Journal of Molecular Modeling (2022) 28:334

https://doi.org/10.1007/s00894-022-05331-4

ORIGINAL PAPER

ZORA Gaussian basis sets for Fr, Ra, and Ac

Antônio Canal Neto1 · Francisco Elias Jorge1 · Thieberson Gomes1

Received: 21 June 2022 / Accepted: 21 September 2022 / Published online: 29 September 2022
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
Segmented all-electron basis sets of double and triple zeta valence qualities plus polarization functions (DZP and TZP) for
the elements Fr, Ra, and Ac to be used with the zeroth-order regular approximation (ZORA) were presented. These sets were
constructed from the reoptimization of the contraction coefficients of the corresponding non-relativistic basis sets. In order
to adequately describe electrons distant from the atomic nuclei, these sets were augmented with diffuse functions and were,
respectively, designated as ADZP-ZORA and ATZP-ZORA. At the ZORA-B3LYP theory level, the relativistic sets were
employed to calculate ionization energies of Fr, Ra, and Ac as well as bond lengths, dissociation energies, harmonic vibrational
frequencies, and static mean dipole polarizabilities of some diatomics. Comparing with benchmark theoretical results and
with experimental data available in the literature, it can be verified that our basis sets are able to produce reliable and accurate
results. Evaluation of the performances of ZORA and second-order Douglas-Kroll-Hess Hamiltonians was performed.

Keywords ZORA basis sets · Fr, Ra, and Ac elements · ZORA-B3LYP method · Atomic and molecular property
calculations · Performances of the ZORA and DKH2 Hamiltonians

Introduction Hamiltonians give highly accurate results, neither of

In recent years it has become common to use Gaussian-type
functions (GTFs) to perform ab initio and density functional
theory (DFT) calculations, since it has been verified that is
possible to build a Gaussian basis set, which is both compact
and accurate. In addition to meeting these two criteria, it is
also desirable that this basis set belongs to a hierarchical
sequence of basis sets that systematically reduce the basis
set truncation error.
It is everyone’s knowledge that complexity increases
significantly when treating molecules and/or clusters
containing heavy atoms [1–3], since quantum chemistry
methods must simultaneously consider the high num-
bers of electrons and orbitals as well as the correlation of
electrons and relativistic effects. In these cases, there are
two obvious options. The Dirac-Coulomb Hamiltonian or
the Dirac-Breit Hamiltonian, which consider the interac-
tions of electrons relativistically. Even knowing that the
solutions (four-component wave functions) of these two
* Francisco Elias Jorge
francisco.jorge@ufes.br
1
Departamento de Física, Universidade Federal Do Espírito
Santo, Vitória, ES 29060‑900, Brazil
these options is the most feasible, since the computational
cost becomes practically prohibitive for systems contain-
ing many atoms. A proposal whose main objective is to
reduce the number of electrons to be handled during calcu-
lations and that has been used by several researchers is the
relativistic effective core potential (ECP) [4]. In the case
of calculations of geometries and/or relative energies of
molecules containing heavy elements, the results obtained
with the relativistic ECP approximation are comparable
to those computed with theoretical models that consider
all electrons [5]. Some negative points of ECPs have been
discussed in the literature [6–8]. However, the deficiencies
of ECPs become evident in the case of properties involv-
ing electrons of inner-shells, for example, electron density
topological analysis, electron paramagnetic resonance, and
Mössbauer and X-ray absorption spectra. To overcome all
these problems, it is necessary to use a Hamiltonian, which
takes into account most of the scalar relativistic effects,
along with an all-electron basis set. Both the Douglas-
Kroll-Hess (DKH) unitary transformation [9–11] and the
zero-order regular approximation (ZORA) [12] satisfy the
condition mentioned in the previous sentence. We remind
you that the spin–orbit effect can be calculated a posteriori
through perturbation theory.

