Received: 29 December 2023 Revised: 14 February 2024 Accepted: 16 February 2024

DOI: 10.1002/jcc.27361

RESEARCH ARTICLE

Quantum mechanical study of transition metal hydrides:

Comparison of determined molecular properties with
experimental data

Adam Vavrečka | Kateřina Fatková | Jaroslav V. Burda

Department of Chemical Physics and Optics,

Faculty of Mathematics and Physics, Charles
University, Prague, Czech Republic
Correspondence
Jaroslav V. Burda, Department of Chemical
Physics and Optics, Faculty of Mathematics
and Physics, Charles University, Ke Karlovu
3, 12116 Prague, Czech Republic.
Email: jaroslav.burda@matfyz.cuni.cz
Funding information
Grantová Agentura České Republiky,
Grant/Award Number: 23-06909S
Abstract
This study compares results of four relativistic pseudopotential basis sets, which
differ mainly by their size: double-zeta introduced by Hay and Wadt from Los Alamos
National Laboratory (LANL2DZ), triple-zeta based on Stuttgart energy-consistent
scalar-relativistic pseudopotential (SDD3), its extension with 2fg polarization func-
tions, and combination of Stuttgart pseudopotentials with quintuple-zeta cc-pV5Z
base (SDD5). Hydrides of transition metals from Cr to Zn group are chosen as refer-
ence molecules. The coupled cluster method (CCSD(T)) is used for evaluation of
selected molecular characteristics. Interatomic distances, dissociation energies, vibra-
tion modes, and anharmonicity constants are determined and compared with avail-
able experimental data. As expected, the accuracy of basis depends mainly on its
size. However, only moderate modification of SDD3 basis set significantly improves
its accuracy, which becomes comparable to the largest basis set. Nevertheless, the
time consumption is significantly lower.

KEYWORDS
anharmonic vibration spectra, basis set, diatomic molecule, quantum-mechanical calculations

1 | I N T RO DU CT I O N published by Morse in 1929.15 In 30s, further improvements of that

The aim of this study is to compare several selected relativistic
pseudopotentials and corresponding basis sets for calculations containing
transition metals (TM). Transition metal hydrides have been chosen as
reference molecules for this comparison. There are two substantial
advantages for it, mainly such systems are not extensive, and moreover,
very accurate experimental data exists, including anharmonicities of cor-
responding vibrational modes.1,2 The compared quantities therefore
include interatomic distances, bond dissociation energies (DEs), vibration
frequencies, and anharmonicity constants. Some additional sets of
experimental data for transition metal hydrides were measured later for
example by Squires3 and by many other researchers, for instance in
References 4–14. First theoretical study on molecular potential was
potential were suggested by Dunham16 and Coolidge et al.17 and slightly
later by Hulburt and Hirschfelder,18 whose five-parameter potential was
adopted and employed besides the original Morse potential function for
fitting procedure in our study. Recently newer potentials appeared for
determination of vibrational-rotational levels in diatomic molecules.19,20
Especially interesting work was presented by Desai et al.21 where
another modification of the Morse potential for diatomic molecules
appeared. In this paper, a comparison with Hulburt-Hirschfelder (H-H)
potential curve was also mentioned. Nevertheless, from the paper, it fol-
lows that H-H approach is relatively stable and similarly accurate.
Authors also presented a Python solution for the time independent
Schrödinger equation and Matrix Numerov methods applied on Morse
potential function. Another numerical solution based on Matrix Numerov

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium,
provided the original work is properly cited.
© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.

