the calculation of the
modified two-body RDM scales as ∼N 6 . In the case of MP2, the
modifications lead to the MP3 two-particle RDM.
III. IMPLEMENTATION AND COMPUTATIONAL DETAILS
The modified two-body RDMs for the calculation of the Ŝ2
expectation value in CC2 and MP2 have been implemented in the
QCUMBRE program suite.20 In the case of CC2, since the scaling of
the calculation cannot be lowered to ∼N 5 anyways, the procedure
simply uses the code already available for the two-particle RDMs
in CCSD20–22 and removes the λ2 t22 contributions from the ijab
block.
The necessary integrals and the UHF reference wavefunc-
tion are provided via an interface to the LONDON program
package.23,24
We investigate a set of molecules that consists of closed-shell
cases (LiH, HF, H2 O, and NH3 ) as well as open-shell cases (CH,
OH, CH3 , CN, NO, and CH2 O+ ). The calculations have been car-
ried out using the Cartesian cc-pVTZ and cc-pVQZ basis sets.25 For
every molecule, a corresponding geometry optimization at the same
level of theory has been performed with the CFOUR program pack-
age,26,27 using the same basis set as for the following calculation of
the Ŝ2 expectation value.
FIG. 2. Contributions to the two-body
RDM for CC2. For MP2, only the terms
inside the square brackets contribute.
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FIG. 3. Second-order contributions to the

two-body RDM (ΓN )mod for CC2 for cal-
culation of �Ŝ2 � . For MP2, only the
mod

terms inside the square brackets con-

tribute, which correspond to the MP3
two-particle RDM.

IV. RESULTS AND DISCUSSION theory. This holds in the case of �Ŝ2 �proj . However, using the unmod-
A. Closed-shell systems ified expectation-value approach �Ŝ2 �, the results are non-zero at the
MP2 and CC2 levels of theory, which is unphysical.
The results for the molecules LiH, HF, H2 O, and NH3 are To be more specific, when dividing Eq. (5) into one- and two-
shown in Table I. For closed-shell systems, no spin contamination body contribution parts C1 and C2 ,
should occur, neither for the reference nor at correlated levels of
C1 = � S−p̄a S+as̄ (γN )p̄s̄ − � S−īq S+rī (γN )rq ,
p̄s̄a īqr
(6)
TABLE I. Total energies in E h as well as modified and unmodified �Ŝ2 � expectation
values in h�2 for closed-shell systems using the cc-pVQZ basis set at the MP2 and C2 = − � S−p̄q S+rs̄ (ΓN )p̄rs̄q .
p̄qrs̄
CC2 levels of theory. The final modified spin-expectation values are printed in bold
face. C2 should exactly cancel out C1 for the theory to be physically sound.
Instead, as seen in Table I, when the unmodified densities are used to
LiH HF H2 O NH3 calculate these contributions at the MP2 level, C2 is zero. This can be
MP2 understood because for closed-shell systems in MP2, the only non-
vanishing blocks in the unmodified (ΓN ) are (ΓN )ijab and (ΓN )abij .
Etot −8.045 149 −100.404 641 −76.388 141 −56.515 938 Therefore, according to Eq. (6), the overlap integrals that contribute
�Ŝ2 �unmod 0.035 894 0.104 758 0.127 882 0.135 181 to C2 are S+iā , S−īa , S+aī , and S+āi , which for the closed-shell RHF case
C1 0.035 894 0.104 758 0.127 882 0.135 181 are all zero. The one-electron contributions C1 on the other hand
C2unmod 0 0 0 0 are non-zero and depend strongly on the system at hand. A similar
situation is observed at the CC2 level of theory. Even though C2 has
�Ŝ2 �mod 0 0 0 0
non-zero contributions, it is still by two to three orders of magnitude
C2mod −0.035 894 −0.104 758 −0.127 882 −0.135 181
smaller than C1 .
CC2 Since for MP2 and CC2, (ΓN )pqrs is defined only up to the first
order of the perturbation, but (γN )pq has contributions up to the
Etot −8.045275 −100.406880 −76.390367 −56.517 721 second order, it follows that C2 cannot cancel out C1 . When this
�Ŝ2 �unmod 0.035995 0.108436 0.131697 0.137 845 inconsistency is corrected using (ΓN )mod pqrs defined up to the second
C1 0.036167 0.109726 0.133068 0.138 939 order for MP2 and CC2, C1 and C2 correctly add up to 0.
C2unmod −0.000172 −0.001290 −0.001371 −0.001 094
�Ŝ2 �mod 0 0 0 0 B. Open-shell radicals
C2mod −0.036 167 −0.109 726 −0.133 068 −0.138 939 Next, we investigate the spin contamination for the MP2 and
CC2 methods in open-shell systems, specifically, in monoradical