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As for the method to be employed, it is worth drawing
attention to the accuracy of ab initio methods. However,
when it comes to systems with many electrons, the DFT
is more efficient because, in addition to considering elec-
tron correlation, it significantly reduces computational time,
making it not much different from that of a Hartree–Fock
(HF) calculation.
Since 2009, our research group has developed relativistic
basis sets of different qualities to be used in DFT or ab initio
calculations. For the H–La and Hf–Rn elements, all-electron
segmented basis sets of double and triple zeta valence quali-
ties plus polarization functions (DZP-DKH and TZP-DKH)
were reported [13–18]. These sets have been successfully
used in the determination of electronic structures of atoms,
molecules, and clusters (see, e.g., Refs. [19–22]).
To our knowledge, there are few all-electron contracted
basis sets for Fr, Ra, and Ac available in the literature. The
atomic natural orbital (ANO) sets of Roos et al. [23, 24] are
very accurate in determining electronic structures, but were
constructed to be used primarily with the DKH2-CASPT2
method in small molecule calculations. As these sets were
generated from the general contraction scheme, their perfor-
mances are reduced in DFT calculations of large molecules,
since the computational cost is proportional to the number of
two-electron integrals to be evaluated. In the ADF program
[25], ZORA basis sets of different qualities generated from
Slater-type functions (STFs) can be found. The applicabil-
ity of these sets is limited because the number of programs
that are prepared to handle STFs is reduced. We cannot help
but mention the DKH basis sets of double up to quadruple
and those of double and triple zeta qualities presented by
Peterson et al. [26, 27] and Campos et al. [28], respectively.
For Ac, SARC basis sets for DKH2 and ZORA calculations
were developed by Pantazis and Neese [29].
As specific basis sets to be used together with ZORA
Hamiltonian are scarce in the literature and as the number of
quantum chemistry codes (DIRAC, ORCA, ADF, NWChem,
etc.) containing this Hamiltonian is large, recently Jorge
et al., in order to address this deficiency, developed com-
pact and accurate DZP-ZORA and TZP-ZORA sets for the
elements from H to La and from Hf to Rn [30–32]. Here, it
is worth mentioning that these sets are linear combinations
of Gaussian type functions (GTFs) rather than STFs.
The main objective of this work is to extend the ZORA
basis sets to include Fr, Ra, and Ac elements. For a better
description of electrons distant from atomic nuclei, diffuse
functions were added to these sets, which were designated
as ADZP-ZORA and ATZP-ZORA. To evaluate the perfor-
mances of these sets at the ZORA-B3LYP level of theory,
atomic ionization energies (Ei) and bond lengths (re), har-
monic vibrational frequencies (ωe), and dissociation energies
(De) of F­ r2, ­Ra2, ­Ac2, AcH, AcO, and AcF were computed
and then compared with theoretical and experimental data
13
Journal of Molecular Modeling (2022) 28:334
found in the literature. Evaluation of the performances of
ZORA and second-order DKH (DKH2) Hamiltonians was
performed.
Generation of ZORA Gaussian basis sets
To generate the DZP-ZORA and TZP-ZORA basis sets for
Fr, Ra, and Ac, we used a procedure similar to that employed
in Refs. [30–32]; namely, the coefficients of contraction of
s, p, d, and f symmetries of the non-relativistic DZP and
TZP [28] sets were reoptimized taking into account the
minimum ZORA-ROHF (restricted open-shell HF) ground
state energy criterion of each element [Fr (2S), Ra (1S), and
Ac (2D)]. In the process of determining the ZORA contrac-
tion coefficients, the method of optimization of nonlinear
parameters presented by Jorge and Canal Neto [33] in 2020
and the ORCA code [34] were used. It is worth remember-
ing that the exponents of the GTFs and the segmented con-
traction schemes remained unchanged going from the DZP
and TZP sets to the DZP-ZORA and TZP-ZORA sets; that
is, the only difference between the non-relativistic and the
corresponding relativistic set is the contraction coefficients.
SARC-ZORA basis sets were also originated from the reop-
timization of contraction coefficients of non-relativistic sets
(see, e.g., Ref. [29]).
Here, it is worth mentioning some peculiarities of the
DZP-ZORA and TZP-ZORA basis sets: (i) In the process of
re-optimizing the contraction coefficients of the non-relativ-
istic DZP and TZP basis sets, some contraction coefficients
went to zero. In these cases, the corresponding exponents
of the GTFs were eliminated from the contraction scheme.
This is the reason why the number of p-symmetry func-
tions of the TZP-ZORA set for Fr is smaller than that of the
DZP-ZORA set. (ii) For the ground state of Fr and Ra, the
valence orbitals considered were 7 s and 7p, while for Ac
the 6d orbital also was included. Therefore, the polarization
functions added to the DZ and TZ sets of Fr and Ra were 1d
and 2d1f, respectively, while for Ac, 1f was added to the DZ
set and 2f1g to the TZ set (for more details, see Ref. [28]).
Relativistic effects increase through the Periodic Table,
causing a significant contraction of the core orbitals of the
heavier elements and, consequently, an expansion of valence
orbitals. These effects make the radial behaviors of non-rel-
ativistic and relativistic wave functions very different [35].
Therefore, non-relativistic basis sets can give undesirable
results when used together with a relativistic Hamiltonian
[35]. Jorge et al. [31] have shown that undesirable results can
also arise when a DKH basis set is used in ZORA calcula-
tions. Given these facts, it is clear the main motivation that
led us to construct basis sets for Fr, Ra, and Ac specific to
the ZORA Hamiltonian.
Journal of Molecular Modeling (2022) 28:334 Page 3 of 7 334