J Comput Chem. 2024;1–10. wileyonlinelibrary.com/journal/jcc 1


2 VAVREČKA ET AL.
method was suggested in Reference 22, which was applied also for TM
(Ni, Co) interactions with CO2 and N2O molecules.23 Experimental study
on hydrides and deuterated hydrides of coinage metals was published by
Le Roy group24,25 where a careful isotopomer analysis of metals is also
presented. Based on vibrational-rotational parameters dissociation ener-
gies and equilibrium distances are presented: D0 = 65.8 (Cu), 55.2 (Ag),
and 77.8 (Au) kcal/mol; rO = 1.463 (Cu), 1.618 (Ag), and 1.524 (Au) Å.
Recently Li et al.26 published magneto-infrared spectra of NiH measured
in several noble gas matrices supported by ab initio or DFT calculations
demonstrating a very good match with Herzberg Table 2. Another inter-
ested study dealt with tungsten hydrides and deuterated hydrates
WH/WD
WH6/WD627 measured in rare gas matrices (Ne, Ag).
Authors supported their experiments by calculations (among other)
BPW91/6-311++G(3df,3pd)/SDD obtaining optimal r = 1.714 Å with
harmonic frequencies: ωe = 1911 (WH) and 1354 (WD) cm
1. The same
authors also explored rhenium and manganese hydrides using similar
approach.28 They observed harmonic frequencies: ωe = 1478 (MnH),
1066 (MnD), 1985 (ReH), and 1423 (ReD) cm
1 in Ar matrix.
We are aware of the fact that a large number of theoretical calcula-
tions were performed on the topics of transition metal hydrides, how-
ever, just a few most relevant computational studies are mentioned
here. One of the very early papers on this topics comes from Baerends
29
laboratory where authors explored relativistic effects on hydrides of
coinage and zinc group metals. The predicted distances, dissociation
energies, and vibrational frequencies were in good accord to experi-
mental values from Handbook of Molecular Constants.30 A year later,
31
Lee and McLean published similar paper on Ag and Au hydrides by
Dirac-HF method. One of the first applications of pseudopotential on
gold hydride was performed by Schwerdtfeger et al.32 using CISD and
CEPA methods. Much more recent results were published in methodo-
33
logical paper from Head-Gordon laboratory where dissociation ener-
gies of the first-row transition metal hydrides were explored. Their
CCSDTQ results differ from our approach using the S2FG basis set for
DeA values by RMSD = 2.3 kcal/mol. (In this case, it was not possible
correctly compare SDD5 approach due to a small number of available
values because of missing basis sets of several elements, cf. below.) In
similar methodological study employing large set of DFT functional,34
authors claimed that larger amount of HF exchange is necessary (up to
50%) for hydrides of TM and therefore, these hydrides represent specif-
ically challenging systems for DFT. Nevertheless, CAM-B3LYP per-
formed as one of the best functionals together with some variants of
B97 functional. They have used all-electron def2-QZVPPD for TM in
optimal experimental geometries from Reference 35 evaluating ener-
gies without any relativistic corrections so that the RMSD comparing to
our results is relatively large (13.7 kcal/mol). Another computational
study considering ZnH molecule appeared recently by Zhao et al.36
Despite we could not find experimental data systematically for all
transition metal hydrides, the calculations are performed for the TM
from the sixth (Cr) to the twelfth (Zn) group. Great attention is also
paid to determination of the correct ground state multiplicity of the
explored hydrates.
Selection of compared basis sets follows from general availability.
The all-electron (AE) basis sets were excluded in preliminary part of
1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
this study since they do not consider relativistic effect and in this way,
they failed to predict experimental data with sufficient accuracy. In
order to demonstrate this fact, the well-tempered basis set for TM
(WTBS References 37,38) and ANO-RCC for H (Reference 39) were
used for the first row of transition metal hydrides. Even such a very
large basis sets were not able to predict bond distances of the studied
hydrides even qualitatively correctly; large difference of equilibrium
distance for MnH: rexp = 1.731 and ropt = 1.450 Å led to too high
bonding energy (D0M = 68 kcal/mol vs. experimental estimation
De < 55 kcal/mol) at the CCSD level of calculations. Similarly, also in
the CuH case, the measured equilibrium distance (rexp = 1.463) is
much longer in comparison with AE-calculations: ropt = 1.289 Å with
analogous overestimation of the calculated DE: D0M = 115 kcal/mol
versus 60 kcal/mol determined experimentally. Therefore, only a
group of three quazi-relativistic small-core pseudopotentials is chosen
with corresponding basis sets taken from the Basis Set Exchange
Library40–42; namely Hay-Wadt LANL2DZ,43,44 Stuttgart relativistic
small core (RSC 1997) pseudopotentials and corresponding basis sets
(labeled as SDD3 here after),45–47 and another basis set, which can be
found at the Basis Set Exchange Library under acronym cc-pV5Z-
PP,48,49 in combination with a similar set of pseudopotentials as
Stuttgart RSC 1997 (abbreviated as SDD5 later on). One of the main
goals of this work is to demonstrate that relatively mild extension of
the original SDD3 pseudoorbitals can give relatively very accurate
results. We simply added (or replaced a single set of f-polarization
functions by) a group of 2fg polarization functions. This basis set will
be called S2FG here after.
For these four basis sets, geometry optimizations and scans of
potential energy curves of all the hydrides are performed. From the
optimization step, distances, harmonic frequencies, and dissociation
energies (obtained by subtracting atomic energies and including Zero-
Point Vibration Energies—ZPVE) are determined. Energies of scanned
interatomic distances are fitted on (a) Morse potential, (b) Morse poly-
nomial function, and (c) five-parameter potential function suggested
by Hulburt and Hirschfelder.18 From those fitted potentials, all exam-
ined molecular parameters (optimal distances, bonding energies, fre-
quencies, and anharmonicity constants) are also evaluated. The
received parameters are compared with available experimental data.
2 | COMPUTATIONAL DETAILS
The computationally fastest pseudopotentials and basis sets used in
this work are Hay-Wadt LANL2DZ,43,44 which are frequently applied
for calculations when TM are presented. Pseudopotentials for sixth to
eleventh group of TM cover 10, 28, and 60 inner electrons for fourth,
fifth, and sixth row of elements, respectively. Pseudoorbitals of
double-zeta character [3s3p2d] are used for description of lower sp-
shell plus valence electrons. In the case of Zn-group, just valence elec-
trons are described explicitly [2s2p2d].
Stuttgart relativistic small core pseudopotentials with atomic
basis set is of extended triple-zeta quality (SDD3),45–47 which describes
valence shell plus sp-electrons from the previous lower shell.
 1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
VAVREČKA ET AL. 3

Primitive gaussian functions are contracted to [6s5p3d] pseudo-orbitals. 6-311G(2df,2pd)66 for the S2FG group, and with cc-pV5Z base67 in cal-
Also, projector operators of the pseudopotentials contain one additional culation where metals were treated by SDD5 basis sets.
set of polarization projectors (i.e., f-projectors for third row of TM, up to These four different basis sets are used for optimization at the CCSD
the h-projector in the case of third row of TM). level of theory and for scanning of the CCSD(T) energies in dependence
The third approach is based on modified pseudopotentials on interatomic distances. All the calculations are performed with Gauss-
(Stuttgart RSC 1997) in combination with Dunning's cc-pV5Z-PP basis ian 09 program package. In the scan evaluation, energies of ca. 70 points
48,49
set, with substantially extended description of outer electrons with united step of 0.05 Å are determined. Then, the scanned potential
including up to one set of i-polarization functions. In the SDD5 group, energy points are fitted by the Morse potential (M)15:
all the TM are uniquely described by (16s13p12d)/[6s6p5d] generally

2
contracted functions plus additional spd-set of primitive GFs.48–51 V M ðxÞ ¼ DeM 1
e
aðx
rM Þ , ð1Þ
Polarization functions consist of uncontracted 4f3g2h1i orbitals. The
corresponding pseudopotentials are the original SDD3 ones extended
by additional sets of two s, p, and d projectors. Unfortunately, this basis From the a parameter and/or k parameter of the harmonic poten-
set is not available for the first-row elements: Cr, Mn, Fe, Co, and Ni. tial (Equation 14), vibrational frequencies of the given hydrides are
Concerning the S2FG level, the polarization functions were evaluated using equations:
obtained by optimizing electronic structure of atomic ground state
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
using CCSD method within Molpro program52 taking into in account 1 2a2 DeM
νM ¼ ð2aÞ
work of Kahn and colleagues53,54 and other researchers involved in 2π M
pseudopotential development, for example References 43–46,55.
Obtained values are summarized in Table 1 below and some closer and/or
details can be found in References 56–63.
rffiffiffiffiffi
Hydrogen atom is considered consistently to individual pseudoor- 1 k
νH ¼ ð2bÞ
bitals; that is, Dunning Hay (31s)/[2s] DZ base64,65 is used in LANL2DZ 2π M
calculations, Pople's 6-311G(d,p) base,60 in the case of SDD3, extended
where M is reduced mass of the given hydride. Since the Morse curve
is not symmetrical the anharmonicity constant is defined by formula:
T A B L E 1 Exponents of the 2fg polarization primitive gaussian
function optimized with CCSD method using the original SDD3 basis hνM
βM ¼ ð3Þ
set and pseudopotentials. 4DeM