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systems, for which Se.v. = 0.75 h�2 . We first discuss results for CH,
OH, and CH3 , which have a weakly spin-contaminated reference.
Next, we discuss systems with a strongly spin-contaminated refer-
ence: CN, NO, and CH2 O+ . The respective results are collected in
Table II.
For CH, OH, and CH3 , |�Sref | is smaller than 0.02 h�2 . �Ŝ2 �proj
largely reduces spin contamination at both the MP2 and the CC2
levels of theory, i.e., �Ŝ2 �MP2 �2
proj is ∼0.004 h lower than �Ŝ �ref , while
2
�Ŝ �proj is lower by ∼0.006 h� . In these cases, it is found that
2 CC2 2 tamination can be understood as an indicator of the failure of HF
the stronger the contamination in the reference, the greater the
improvement by the treatment of correlation.
Turning to the expectation-value approach, as seen in Table II
and discussed by Chen and Schlegel,5 results at the CCSD level
of theory show ��SCCSD proj � > ��S
CCSD
�. This trend, however, does
not hold at the MP2 and CC2 levels of theory when using the
unmodified expectation value. Specifically, the spin contamination
contamination is indeed lower by ∼0.006 h�2 at the MP2 level and
∼0.008 h�2 at the CC2 level. The modified two-electron contributions
C2mod are now of the same order of magnitude as the one-electron
contributions. For these three cases at the CC2 level, �Ŝ2 �mod
CC2 ranges
between 0.751 and 0.752 h�2 .
All three radicals CN, NO, and CH2 O+ have a strongly spin-
contaminated reference. For CN, it even reaches �Ŝ2 �ref = 1.090 h�2
for a cc-pVQZ/CC2 geometry. As discussed by Krylov, spin con-
theory and suggests a multi-configurational character for the wave-
function.6,11 Non-dynamical electron correlation is thus expected to
play an important role for these cases.
As shown by the results in Table II, MP2 does not show an
adequate improvement for such strongly contaminated systems.
�Ŝ2 �MP2 �2
proj calculations lower the spin contamination by about 0.01 h .
2 MP2 �
For CN, �Ŝ �proj is 0.96 h , while for the other two systems, it
2

is |�Sunmod | ∼ 0.1 h�2 > |�Sproj | for CH, OH, and CH3 . At both MP2 ranges between 0.77 and 0.78 h�2 , which is still very far from Se.v.
and CC2 levels of theory, the absolute value of the unmodified two- = 0.75 h�2 . The unmodified �Ŝ2 �unmod ranges around 0.9–1.1 h�2 .
In contrast, the results for �Ŝ �MP2 are closer to Se.v. by ∼10−3 h�2
MP2
electron contribution C2unmod is also one order of magnitude smaller 2 mod

than the one-electron contribution C1 . Instead, for �Ŝ2 �mod , the for NO and CH2 O+ and by 0.03 h�2 for CN as compared to �Ŝ2 �MP2 proj
expected trend |�Smod | < |�Sproj | re-emerges and the extent of spin but are still off by >0.01 h�2 . These findings indicate that MP2

TABLE II. Total energies in E h as well as modified and unmodified �Ŝ2 � expectation values in h�2 for open-shell systems using the cc-pVQZ basis set at the MP2, CC2, and
CCSD levels of theory. The final modified spin-expectation values are printed in bold face.