For an appropriate description of electrons distant from
atomic nuclei, it is necessary to add diffuse functions to a
basis set. These augmented sets are typically employed in
calculations of polarizabilities, electron affinity, hydrogen
binding, electronic circular dichroism, and optical rotation.
To the DZP-ZORA and TZP-ZORA sets for the Fr, Ra, and
Ac elements, we added a diffuse function to each atomic
symmetry s, p, d, and f to originate the sets designated as
ADZP-ZORA and ATZP-ZORA. These diffuse functions
were taken directly from the non-relativistic ADZP and
ATZP sets reported in Ref. [28]. The numbers of GTFs used
to describe each atomic orbital of the uncontracted and con-
tracted DZP-ZORA, ADZP-ZORA, TZP-ZORA, and ATZP-
ZORA sets are listed in Table 1.
and from Ra to Ac. When compared to the experimental
values, the ionization energies always improve going from
ADZP-ZORA to ATZP-ZORA. The agreement between
the ZORA-B3LYP/ATZP-ZORA and experimental results
is excellent, the largest difference of 3.0% occurring for Ac.
For Ac, Pantazis and Neese [29] found 5.18 eV with the
DKH2-B3LYP/[21s13p10d7f] theoretical procedure, which
is close to our ZORA-B3LYP/ATZP-ZORA value. For Fr
and Ra, the ZORA-B3LYP/ATZP-ZORA results also agree
well with benchmark theoretical values [26] obtained with
the DKH3-CCSD(T) method in conjunction with the all-
electron awCVQZ-DK3 basis set.
Bond length

For the six diatomics studied in this work, Table 3 shows

Results and discussion
All atomic and molecular calculations were performed with
the ZORA-B3LYP method available in the ORCA program
[34]. Initially, the geometries of the molecules were opti-
mized and, then, dissociation energies, harmonic vibrational
frequencies, and static medium dipole polarizabilities were
determined.
First ionization energy
Theoretical and experimental [36] ionization energies are
displayed in Table 2.
The trend of all theoretical results is similar to that of
the experimental data, that is, it increases from Fr to Ra
the bond lengths, dissociation energies, and harmonic vibra-
tional frequencies calculated with the ZORA-B3LYP/ATZP-
ZORA and DKH2-B3LYP/ATZP-DKH2 theoretical models.
No experimental value was found in the literature. Especially
for dimers, as the bond lengths are large, it is necessary to
use our largest basis set containing diffuse functions. This
is why we present only ATZP-ZORA results from now on.
For dimers, even theoretical results are scarce.
Except for ­Fr2, whose difference is 0.072 Å, the other
ATZP-ZORA and ATZP-DKH2 bond lengths are very
similar, since the differences do not exceed 0.015 Å. It is
worth noting that, even for ­Fr2, the DKH2-B3LYP/ATZP-
DKH bond length is only 1.6% longer than that obtained
with the ZORA-B3LYP/ATZP-ZORA procedure. For ­Fr2,
­Ra2, and A ­ c2, the only values available in the literature
that take into account all electrons are those reported by