Atom/exponents f f g
Cr 3.1656 0.9934 1.9382 and then the energy of eigenstates of Morse oscillator can be evalu-
Mo 2.0636 0.5578 1.5027 ated as:
W 2.0195 0.5137 1.4586
    
1 hνM 1 2
Mn 2.6189 1.6131 2.6580 EnM ¼ hνM n þ
pffiffiffiffiffiffiffiffiffi n þ ð4Þ
2 2 DeM 2
Tc 2.1264 0.6205 1.5654
Re 2.0845 0.5787 1.5236
where the ZPVE values can be obtained by assuming n = 0. Finally,
Fe 6.2573 0.5372 1.9108
for the comparison with experimental data, the anharmonicity con-
Ru 2.2330 0.6503 1.4222
stants were also evaluated:
Os 1.1870 0.3750 1.0329
Co 3.9044 1.5986 2.4435 ωe xeM ¼ βM νM : ð5Þ
Rh 1.9676 0.5493 1.2302
Ir 1.4929 0.4969 1.5157 In order to increase the accuracy of explored molecular parame-
Ni 4.9683 1.2990 3.2791 ters two modified Morse potential functions are considered. First, the
Pd 2.1881 0.6064 1.3710 so-called Morse polynomial to the fourth degree (MP) in the form:
Pt 1.4193 0.4662 1.2077 
2
3
Cu 4.2219 2.7600 3.1600 V MP ðxÞ ¼ DeMP c2 1
e
aðx
rMP Þ þ c3 1
e
aðx
rMP Þ
Ag 2.1045 0.7987 1.8436

4
Au 1.5344 0.6119 1.5118 þ c4 ð1
e
aðx
rMP Þ Þ ð6Þ
Zn 4.3272 2.7214 4.3662
Cd 2.0340 0.2922 0.3555
where c2 þ c3 þ c4 ¼ 1: Second, the Hulburt-Hirschfelder 5-parameter
Hg 1.3426 0.4202 1.3277
potential function (HH)18:
 1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
4 VAVREČKA ET AL.


2   
3 5
V HH ðxÞ ¼ DeHH 1
e
aðx
rHH Þ þ c:a3 ðx
rHH Þ3 e
2aðx
rHH Þ ð1 þ bðx
r HH ÞÞ : ωe xe ¼
Be a2
a21 ð12Þ
2 4
ð7Þ

where Be ¼ h= 8π 2 μr2e c is a rotational constant. ZPVE corrected DE

Here, the first term in the square bracket represents the for an arbitrary potential can be evaluated as:
original Morse potential. Please, note that DeX denotes dissociation
1 1
energy obtained based on corresponding method without Zero-Point D0 ≈ De þ ωe
ωe xe ð13Þ
2 4
Vibration Energies (ZPVE). If ZPVE is included label D0X is used
instead. as approximated by Dunham16 and Hirschfelder.18
An arbitrary potential energy function can be expanded about re
in powers of ξ ¼ ðx
re Þ=re ,
2.1 | Determination of equilibrium interatomic
V ðxÞ ¼ a0 ξ2 1 þ a1 ξ þ a2 ξ2 þ … : ð8Þ distances and dissociation energies

This expression, introduced by Dunham,16 defines coefficients an. The equilibrium distances are determined at the harmonic approxima-
They are related to the parameters cn of the Morse polynomial tion using the optimization algorithm (rO) and also by fitting procedure
(Equation 6) as follows (Coolidge et al.17): of the scanned energies (applying the least square methods) to the
above-mentioned potentials.
a0 ¼ 4β De c2 2
For the determination of DEs, two different approaches are uti-
 
c3 lized. The first one is based on definition of dissociation energy, that
a1 ¼ β
2 þ 2 ,
c2
  is, energy difference between the given hydride (SP calculation using
7 c3 c4
a2 ¼ β2
6 þ 4 , CCSD(T) method with CCSD optimized bond length) and both atoms
3 c2 c2
  (in their ground states) DeA and with ZPVE correction
D0A. The sec-
c3 c4
a3 ¼ β3
2 þ 10
16 , ond approach uses fits of: (a) the Morse potential (Equation 1), (b) the
c2 c2
 
62 c3 104 c4 Morse polynomial function (Equation 6), and (c) the H-H modification
a4 ¼ β 4
12 þ ,
45 c2 3 c2 of the Morse potential (Equation 7).
 
4 172 c3 160 c4
a5 ¼ β 5
þ
,
5 15 c2 3 c2
 
127 46 c3 324 c4
a6 ¼ β 6
þ : ð9Þ 2.2 | Vibration analysis and first anharmonicities
315 5 c2 5 c2

The above-mentioned fitted potentials are employed also for determina-

Concerning the H-H function (Equation 7), they are found to be tion of vibrational frequencies and anharmonicity constants. However, to
determined by the relations: get more accurate fitted data, different strategy is adopted. Here, only
relevant part of the points in the close vicinity of the potential minimum
a0 ¼ 4β De , 2
(usually about 20–30 points) are employed within the fitting procedure.
 1=2
a0 In previous fit for determination of DEs, the whole energy scan is used
a1 ¼ ð
1 þ cÞ
De ,
  so that fitted potential curves are somehow worse reproduced. The bond
7 a0
a2 ¼ þ ðb
2Þc , lengths are always slightly underestimated and vibration parameters are
12 De
also not so accurate. Therefore, in this second (or partial) fit, bond lengths
  3=2
1 a0 and vibrational parameters are evaluated with substantially higher accu-
a3 ¼

2ðb
1Þc ,
4 De
    2 racy (overestimating bonding energy).
31 4 a0
a4 ¼ þ 2b
c , Moreover, from the closest points to the potential energy mini-
360 3 De
  5=2 mum (usually eight lowest points) also harmonic frequencies are
1 2 a0
a5 ¼

ð2b
1Þc , determined, fitted by parabolic curve:
40 3 De
  6
127 2 a0
a6 ¼ þ ð5b
2Þc : ð10Þ 1
20160 15 De V H ðxÞ ¼ kðx
r H Þ2 þ DeH , ð14Þ
2