CH(2 Π) OH(2 Π) CH3 (2 A′′

2) CN(2 Σ+ ) NO(2 Π) CH2 O+ (2 B1 )

MP2

Etot −38.426 400 −75.681 812 −39.786 070 −92.616 357 −129.809 600 −114.004 055
�Ŝ2 �ref 0.759 442 0.756 657 0.761 483 0.985 386 0.774 143 0.783 873
�Ŝ2 �proj 0.755 549 0.753 838 0.757 175 0.956 069 0.767 243 0.775 764
�Ŝ2 �unmod 0.811 902 0.827 698 0.835 976 1.081 046 0.943 159 0.917 911
C1 0.060 246 0.076 679 0.083 108 0.154 294 0.182 816 0.150 255
C2unmod −0.007 786 −0.005 639 −0.008 615 −0.058 634 −0.013 800 −0.016 217
�Ŝ2 �mod 0.753 313 0.752 369 0.754 604 0.925 210 0.762 798 0.770 137
C2mod −0.066 375 −0.080 968 −0.089 987 −0.214 470 −0.194 161 −0.163 990

CC2

Etot −38.427 290 −75.683 383 −39.787 259 −92.644 981 −129.821 743 −114.018 357
�Ŝ2 �ref 0.759 449 0.756 679 0.761 516 1.090 092 0.795 790 0.784 701
�Ŝ2 �proj 0.753 269 0.752 521 0.754 245 0.841 376 0.755 196 0.762 381
�Ŝ2 �unmod 0.810 700 0.828 373 0.833967 0.948 336 0.947 794 0.920 700
C1 0.057 378 0.076 581 0.078 820 −0.228 600 0.146 364 0.156 188
C2unmod −0.006 127 −0.004 887 −0.006 369 0.086844 0.005640 −0.020189
�Ŝ2 �mod 0.751 332 0.751 190 0.751 708 0.757 992 0.751 318 0.754 574
C2mod −0.065 495 −0.082 070 −0.088 627 −0.103 500 −0.190 837 −0.186 315

CCSD

Etot −38.450 330 −75.694 211 −39.806 134 −92.645 390 −129.812 062 −114.030 822
�Ŝ2 �ref 0.759 479 0.756 669 0.761 614 1.110 029 0.779 116 0.784 357
�Ŝ2 �proj 0.750 385 0.750 422 0.750 678 0.791 755 0.752 663 0.755 164
�Ŝ2 �CC 0.750 197 0.750 161 0.750 261 0.754 323 0.750 603 0.751 500

J. Chem. Phys. 154, 131101 (2021); doi: 10.1063/5.0044362 154, 131101-6

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theory does not efficiently remove spin contamination from the
wavefunction as it does not adequately account for non-dynamical
correlation.
Similar to MP2, results for the unmodified expectation values
�Ŝ2 �unmod �2
CC2 show large deviations from 0.75 h , with ��SCC2 � ∼ 0.2 h .
unmod
CN at the CC2 level of theory is the only case in which �Ŝ �CC2
improves upon �Ŝ2 �ref . Compared to MP2, although, at the CC2 level
of theory, spin contamination of the reference is largely reduced
when considering �Ŝ2 �CC2 �2
proj , which is 0.841 h for CN, 0.762 h for
CH2 O , and 0.755 h� for NO. Again, the �Ŝ �CC2 values seem to
+ 2 2 unmod
the MP partitioning of the Hamiltonian such as MPn and CCn, the
two-particle RDM is of order n − 1, while it needs to be of order
n to compute the Ŝ2 expectation value. There is no such inconsis-
tency in full non-perturbative bivariational CC truncations such as
�2
CCD, CCSD, and so on. The results show that after modifying the
2 unmod RDMs, MP2 removes spin contamination from systems that have a
weakly spin-contaminated reference but fails for strongly contami-
nated cases. CC2 has a superior performance over MP2 and is able to
�2 bring the spin contamination of even strongly contaminated systems
down to ∼10−3 , which is comparable to CCSD.