Table 1  Details regarding the Fr Ra Ac

DZP-ZORA, ADZP-ZORA,
TZP-ZORA, and ATZP-ZORA DZP-ZORA uncontracted (19s16p10d4f) (20s15p10d4f) (19s15p11d5f)
basis sets for Fr, Ra, and Ac
ADZP-ZORA uncontracted set (20s17p11d5f) (21s16p11d5f) (20s16p12d6f)
DZP-ZORA contracted [9s7p4d1f] [9s6p4d1f] [9s6p5d2f]
ADZP-ZORA contracted [10s8p5d2f] [10s7p5d2f] [10s7p6d3f]
TZP-ZORA uncontracted (21s15p12d5f) (21s15p12d5f) (22s15p13d6f1g)
ATZP-ZORA uncontracted set (22s16p13d6f) (22s16p13d6f) (23s16p14d7f2g)
TZP-ZORA contracted [10s6p5d2f] [10s6p5d2f] [10s6p6d3f1g]
ATZP-ZORA contracted [11s7p6d3f] [11s7p6d3f] [11s7p7d4f2g]

Table 2  First ionization ADZP-ZORAa ATZP-ZORAa awCVQZ-DK3b Expt.c

energies (in eV)
Fr (2S) → ­Fr+ (1S) 3.830 4.051 4.018 4.0727
Ra (1S) → ­Ra+ (2S) 5.170 5.199 5.221 5.2784
Ac (2D) → ­Ac+ (1S) 5.578 5.221 − 5.3802
a
Present investigation (ZORA-B3LYP calculations). Basis set generated in this work. bResults from Ref.
[26]. DKH3-CCSD(T) calculations. cExperimental data from Ref [36]

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Table 3  Theoretical bond lengths (re in Å), dissociation energies (De universal Gaussian basis set (UGBS), the agreement is still
in eV), and harmonic vibrational frequencies (ωe in ­cm−1) for the good. Agreement improves when our results are compared
ground states of some diatomics
with those obtained with the theoretical procedures PP-
Molecule ATZP-ZORAa ATZP-DKHb Previous values CCSD(T)/[8s7p6d5f2g] for Ac and aug-cc-pVQZ for H, O,
and F (2.125, 1.930, and 2.118 Å) [39] and DKH2-PBE0/
Fr2 (1Σ g+) re 4.588 4.660 4.665c
SARC (2.128, 1.915, and 2.098 Å) [29].
De 0.564 0.546 0.409c
ωe 32.07 − 33c
Ra2 (1Σ g+) re 5.445 5.460 5.478c Dissociation energy
De 0.087 0.089 0.079c
ωe 16.93 − 17c It is known that the ground state alkali and alkaline earth
Ac2 (3Σg−) re 3.714 3.700 3.635c dimers besides being stable molecules and having large
De 1.468 1.461 1.336c bond lengths, they have small dissociation energies. These
ωe 83.02 − − statements can be confirmed through the results shown in
AcH (1Σ+) re 2.051 2.063 2.159d Table 3. As mentioned earlier, the origin of the chemical
De 3.744 3.670 3.57d bonds in R­ a2, ­Ac2, and AcH is due to the pairing of electrons
ωe 1492.64 − 1373d 7s, 6d, and 6d and 1s, respectively. Unlike bond lengths, dis-
AcO (2Σ+) re 1.956 1.967 2.020d sociation energies increase over the course of this series. As
De 7.706 7.732 7.11d in AcF and AcO, there is a pairing of electrons 6d and 2p, it
ωe 758.99 − 708d is also expected that the dissociation energies of these two
AcF (1Σ+) re 2.118 2.117 2.163d molecules are greater than that of ­Ac2 (cf. Table 3).
De 7.663 7.638 7.00d The ZORA-B3LYP/ATZP-ZORA and DKH2-B3LYP/
ωe 559.73 − 521d ATZP-DKH2 corresponding dissociation energies are very
a close to each other, and the largest difference of 0.074 eV
Present investigation (ZORA-B3LYP calculations). All-electron
basis set generated in Ref. [13] and in this work (sixth-row elements). occurs for AcH. For all dimers, even if the ZORA-B3LYP/