Frequencies and anharmonic corrections can be evaluated using

Dunham's coefficients as follows18: at the same CCSD(T) computational level for all four basis sets. In this
way, other optimal bonding distances (rH, rM, rMP, and rHH) are
pffiffiffiffiffiffiffiffiffiffiffi
ωe ¼ 4β Be De , ð11Þ obtained and will be used in further discussion.
 1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
VAVREČKA ET AL. 5

3 | RESULTS AND DISCUSSION confirmed quintuplet as the ground state, with the only exception of
SDD5 basis set where the preferred ground state is septuplet. In the case
3.1 | Search for the ground state multiplicity of ReH, all basis sets prefer quintuplet despite small differences between
both states.
It is very important to optimize correct ground state geometry. Therefore,
special accent is laid on the correct multiplicity and corresponding elec-
tronic structure. In the first step, the optimal geometries for several possi- 3.2 | Interatomic distances
ble multiplicities were searched at the CCSD/SDD3 computational level
and the global minimum was found (the electronic structure corresponds In this study, several different sets of interatomic distances are deter-
to single sigma bond, usually slightly enhanced by some π-backdonation mined. From the optimization part, bond lengths (rO) are obtained at
to p-AO of hydrogen). If the energy difference between the lowest and the CCSD level. Since potential energy curves with the scan calcula-
the second lowest multiplicities was greater than 0.25 eV (ca. 7 kcal/mol) tions for each hydride are evaluated, the distances corresponding to
the same spin state for the other basis sets was expected to be the the lowest values based on the fitted harmonic (rH), Morse (rM),
ground state as in the SDD3 basis. The energy differences for searched extended Morse (rMP), and H-H (rHH) potentials are determined. In
multiplicities are displayed at the CCSD/SDD3 computational level in Table 3, the interatomic distances for individual basis sets can be
Table 2. When the energy differences among the calculated multiplicities compared with experimentally known bond lengths. From this table, it
were smaller than 0.25 eV the optimization procedure was repeated for follows that while distances obtained with LAN and SDD3 bases are
the remaining basis sets independently. This situation occurred only for
two hydrides: TcH and ReH. In the TcH case, calculations in all basis sets
T A B L E 3 Comparison of the experimentally known bond
lengths1,2 with values determined using the CCSD(T) method based
on the H-H potential.
T A B L E 2 Energy difference between ground state and other Hydride Exp. LAN SDD3 S2FG SDD5a
considered multiplicities ΔEX (X = 1 for singlet, 2 for doublet, etc.)
determined at the CCSD/SDD3 computational level for each hydride CrH 1.656 1.755 1.710 1.659 -
(in eV). In the last column, the chosen multiplicity for the given MnH 1.731 1.824 1.793 1.731 -
hydride is displayed. FeH 1.589 1.772 1.733 1.671 -

E2 E4 E6 E8 References MS CoH 1.542 1.619 1.560 1.499 -

7
CrH 3.46 1.69 0 1.74 6 34
Σ 6 RhH 1.590 1.739 1.617 1.548 1.552

MoH 2.91 1.81 0 6 5

Σ 6 NiH 1.476 1.529 1.486 1.500 -

WH 2.50 1.93 0 6 PtH 1.529 1.570 1.562 1.500 1.523

FeH 2.95 0.74 0 4

Δ 5,34
4 CuH 1.46311,24 1.558 1.453 1.440 1.487

RuH 2.15 0 0.97 4

Φ5 4 AgH 1.61824 1.726 1.791 1.618 1.622

OsH 1.78 0 0.48 4 AuH 1.52424 1.593 1.588 1.501 1.526

NiH 0 0.50 4.64 2

Δ5,34 2 ZnH 1.595 1.694 1.632 1.573 1.582

PdH 0 2.57 7.65 2 5

Σ 2 CdH 1.775 1.836 1.807 1.770 1.755

PtH 0 3.18 6.95 2 HgH 1.766 1.889 1.824 1.727 1.747

ZnH 0 4.44 15.02 2 34

Σ 2 CrD 1.664 1.755 1.710 1.659 -

CdH 0 3.98 15.30 2 MnD 1.731 1.824 1.793 1.731 -

HgH 0 4.32 13.88 2 FeD 1.589 1.772 1.733 1.671 -

E1 E3 E5 E7 CoD 1.518 1.619 1.560 1.499 -

MnH 5.94 4.77 2.20 0 7 34

Σ 7 RhD 1.4657 1.739 1.617 1.548 1.552

TcH 3.98 2.60 0a 0.14 5 NiD 1.465 1.529 1.486 1.500 -

ReH 3.71 2.24 0 b

0.17 5 PdD 1.529 1.606 1.596 1.522 1.530

CoH 2.27 0 0.32 3

Φ5,34 3 PtD 1.524 1.570 1.562 1.500 1.523

RhH 0.78 0 2.06 3

Φ / Δ
5 3 7
3 CuD 1.463 1.558 1.453 1.440 1.487

IrH 0.90 0 1.54 3

Φ 5,12
3 AgD 1.618 1.726 1.791 1.618 1.622

CuH 0 2.55 6.51 1 34

Σ 1 AuD 1.524 1.593 1.588 1.501 1.526

AgH 0 1.90 8.40 1 ZnD 1.605 1.694 1.632 1.573 1.582

AuH 0 3.92 8.38 1 CdD 1.748 1.836 1.807 1.770 1.755

a
HgD 1.757 1.889 1.824 1.727 1.747
For all basis sets except SDD5.
b a
For all basis sets. If basis set available.
 1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
6 VAVREČKA ET AL.