indicate higher spin contamination as compared to �Ŝ2 �CC2 proj . This

DEDICATION
behavior is corrected for �Ŝ2 �mod CC2 . Comparing the two-body con-
tribution C2mod to C2unmod , one observes that they change sign for S. Stopkowicz dedicates this contribution to Professor Dr. Anna
CN and NO. Also, C2mod becomes more negative for CH2 O+ . The Krylov. Since we met, she has been an inspiration and has become
second-order contributions for these three cases are hence neg- an encouraging mentor and a friend with whom to discuss both
ative. The final results for �Ŝ2 �mod CC2 are promising. Treatment of
science and personal growth. I also thank Anna for actively pro-
electron correlation at the CC2 level manages to lower the spin- moting women in theoretical chemistry by starting a list of female
expectation value of CN from 1.050 h�2 for the reference to 0.758 h�2 . scientists in the field and by informing about and fighting against
The same is true for the other two “difficult” systems, for which biases.
�Ŝ2 �mod �2
CC2 values are closer to 0.75 h . These observations suggest
an adequate ability of CC2 to address strongly spin-contaminated ACKNOWLEDGMENTS
systems.
The authors thank Professor Dr. Jürgen Gauss and Profes-
Finally, we compare the MP2 and CC2 results with those at
the CCSD level. As expected, the projected �Ŝ2 �CC2
sor Dr. Anna Krylov for valuable discussions. This work was sup-
proj results are closer
ported by the Deutsche Forschungsgmeinschaft under Grant No.
to �Ŝ2 �CCSD
proj than the corresponding � Ŝ �
2 MP2
proj values. Specifically for STO 1239/1-1.
CN, �Ŝ2 �CCSD with a value of 0.792 �2 indicates a strong contami-
h
proj
nation even at the CCSD level of theory. �Ŝ2 �CC2 �2
proj is 0.841 h , while APPENDIX: RESULTS USING THE cc-pVTZ BASIS SET
�Ŝ2 �MP2 �2
proj is 0.956 h , both suggesting a failure of the methods to
Table III reports total energies in Eh as well as modified and
unmodified �Ŝ2 � expectation values in h�2 for closed-shell systems
describe the system adequately. However, focusing on the modi-
fied expectation value, one observes that the CC2 result (0.758 h�2 )
is similar to that of CCSD (0.754 h�2 ), while the MP2 result at 0.925
h�2 is still far off. The mean spin contamination of the “difficult” sys-
tems at the CCSD level ��S�CCSD is 2.1 ⋅ 10−3 h�2 , less than half that of TABLE III. Total energies in E h as well as modified and unmodified �Ŝ2 � expectation
values in h�2 for closed-shell systems using the cc-pVTZ basis set at the MP2 and
��S�CC2 = 4.6 ⋅ 10−3 h�2 . These results show the importance of includ-
mod
CC2 levels of theory. The final modified spin-expectation values are printed in bold
ing the T 1 amplitudes at zeroth order as an approximate treatment face.
of orbital relaxation, which are missing in MP2.
Comparing in general the different basis sets used in this study LiH HF H2 O NH3
(for calculations using the cc-pVTZ basis set, see the Appendix),
one notices that the differences are rather small and at the order of MP2
∼10−4 h�2 . The spin contamination for both MP2 and CC2 is, in gen- Etot −8.029 213 −100.348 385 −76.336 700 −56.472 144
�Ŝ2 �unmod 0.032 637
eral, lower with the larger basis set cc-pVQZ for the systems with
0.098 444 0.121 535 0.129 509
stronger spin contamination, but it is the choice of method for the
C1 0.032 637 0.098 444 0.121 535 0.129 509
treatment of correlation that has the deciding impact.
C2unmod 0 0 0 0
�Ŝ2 �mod 0 0 0 0
C2mod −0.032 637 −0.098 444 −0.121 535 −0.129 509
V. CONCLUSIONS
In this Communication, a recipe for the calculation of the Ŝ2 CC2
expectation value at the MP2 and CC2 levels of theory has been
introduced and the basis for the generalization to the MPn and CCn Etot −8.029 357 −100.350 263 −76.338 533 −56.473 588
series has been given. The main point here is that within perturbative �Ŝ2 �unmod 0.032 839 0.101 328 0.124 579 0.131 740
schemes such as MPn and CCn, the one- and two-body RDMs used C1 0.033 011 0.102 224 0.125 526 0.132 521
for the Ŝ2 expectation value must be defined up to the same order of C2unmod −0.000 172 −0.000 896 −0.000 947 −0.000 781
perturbation for the results to be physically meaningful. Conversely, �Ŝ2 �mod 0 0 0 0
the two-particle RDM used to compute �Ŝ2 � is different from the C2mod −0.033 011 −0.102 224 −0.125 526 −0.132 521
one that would reproduce the energy. Usually, for methods based on