b
DKH2-B3LYP results from Ref. [28]. cDKH2-CASPT2 results ATZP-ZORA results are systematically higher than the
from Refs. [23, 24]. All-electron ANO basis sets ([12s11p8d5f] and DKH2-CASPT2/ANO ones, the orders of magnitude of
[9s8p6d5f2g1h] for Fr and for Ra and Ac, respectively. dResults from
the ZORA-B3LYP and DKH2-CASPT2 dissociation ener-
Ref. [38]. ZORA-BP86 method together with the large uncontracted
universal Gaussian basis set gies are the same. For ­Fr2, Lim et al. [37] found 0.431 eV.
Here, it is important to emphasize that as these dissocia-
tion energies are small, they become very susceptible to
Roos et al. [23, 24]. These calculations are a combination
the theoretical procedure employed. For AcH, AcO, and
of the DKH2-CASPT2 method with the [12s11p8d5f] and
AcF, even though our results are higher than those reported
[9s8p6d5f2g1h] ANO basis sets for Fr and for Ra and Ac,
in Ref. [38], the agreement between them is satisfactory.
respectively. In general, the ZORA-B3LYP/ATZP-ZORA
As occurred for the bond lengths, when we compared
and DKH2-CASPT2/ANO bond lengths are in good agree-
the ZORA-B3LYP/ATZP-ZORA and PP-CCSD(T)/
ment. It can be noted that for F ­ r2, the ATZP-DKH2 bond
[8s7p6d5f2g] for Ac and aug-cc-pVQZ for H, O, and F dis-
length is closer to the ANO than the ATZP-ZORA, while the
sociation energies (3.63, 7.71, and 7.65 eV) [39], the agree-
value (4.593 Å) reported by Lim et al. [37] using relativistic
ment is excellent.
pseudopotential [9-ve PP-CCSD(T)/(14s13p8d5f3g)] is only
0.005 Å higher than ours.
The reason the bond lengths of F ­ r2 and R
­ a2 are greater Harmonic vibrational frequency
than that of ­Ac2 is that the bonds of the first two molecules
are characterized primarily by pairing 7s electrons, while Like dissociation energy, harmonic vibrational frequency is
the latter is by 6d electrons. Another significant reduction small for large bond length. Another determining factor for the
in bond length occurs by going from ­Ac2 to AcH. This was magnitude of vibrational frequency is the mass of the atoms
already predicted by chemical intuition, since for the last that form the chemical bond. Therefore, it is expected that the
molecule, the pairing of electrons is between the orbital 1s harmonic vibrational frequencies of the dimers studied in this
of H with the 6d of the Ac. It is worth mentioning that the work to be small. The results shown in Table 3 confirm our
ionic character of the bond increases from left to right in expectation. Going from ­Ac2 to AcH, the two factors men-
the AcH, AcO, and AcF series. For these diatomics, even tioned above contribute to a significant increase in vibrational
the ZORA-B3LYP/ATZP-ZORA bond lengths being shorter frequency. On the other hand, the main reason for the reduc-
than those obtained from a calculation [38] for all electrons tion of harmonic vibrational frequency through the AcH, AcF
using the ZORA-BP86 method and a large uncontracted and AcO series is the increase in molecular mass.