usually visibly longer by several hundredth of Å, the distances from
SDD5 and S2FG bases give distinctly more accurate estimations. This
trend can be quantitatively expressed in RMSD values displayed in
the first section of Table 7. The interatomic distances of the complete
set of all the explored hydrides in all the basis sets are summarized in
Table S1. In that table, different sets of bond lengths are collected:
from (a) the CCSD optimization rO, (b) fit of the harmonic potential rH,
(c) fit of the Morse potential rM, (d) fit of the Morse polynomial rMP,
and (e) fit with H–H potential rHH. The interatomic distances obtained
from the fit of the harmonic potential are very close to distances
based on the fitted Morse potential (due to manner of fitting proce-
dure). In the case of TcH and ReH, the predicted multiplicity is quintu-
plet. However, the septuplet state is only about 0.15 eV higher. As
one could expect evaluated distances are relatively different (higher
multiplicity has about ca. 0.15 Å longer bond length) so that it would
be possible to make decision based also purely on the experimental
data (at least in the Re case). Unfortunately, according to our knowl-
edge no experimental evidence exists in literature. Another fact can
be noticed in Table S1 where for mercury hydride distances obtained
by LAN and SDD3 basis sets are longer than analogous distances of
cadmium hydride (rO(CdH) = 1.833 and rO(HgH) = 1.883 in LAN and
rO(CdH) = 1.804, and rO(HgH) = 1.820 in SDD3). In all other hydrides
and all the considered basis sets, the “second periodicity” as recog-
nized by Pyykkö68,69 is fulfilled (i.e., the longer distances for hydrides
from second row of TM in comparison with third row). Regarding vari-
ous types of PES potentials, it can be concluded that the Morse poly-
nomial and the H-H potential functions give almost the same RMSD
in S2FG and SDD5 basis sets, so that both these potentials describe
the equilibrium distances equally well. Besides Herzberg tables,2 our
results especially from S2FG and SDD5 are in very good accord with
the above-mentioned experimental data, for example, from Le Roy
group24,25 or Li et al.,26,27 mentioned in Section 1.
3.3 | Dissociation energies
The DEs are estimated based on two approaches. First, as already
mentioned, according to the definition — as a difference between

T A B L E 4 Comparison of dissociation energies D0 (in kcal/mol) obtained from the fitted H-H potential and values obtained from the definition
for some experimentally known hydrides.

Exp. Fitted HH potential Definition

Hydride
LAN SDD3 S2FG SDD5 LAN SDD3 S2FG SDD5
8 5 4 14
CrH 45 ± 2 45 ± 2 41 ± 3 43.9 34.6 39.2 48.5 - 34.9 38.7 46.0 -
MoH 53 ± 55 46 ± 34 38.2 41.3 51.8 52.9 38.5 41.5 49.7 53.3
2 9
MnH (57.7) 30.2 ± 1.6 30 ± 4 24.3 25.8 36.1 - 24.3 25.7 33.6 -
FeH 37 ± 210 43 ± 65 30 ± 34 31.114 20.2 22.1 31.5 - 20.3 22.0 29.1 -
5
RuH 56 ± 5 29 ± 3 44.2 49.3 58.0 57.9 44.4 49.7 55.9 58.6
CoH 45.7 54 ± 105 42 ± 34 47.914 41.8 31.1 42.9 - 42.3 28.1 40.0 -
RhH 59 ± 55 32.2 51.5 63.9 65.1 34.0 52.0 61.6 65.7
NiH ≤702 65 ± 65 51.0 39.3 57.7 - 51.1 36.8 49.1 -
5
PdH 56 ± 6 41.3 42.6 51.8 51.2 40.7 42.4 48.7 50.9
PtH ≤792 64.6 65.7 79.2 78.3 66.8 66.4 76.4 78.7
2 24
CuH 63.0 65.8 46.5 51.5 62.4 61.6 47.2 52.0 60.3 62.2
AgH 52.62 55.224 38.7 41.9 51.6 51.9 39.2 42.3 49.5 52.2
2 24
AuH 74.3 77.8 53.2 53.6 69.1 70.3 53.7 54.1 66.6 70.6
ZnH 19.62 10.4 13.1 20.6 19.7 10.3 12.6 18.3 19.7
2
CdH 15.6 9.3 11.0 16.7 15.5 9.1 10.7 14.6 15.6
HgH 8.62 2.7 7.5 12.7 7.2 2.2 7.0 10.6 7.2
2
MnD (60.0) 24.9 26.4 36.7 - 24.9 26.3 34.2 -
NiD ≤712 51.7 40.1 58.4 - 51.8 37.5 49.8 -
PtD ≤82 2
65.4 66.6 80.1 79.3 67.6 67.3 77.3 79.7
CuD 63.62 47.2 52.2 63.2 62.4 47.9 52.7 61.0 63.0
2
AgD 53.3 39.2 42.5 52.3 52.6 39.8 42.9 50.2 52.9
AuD 75.22 53.9 54.4 70.0 71.2 54.5 54.9 67.5 71.5
2
ZnD 20.3 11.0 13.7 21.3 20.4 10.8 13.2 18.9 20.4
CdD 16.21 9.8 11.6 17.3 16.1 9.7 11.2 15.2 16.2
2
HgD 9.2 3.1 8.0 13.3 7.7 2.6 7.5 11.2 7.8
 1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
VAVREČKA ET AL. 7

corresponding hydride and both atoms in their ground states. Similarly T A B L E 5 Comparison of vibrational frequencies (in cm
1)
to hydrides, energies of metal atoms in several multiplicities were obtained from the fitted H-H potential for some experimentally
known hydrides.1,2
calculated and compared with experimental values. The second
possibility follows from the fitted potentials (Morse function and Hydride Exp. LAN SDD3 S2FG SDD5
polynomial, and H-H function). In Table 4, there are listed DEs for CrH 1656 1378 1389 1546 -
experimentally known hydrides and compared with performance of WH 185327 1698 1768 1956 1904
all four basis sets. All the computed energies are corrected with MnH 1548 1354 1419 1526 -
ZPVE to be comparable with experimental data. RMSD values in 28
ReH 1985 1710 1892 2175 2125
Table 7 show again comparable accuracy of the S2FG and SDD5
FeH 1764 1383 1454 1569 -
levels of calculations. Nevertheless, S2FG basis set saves large
CoH 1925 1549 1693 1838 -
amount of computational time. Regarding various types of PES
RhH 20407 1210 1803 1961 1966
potentials, it can be concluded that all of them give very similar
12
IrH 2216 2137 2243 2482 2411
results that usually do not differ by more than 1 kcal/mol. How-
NiH 192726 1758 1802 1814 -
ever, DEs obtained based on the H-H function are systematically
slightly smaller than values from the Morse polynomial and, in the PtH 2295 2110 2201 2429 2347