J. Chem. Phys. 154, 131101 (2021); doi: 10.1063/5.0044362 154, 131101-7

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 The Journal
COMMUNICATION
of Chemical Physics scitation.org/journal/jcp

TABLE IV. Total energies in E h as well as modified and unmodified �Ŝ2 � expectation values in h�2 for open-shell systems using the cc-pVTZ basis set at the MP2, CC2, and
CCSD levels of theory. The final modified spin-expectation values are printed in bold face.

CH(2 Π) OH(2 Π) CH3 (2 A′′

2) CN(2 Σ+ ) NO(2 Π) CH2 O+ (2 B1 )

MP2

Etot −38.395 620 −75.635 320 −39.753 806 −92.547 788 −129.726 703 −113.929 682
�Ŝ2 �ref 0.758 896 0.756 097 0.761 309 0.990 504 0.774 387 0.783 808
�Ŝ2 �proj 0.755 130 0.753 442 0.757 065 0.960 725 0.767 567 0.775 824
�Ŝ2 �unmod 0.809 024 0.823 065 0.832 958 1.079 052 0.936 750 0.913 148
C1 0.057 659 0.072 279 0.080 137 0.148 106 0.176 002 0.145 308
C2unmod −0.007 531 −0.005 310 −0.008 489 −0.059 558 −0.013 639 −0.015 968
�Ŝ2 �mod 0.752 993 0.752 080 0.754 537 0.929 339 0.763 128 0.770 274
C2mod −0.063 562 −0.076 296 −0.086 910 −0.209 271 −0.187 260 −0.158 842

CC2

Etot −38.396 347 −75.636 610 −39.754 757 −92.575 768 −129.738 411 −113.943 405
�Ŝ2 �ref 0.758 902 0.756 116 0.761 337 1.094 079 0.797 966 0.784 529
�Ŝ2 �proj 0.753 146 0.752 317 0.754 355 0.845 969 0.755 687 0.762 851
�Ŝ2 �unmod 0.808 057 0.823 580 0.831 012 0.942 594 0.940 596 0.915 995
C1 0.055 191 0.072 027 0.076 021 −0.236 940 0.135 475 0.151 898
C2unmod −0.006 036 −0.004 563 −0.006 345 −0.098 460 0.007 155 −0.020 431
�Ŝ2 �mod 0.751 283 0.751 079 0.751 811 0.758 678 0.751 246 0.754 858
C2mod −0.062 810 −0.077 064 −0.085 547 −0.098 460 −0.182 194 −0.181 568

CCSD

Etot −38.420 163 −75.648 995 −39.774 790 −92.578381 −129.731 349 −113.957 979
�Ŝ2 �ref 0.758 933 0.756 115 0.761 427 1.120 451 0.782 809 0.784 282
�Ŝ2 �proj 0.750 306 0 750 330 0.750 632 0.791 040 0.752 874 0.755 110
�Ŝ2 �CC 0.750 167 0.750 128 0.750 245 0.754 095 0.750 579 0.751 491

using the cc-pVTZ basis set at the MP2 and CC2 levels of the-
ory. Table IV reports total energies in Eh as well as modified and
unmodified �Ŝ2 � expectation values in h�2 for open-shell systems
using the cc-pVTZ basis set at the MP2, CC2, and CCSD levels of
theory.
DATA AVAILABILITY
The data that support the findings of this study are available
within the article and its Appendix.
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