13
Journal of Molecular Modeling (2022) 28:334
Table 4  Static electric mean dipole polarizabilities (in a.u.)
ATZP-ZORA a
ATZP-DKH b
Fr2 (1Σg+) 589.00 630.51
Ra2 (1Σg+) 520.41 532.01
Ac2 (3Σg−) 317.65 330.09
a
Present investigation (ZORA-B3LYP calculations). All-electron
basis set generated in this work. bDKH2-B3LYP results from Ref.
[28]. cResult from Ref. [37]. (14s13p8d5f3g) valence basis set for Fr
was used
For ­Fr2 and R­ a2, the ZORA-B3LYP/ATZP-ZORA and
DKH2-CASPT2/ANO harmonic vibrational frequencies
agree very well. For ­Fr2, the value of 33.5 ­cm−1 presented
by Lim et al. [37] adds credibility to the results obtained
by us and Roos et al. [23], while for ­Ac2, we did not find
any results in the literature to compare; therefore, our value
seems to be unique. For AcH, the ZORA-B3LYP/ATZP-
ZORA harmonic vibrational frequency is somewhat larger
than the values of 1373 and 1401 ­cm−1 calculated with the
procedures ZORA-BP86/UGBS [38] and MP2 perturbation
theory for all electrons using the Dirac-Coulomb Hamilto-
nian [40], respectively. The agreement between our results
and those found in Ref. [38] significantly improves from
AcH to AcO and AcF. For AcO, the vibrational frequency
(764 ­cm−1) reported by Konings et al. [41] is close to the
value computed in this work.
Polarizability
In order to compare with the DKH2-B3LYP/ATZP-DKH
mean dipole polarities for ­Fr2, ­Ra2, and ­Ac2 previously cal-
culated by our research group, in this article, the ZORA-
B3LYP/ATZP-ZORA results were also included in Table 4.
It can be seen that the mean dipole polarizability decreases
going from F ­ r2 to R
­ a2. The origin of this reduction is that the
electrons of the 7s valence orbital of Ra and Fr come from
a closed and open subshell, respectively, so Ra electrons are
less diffuse than those of Fr. In the formation of A ­ c2, valence
electrons belong to an inner subshell (6d); therefore, once
again it is expected a reduction in the mean dipole polariz-
ability from ­Ra2 to ­Ac2 (cf. Table 4).
For ­R a 2 and A ­ c 2, the ZORA and DKH2 results are
very close to each other, while for F ­ r2, there is a differ-
ence of approximately 7%. We remind you that the ZORA
bond length is about 0.072 Å smaller than the DKH2 one
(see Table 3), which is enough to affect polarizability.
For ­Fr2, the values obtained with the 9-ve PP-CCSD(T)/
(14s13p8d5f3g) (636.3 a.u.) [37] and DKH2-B3LYP/
Page 5 of 7 334
ATZP-DKH2 approximations agree very well with each
9-ve PP-
other. For ­Ra2 and ­Ac2, we did not find any other theoreti-
CCSD(T)c cal or experimental results; however, from the discussions
presented in the previous paragraph, the ZORA-B3LYP/
636.3
ATZP-ZORA mean dipole polarizabilities are in line with
−
chemical intuition.
−
Conclusions
In this work, the DZP-ZORA and TZP-ZORA basis sets
developed by our research group were extended with the
purpose of encompassing the elements Fr, Ra, and Ac. A
diffuse function was added to each atomic symmetry (s, p,
d, and f), giving rise to the sets called ADZP-ZORA and
ATZP-ZORA. In addition, the main objective of the arti-
cle, which was to generate compact and reliable basis sets,
was achieved. The recommendation is to use them together
with the sets of similar qualities previously published for
the H–La and Hf–Rn elements [30–32].
The most relevant conclusions drawn from our results
are the following:
• With the exception of the mean dipole polarizability of
­Fr2, all other ZORA-B3LYP and DKH2-B3LYP results
listed in Tables 3 and 4 are very close to each other.
Hong et al. [38], studying electronic structures of a set of
selected diatomic molecules containing lanthanides and
actinides, also found that the ZORA and DKH2 results of
various properties were essentially of the same quality.
• For Fr, Ra, and Ac, the ZORA-B3LYP/ATZP-ZORA
ionization potentials agree well with experimental data
[36] and benchmark theoretical values [26].
• In general, the agreement between the bond lengths, dis-
sociation energies, and harmonic vibrational frequencies
calculated in this study and the relativistic all-electron
and pseudopotential results found in the literature is
good, indicating once again that our basis sets are reli-
able to perform ZORA calculations.
• For ­Fr2, ­Ra2, and A
­ c2, the ZORA-B3LYP/ATZP-ZORA