majority cases, also from the original Morse potential. RMSDs of CuH 194111 1656 1809 1952 1936
the individual potentials in a particular basis set are very close, AgH 1760 1484 1595 1705 1718
especially in the S2FG and SDD5 basis sets, where they do not AuH 2305 1942 2036 2311 2263
differ more than 0.2 kcal/mol, cf. Table 7. Therefore, the RMSDs ZnH 1608 1347 1490 1650 1641
to experimental data depend mainly on the used basis set rather CdH 1337 1313 1350 1436 1467
than on the potential curve. Complete set of DEs are for all HgH 1203 1073 1293 1453 1373
hydrides collected in Table S2.
CrD 1182 984 992 1104 -
WD 132827 1204 1254 1387 1351
MnD 1103 967 1012 1090 -
3.4 | Vibrational analysis
ReD 142328 1213 1342 1543 1507
FeD 1259 987 1038 1119 -
Vibrational frequencies and especially anharmonicities represent
CoD 1373 1105 1208 1311 -
relatively sensitive data for basis set testing process. The stretching
mode frequencies represent very perceptive parameter for mole- RhD 14227 860 1281 1394 1398
12
cules. The experimentally known data are compared with frequen- IrD 1610 1516 1591 1761 1710
cies obtained from five chosen models (harmonic analysis from NiD 139026 1254 1286 1294 -
optimization, harmonic potential, Morse potential and polynomial, PdD 1446 1253 1294 1419 1409
and Hulburt-Hirschfelder modification of the Morse potential) PtD 1644 1496 1561 1723 1665
applied on the selected basis sets. Results for the most successful CuD 1384 1180 1290 1391 1380
PES model (H-H potential) are displayed in Table 5. The conclusions AgD 1251 1055 1133 1211 1221
from this part regarding agreement with experimental data are simi-
AuD 1635 1377 1444 1639 1605
lar as for DEs so that it can be repeated that the S2FG and SDD5
ZnD 1072 960 1062 1176 1170
basis sets correspond to the experimental values with very high
HgD 896 761 917 1030 974
accuracy. The RMSD is in both cases below 10% of the average

1
1
value. Clearly, S2FG basis set predicts similar frequencies as the Note: ωe(MnH) = 1478 cm , ωe(MnD) = 1066 cm Reference 28.

SDD5 one. The worst results are for IrH and HgH where both SDD5
and S2FG deviate by slightly less than 200 cm
1 compared to the
measured values, cf. Table 5. The third-row hydrides seem to be a
little bit problematic (with AuH exception) maybe due to the missing
corrections on spin-orbit coupling. The complete collection of
calculated frequencies based on harmonic, Morse potential and
polynomial, and the H-H potential are summarized in Table S3. Fre-
quencies obtained from the H-H potential curve are usually slightly
smaller than those obtained from the Morse polynomial. Also,
results from harmonic fit are almost always visibly higher than from
the H-H potential curve; there are only two exceptions: WH in
S2FG basis set and CuH in SDD5. Concerning deuterated hydrides,
the conclusions are analogous since their values differ from regular
hydrides only by constant (reduced mass). The best results in LAN
and SDD3 basis sets have been obtained by fitting the Morse
potential, whereas the harmonic potential gives the most accurate
estimations for the S2FG and SDD5 basis sets. The RMSD values of
the Morse polynomial and the H-H function are very similar and
comparable to the harmonic potential.
Second part of the vibrational analysis deals with the anharmoni-
city constants obtained from the Morse potential and polynomial, and
H-H function. The results, which can be compared with known experi-
mental data, are collected in Table 6. Here, it can be noticed a little bit
better agreement with measured anharmonicities for SDD3 basis set
 1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
8 VAVREČKA ET AL.

T A B L E 6 Comparison of experimentally1,2 found anharmonic T A B L E 7 RMSD to experimental data for interatomic distances
constants ωexe—with calculated results obtained from the fitted H-H re (in Å), dissociation energiesa D0 (in kcal/mol), vibrational
potentials (in cm
1). frequencies ωe (in cm
1), and for anharmonicity constants ωexe
(in cm
1).
Hydride Exp. LAN SDD3 S2FG SDD5
Parameter Potential LAN SDD3 S2FG SDD5
CrH 30 22 6 15 -
MnH 29 25 27 23 - re (Å) Opt 0.100 0.062 0.033 0.027

FeH 46 32 33 25 - H 0.139 0.098 0.030 0.031

RhH 46 7
13 32 30 29 M 0.117 0.083 0.034 0.031

IrH 39 26 32 27 22 MP 0.119 0.085 0.032 0.028

NiH 38 29 23 29 - HH 0.117 0.084 0.032 0.027

PtH 46 33 37 38 29 D0 (kcal/mol) Opt 14.9 11.2 3.5 3.5

CuH 38 a
31 35 34 33 M 14.4 10.7 3.5 3.6

AgH 34 28 30 25 25 MP 14.6 10.9 3.4 3.4

AuH 43 33 39 42 30 HH 15.0 11.4 3.5 3.5

1
ZnH 55 60 57 48 54 ωe (cm ) H 337 174 98 68

CdH 46 59 57 41 57 M 259 150 106 113

HgH 83 112 68 66 98 MP 289 125 102 100

MnD 14 13 14 12 - HH 295 128 101 86

1
FeD 19 16 17 13 - ωexe (cm ) M 26 6 5 8

CoD 18 13 14 12 - MP 32 7 8 12

RhD 18 7
7 16 15 15 HH 13 8 9 11
a
IrD 21 13 16 14 11 Only for determination of DEs complete set of scanned points was used,
NiD 19 15 12 15 - cf. discussion in the part “Vibrational analysis.”

PdD 20 13 12 10 7
PtD 23 16 19 19 15
manganese and rhenium hydrides: ωe = 1478 (MnH), 1066 (MnD),
CuD 19 16 18 18 17
1985 (ReH), and 1423 (ReD) cm
1 (Table 7).
AgD 17 14 15 12 12
AuD 22 17 20 21 15
ZnD 28 30 29 24 27 4 | CONC LU SIONS
HgD 50 56 34 33 49
In this study, performance of four basis sets is compared for transi-
ωex(CuH) = 37 cm
1 Reference 11.
a

than for the larger S2FG and SDD5 ones. Nevertheless, the RMSD
values of all the basis sets are relatively similar (with exception of
LAN) to make any essential conclusions. The complete collection
of determined anharmonicity constants for all the basis sets and
both hydrides and deuterated hydrides are collected in Table S4.
The H-H potential gives the smallest anharmonicities for almost all
hydrides, nevertheless, there are some exceptions when MP

1
anharmonicities are negligibly smaller (by ca. 1 cm ). In contrast,
the anharmonicities obtained from the fit of the Morse potential
are visibly higher leading to better agreement with experimental
data. This is also confirmed by the RMSD values for the SDD3,
S2FG, and SDD5 computational settings where the anharmonici-
ties obtained by Morse potential exhibits the lowest deviations.
Calculated frequencies are also in reasonable match with the
above-mentioned experimental data from Li et al.26 who found

1
the ωe (WH) frequencies about 1853 and WD 1328 cm and
Wang and Andrews,27,28 evaluating the same WH frequencies:
ωe = 1911 (WH) and 1354 (WD) cm
1 and frequencies for
tion metal hydrides. Besides one of the most frequently used basis
set for TM (LANL2DZ), effectivity of Stuttgart energy-consistent
relativistic (small core) pseudopotentials with triple-zeta quality
base (SDD3) is examined and compared with moderately modified/
extended basis by 2fg polarization functions (S2FG), and with sub-
stantially larger quintuple-zeta cc-pV5Z basis set (SDD5) containing
extended set of SDD3 pseudopotentials by additional two sets of s,
p, and d projection operators. Application of relativistic pseudopo-
tentials is really crucial for employing methods based on the nonrel-
ativistic Schrödinger equation. The highly correlated CCSD(T)
method is applied on determination of examined physico-chemical
properties—interatomic distances, DEs, and vibrational analysis
considering not only stretching vibration mode but also the anhar-
monicity constants. In preliminary part of this study, it was shown
that application of extended well-tempered all-electron basis sets
(WTBS) leads to completely incorrect molecular characterization
even for the first row of the lightest TM arriving to too short intera-
tomic distance and other shortcomings known from literature.
Comparing the quazi-relativistic basis sets, it can be concluded the
best results (in comparison with measured data) are received using