mean dipole polarizabilities are slightly smaller than
those predicted with the DKH2-B3LYP/ATZP-DKH
procedure; however, both theoretical models show a
decrease in polarizability throughout the series, a fact
that is in accordance with chemical intuition.
The XZP-ZORA and AXZP-ZORA (X = D and T) basis
sets for the H–La and Hf–Ac elements are available on dif-
ferent formats at https://​qcgv.​ufes.​br/.
13
334 Page 6 of 7
Author contribution All authors contributed equally to the work.
Funding We would like to acknowledge the financial support of Con-
selho Nacional de Desenvolvimento Científico e Tecnológico (Brazil-
ian Agency).
Data availability Not applicable.
Declarations
Competing interests The authors declare no competing interests.
Conflict of interest The authors declare no competing interests.
References
1. Pyykkö P (1988) Relativistic effects in structural chemistry.
Chem Rev 88:563
2. Zerner MC, Salahub D (1989) The challenge of d- and f-elec-
trons. American Chemical Society, Washington
3. Kaltsoyannis N, Hay PJ, Li J (2006) Blaudeau, J.P., Bursten,
B.E.: The chemistry of the actinide and transactinide elements.
Morss LR, Edelstein N, Fuger J (Eds.), 3rd edn. Springer,
Dordrecht
4. Dolg,M (2000) Effective core potentials. In Modern methods and
algorithms of quantum chemistry. Grotendorst J (Ed.), 2nd edn.
John von Neumann Institute for Computing. Jülich 3
5. Frenking G, Antes I, Böhme M, Dapprich S, Ehlers AW, Jonas V,
Neuhaus A, Otto M, Stegmann R, Veldkamp A, Vyboishchikov
SF (1996) Pseudopotential calculations of transition metal com-
pounds: scope and limitations. Rev Comp Chem 8:63
6. Güell M, Luis JM, Solà M, Swart M (2008) Importance of the
basis set for the spin-state energetics of iron complexes. J Phys
Chem A 112:6384
7. Vyboishchikov SF, Sierraalta A, Frenking G (1997) Topological
analysis of electron density distribution taken from a pseudopo-
tential calculation. J Comput Chem 18:416
8. Cirera J, Ruiz E (2008) Exchange coupling in ­CuIIGdIII dinuclear
complexes: a theoretical perspective. C R Chim 11:1227
9. Douglas M, Kroll NM (1974) Quantum electrodynamical correc-
tions to the fine structure of helium. Ann Phys (NY) 82:89
10. Hess BA (1985) Applicability of the no-pair equation with free-
particle projection operators to atomic and molecular structure
calculations. Phys Rev A 32:756
11. Hess BA (1986) Relativistic electronic-structure calculations
employing a two-component no-pair formalism with external-field
projection operators. Phys Rev A 33:3742
12. Van Lenthe E, Baerends EJ, Snijders JG (1993) Relativistic regu-
lar two-component Hamiltonians. J Chem Phys 99:4597
13. Jorge FE, Canal Neto A, Camiletti GG, Machado SF (2009) Con-
tracted Gaussian basis sets for Douglas–Kroll–Hess calculations:
estimating scalar relativistic effects of some atomic and molecular
properties. J Chem Phys 130:064108
14. Barros CL, de Oliveira PJP, Jorge FE, Canal Neto A, Campos
M (2010) Gaussian basis set of double zeta quality for atoms
Rb through Xe: application in non-relativistic and relativis-
tic calculations of atomic and molecular properties. Mol Phys
108:1965
15. de Berrêdo RC, Jorge FE (2010) All-electron double zeta basis sets
for platinum: estimating scalar relativistic effects on platinum(II)
anticancer drugs. J Mol Struct THEOCHEM 961:107
13
Journal of Molecular Modeling (2022) 28:334
16. Canal Neto A, Jorge FE (2013) All-electron double zeta basis sets
for the most fifth-row atoms:application in DFT spectroscopic
constant calculations. Chem Phys Lett 582:158
17. Campos CT, Jorge FE (2013) Triple zeta quality basis sets for
atoms Rb through Xe: application in CCSD(T) atomic and molec-
ular property calculations. Mol Phys 111:167
18. Martins LSC, Jorge FE, Machado SF (2015) All-electron seg-
mented contraction basis sets of triple zeta valence quality for the
fifth-row elements. Mol Phys 113:3578
19. Baykova SV, Semenova AV, Presnukhinaa SI, Novikova AS, Shet-
nev AA, Boyarskiy VP (2022) Hydrogen vs halogen bonding in
crystals of 2,5-dibromothiophene-3-carboxylic acid derivatives.
J Mol Struct. 260:132785
20. Grudova MV, Novikov AS, Kubasov AS, Khrustalev VN, Kiri-
chuk AA, Nenajdenko VG, Tskhovrebov AG (2022) Aurophilic
interactions in cationic three-coordinate gold(I) bipyridyl/isocya-
nide complex. Curr Comput-Aided Drug Des 12:613
21. Mironova AD, Mikhaylov MA, Maksimov AM, Brylev KA,
Gushchin AL, Stass DV, Novikov AS, Eltsov IV, Abramov PA,
Sokolov MN (2022) Phosphorescent complexes of {Mo6I8}4+
and {W6I8}4+ with perfluorinated aryl thiolates featuring unusual
molecular structures. Eur J Inorg Chem 2022:e202100890
22. De Almeida CA, Pinto LPNM, dos Santos HF, Paschoal DFS
(2021) Vibrational frequencies and intramolecular force constants
for cisplatin: assessing the role of the platinum basis set and rela-
tivistic efects. J Mol Model 27:322
23. Roos BO, Veryazov V, Widmark P-O (2004) Relativistic atomic
natural orbital type basis sets for the alcaline and alkaline-earth
atoms applied to the ground-state potentials for the corresponding
dimers. Theor Chem Acc 111:345
24. Roos BO, Lindh R, Malmqvist P-A, Veryazov V, Widmark P-O
(2005) New relativistic ANO basis sets for actinide atoms. Chem
Phys Lett 409:295
25. Te Velde G, Bickelhaupt FM, Baerends EJ, Fonseca Guerra C,
van Gisbergen SJA, Snijders JG, Ziegler T (2001) Chemistry with
ADF. J Comput Chem 22:931
26 Hill JG, Peterson KA (2017) Gaussian basis sets for use in cor-
related molecular calculations. XI. Pseudopotential-based and all-
electron relativistic basis sets for alkali metal (K-Fr) and alkaline
earth (Ca-Ra) elements. J Chem Phys. 147:244106
27 Feng R, Peterson KA (2017) Correlation consistent basis sets for
actinides. II. The atoms Ac and Np–Lr. J Chem Phys. 147:084108
28. Campos CT, de Oliveira AZ, Ferreira IB, Jorge FE, Martins LSC
(2017) Segmented all-electron Gaussian basis sets of double and
triple zeta qualities for Fr, Ra, and Ac. Chem Phys Lett 675:1
29. Pantazis DA, Neese F (2011) All-electron scalar relativistic basis
sets for the actinides. J Chem Theory Comput 7:677
30. Canal Neto A, de Oliveira AZ, Jorge FE, Camiletti GG (2021)
ZORA all-electron double zeta basis sets for the elements from H
to Xe: application in atomic and molecular property calculations.
J Mol Model 27:232
31. Centoducatte R, de Oliveira AZ, Jorge FE, Camiletti GG (2022)
ZORA double zeta basis sets for fifth row elements: application in
studies of electronic structures of atoms and molecules. Comput
Theor Chem 1207:113511
32. Canal Neto A, Ferreira IB, Jorge FE, de Oliveira AZ (2021)
All-electron triple zeta basis sets for ZORA calculations:
application in studies of atoms and molecules. Chem Phys Lett
771:138548
33. Jorge FE, Canal Neto A (2020) A new method for optimizing a set
of nonlinear parameters: application in total Hartree-Fock atomic
energy calculations. Theor Chem Acc 139:76
34. Neese F (2012) The ORCA program system. Wiley Interdiscip
Rev Comput Mol Sci 2:73
35. de Jong WA, Harrison RJ, Dixon DA (2001) Parallel Douglas-
Kroll energy and gradients in NWChem: estimating scalar
Journal of Molecular Modeling (2022) 28:334
relativistic effects using Douglas-Kroll contracted basis sets. J
Chem Phys 114:48
36. Kramida A, Ralchenko Yu, Reader J, and NIST ASD Team
(2021) NIST Atomic Spectra Database (ver. 5.9), [Online].
Available: https:// ​ p hysi ​ c s. ​ n ist. ​ g ov/ ​ a sd [2022, July 25].
National Institute of Standards and Technology, Gaithersburg,
MD
37 Lim IS, Schwerdtfeger P, Söhnel T, Stoll H (2005) Ground-
state properties and static dipole polarizabilities of the álcali
dimers from to ( = 0, +1). from scalar relativistic pseudopoten-
tial coupled cluster and density functional studies. J Chem Phys
122:134307
38. Hong G, Dolg M, Li L (2001) A comparison of scalar-relativistic
ZORA and DKH density functional schemes: monohydrides,
monooxides and monofluorides of La, Lu. Ac and Lr Chem Phys
Lett 334:396
39. Küchle W, Dolg M, Stoll H (1997) Ab initio study of the lantha-
nide and actinide contraction. J Phys Chem A 101:7128
Page 7 of 7 334
40. Laerdahl JK, Faegri K, Visscher L, Saue T (1998) A fully rela-
tivistic Dirac–Hartree–Fock and second-order Möller-Plesset
study of the lanthanide and actinide contraction. J Chem Phys
109:10806
41. Konings RJM, Beneš O, Kovács A, Manara D, Sedmidubský D,
Gorokhov L, Iorish VS, Yungman V, Shenyavskaya E, Osina E
(2014) The thermodynamic properties of the f-elements and their
compounds Part. 2. The lanthanide and actinide oxides. J Phys
Chem Ref Data 43:013101
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