VAVREČKA ET AL.
S2FG and SDD5 basis sets. However, applying the latter basis set is
very time consuming (the CCSD(T) SP calculation for HgH took
approx. 850,000 s on Intel Xeon E7). Using the S2FG basis set
(relatively smaller set of triple-zeta quality with the original pseu-
doorbitals extended by additional 2fg polarization functions), very
similar molecular characteristics are obtained. However, the timing
of these calculations needed only approx. 4400 s, which is compa-
rable with original SDD3 group (approx. 850 s).
ACKNOWLEDGMENTS
The authors are grateful to the Grant Agency of Czech Republic
No. 23-06909S for support of this project. Computational resources
were provided by the e-INFRA CZ project (ID: 90140), supported by
the Ministry of Education, Youth and Sports of the Czech Republic.
Open access publishing facilitated by Univerzita Karlova, as part of
the Wiley - CzechELib agreement.
DATA AVAI LAB ILITY S TATEMENT
The data that support the findings of this study are openly available in
DOI: 10.1002/jcc.XXX and will be included in paper.
ORCID
Jaroslav V. Burda https://orcid.org/0000-0001-9909-8797
RE FE R ENC E S
[1] K. P. Huber, G. Herzberg, Molecular Spectra and Molecular-Structure;
IV. Constants of Diatomic Molecules, Van Nostrand Reinhold Company,
New York, NY 1979.
[2] G. Herzberg, Molecular Spectra and Molecular Structure; I Spectra of
Diatomic Molecules, D. Van Nortrand Comp, Toronto, Canada 1989.
[3] R. R. Squires, J. Am. Chem. Soc. 1985, 107, 4385.
[4] L. Sallans, K. R. Lane, R. R. Squires, B. S. Freiser, J. Am. Chem. Soc.
1985, 107, 107.
[5] M. A. Tolbert, J. L. Beauchamp, J. Phys. Chem. 1986, 90, 5015.
[6] W. J. Balfour, B. Jindgren, S. O'Connor, Phys. Scr. 1983, 28, 551.
[7] W. J. Balfour, J. Cao, C. X. W. Qian, J Mol Spect 2000, 201, 244.
[8] Y. M. Chen, D. E. Clemmer, P. B. Armentrout, J Chem Phys 1993,
98, 4929.
[9] L. S. Sunderlin, P. B. Armentrout, J. Phys. Chem. 1990, 94, 3589.
[10] R. H. Schultz, P. B. Armentrout, J Chern Phys 1991, 94, 2262.
[11] R. S. Ram, P. F. Bernath, J. W. Brault, J Mol Spectr 1985, 113, 269.
[12] A. G. Adam, A. D. Granger, C. Linton, D. W. Tokaryk, Chem. Phys. Lett.
2012, 535, 21.
[13] P. B. Armentrout, L. F. Halle, J. L. Beauchamp, J. Am. Chem. Soc.
1981, 103, 6501.
[14] G. Das, J Chem Phys 1981, 74, 5766.
[15] P. M. Morse, Phys Rev 1929, 34, 57.
[16] J. L. Dunham, Phys Rev 1932, 41, 721.
[17] A. S. Coolidge, H. M. James, E. L. Vernon, Phys Rev 1938, 54, 726.
[18] H. M. Hulburt, J. O. Hirschfelder, J Chem Phys 1941, 9, 61.
[19] J. A. Kunc, F. J. Gordillo-Vazquez, J Phys Chem A 1997, 101, 1595.
[20] A. B. Al-Othman, A. S. Sandouqa, Phys. Scr. 2022, 97, 035401.
[21] A. M. Desai, N. Mesquita, V. Fernandes, Phys. Scr. 2020,
95, 085401.
[22] R. H. Landau, M. J. Paez, C. C. Bordeianu, A Survey of Computational
Physics, Princeton University Press, Princeton, NJ 2008.
[23] J. V. Burda, Chem. Phys. 1998, 230, 13.
[24] J. Y. Seto, Z. Morbi, F. Charron, S. K. Lee, P. F. Bernath, R. J. Le Roy,
J Chem Phys 1999, 110, 11756.
1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
9
[25] R. J. Le Roy, D. R. T. Appadoo, K. Anderson, A. Shayesteh, I. E.
Gordon, P. F. Bernath, J Chem Phys 2005, 123, 204304.
[26] S. Li, R. J. Van Zee, W. J. Weltner, M. G. Cory, M. C. Zerner, J Chem
Phys 1997, 106, 2055.
[27] X. Wang, L. Andrews, J Phys Chem A 2002, 106, 6720.
[28] X. Wang, L. Andrews, J Phys Chem A 2003, 107, 4081.
[29] T. Ziegler, J. G. Snijders, E. J. Baerends, J Chern Phys 1981,
74, 1271.
[30] K. S. Krasnov, V. S. Timoshinin, T. G. A. Danilova, S. V. Khandozhko,
Handbook of Molecular Constants of Inorganic Compounds, Israel
Program for Scientific Translations, Jerusalem 1970.
[31] Y. S. Lee, A. D. McLean, J Chem Phys 1982, 76, 735.
[32] P. Schwerdtfeger, M. Dolg, W. H. E. Schwarz, G. A. Bowmaker,
P. D. W. Boyd, J Chem Phys 1989, 91, 1762.
[33] D. Hait, N. M. Tubman, D. S. Levine, K. B. Whaley, M. Head-Gordon,
J. Chem. Theory Comput. 2019, 15, 5370.
[34] K. A. Moltved, K. P. Kepp, J. Chem. Theory Comput. 2018,
14, 3479.
[35] K. P. Jensen, B. O. Roos, U. Ryde, J Chem Phys 2007, 126,
014103.
[36] S.-T. Zhao, G.-Y. Liang, R. Li, Q.-N. Li, Z.-G. Zhang, B. Yan, Acta Phys.
Sin. 2017, 66, 063103.
[37] S. Huzinaga, B. Miguel, Chem Phys Lett 1990, 175, 289.
[38] S. Huzinaga, M. Klobukowski, Chem Phys Lett 1993, 212, 260.
[39] P.-O. Widmark, P.-Å. Malmqvist, B. O. Roos, Theor. Chim. Acta 1990,
77, 291.
[40] B. P. Pritchard, D. Altarawy, B. Didier, T. D. Gibson, T. L. Windus,
J. Chem. Inf. Model. 2019, 59, 4814.
[41] D. Feller, J. Comput. Chem. 1996, 17, 1571.
[42] K. L. Schuchardt, B. T. Didier, T. Elsethagen, L. Sun, V. Gurumoorthi,
J. Chase, J. Li, T. L. Windus, J. Chem. Inf. Model. 2007, 47, 1045.
[43] P. J. Hay, W. R. Wadt, J Chem Phys 1985, 82, 270.
[44] P. J. Hay, W. R. Wadt, J Chem Phys 1985, 82, 299.
[45] D. Andrae, U. Haussermann, M. Dolg, H. Stoll, H. Preuss, Theor. Chim.
Acta 1990, 77, 123.
[46] A. Bergner, M. Dolg, W. Kuechle, H. Stoll, H. Preuss, Mol. Phys. 1993,
80, 1431.
[47] A. Bergner, M. Dolg, W. Kuchle, H. Stoll, H. Preuss, Mol. Phys. 2006,
80, 1431.
[48] D. Figgen, K. A. Peterson, M. Dolg, H. Stoll, J Chem Phys 2009,
130, 164108.
[49] K. A. Peterson, D. Figgen, M. Dolg, H. Stoll, J Chem Phys 2007,
126, 124101.
[50] D. Figgen, G. Rauhut, M. Dolg, H. Stoll, J Chem Phys 2005,
311, 227.
[51] K. A. Peterson, C. Puzzarini, Theor. Chem. Acc. 2005, 114, 283.
[52] H. J. Werner, P. J. Knowles, Molpro 98, University of Sussex, UK
1998.
[53] L. R. Kahn, P. Baybutt, D. G. Truhlar, J Chem Phys 1976, 65, 3826.
[54] P. J. Hay, W. R. Wadt, L. R. Kahn, J Chem Phys 1978, 68, 3059.
[55] D. Andrae, U. Haussermann, M. Dolg, H. Stoll, H. Preuss, Theor. Chim.
Acta 1991, 78, 247.
[56] J. V. Burda, N. Runeberg, P. Pyykko, Chem. Phys. Lett. 1998,
288, 635.
[57] J. V. Burda, M. Zeizinger, J. Sponer, J. Leszczynski, J Chem Phys 2000,
113, 2224.
[58] M. Zeizinger, J. V. Burda, J. Šponer, V. Kapsa, J. Leszczynski, J Phys
Chem A 2001, 105, 8086.
[59] J. V. Burda, M. Pavelka, M. Simanek, Theochem-J Mol Struct 2004,
683, 183.
[60] J. V. Burda, J. Gu, J. Inorg. Biochem. 2008, 102, 53.
[61] Z. Chval, Z. Futera, J. V. Burda, J Chem Phys 2011, 134, 024520.
[62] F. Šebesta, V. Sláma, J. Melcr, Z. Futera, J. V. Burda, J. Chem. Theory
Comput. 2016, 12, 3681.
 1096987x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/jcc.27361, Wiley Online Library on [15/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
10 VAVREČKA ET AL.

[63] F. Šebesta, M. Z. Brela, S. Diaz, S. Miranda, J. S. Murray, S. Gutiierrez- SUPPORTING INF ORMATION
Oliva, A. Toro-Labbe, A. Michalak, J. V. Burda, J. Comput. Chem. 2017, Additional supporting information can be found online in the Support-
38, 2680.
ing Information section at the end of this article.
[64] J. Dunning, J Chem Phys 1970, 53, 2823.
[65] R. Krishnan, J. S. Binkley, J. A. Pople, J Chem Phys 1980, 72, 650.
[66] M. J. Frisch, J. A. Pople, J. S. Binkley, J Chem Phys 1984, 80, 3265.
[67] T. H. Dunning Jr., J Chem Phys 1989, 90, 1007. How to cite this article: A. Vavrečka, K. Fatková, J. V. Burda, J.
[68] P. Pyykko, Effects Relativity on Atoms, Molecules, and Solid State, Comput. Chem. 2024, 1. https://doi.org/10.1002/jcc.27361
Abingdon, Oxfordshire, UK 1990.
[69] P. Pyykko, Chem. Rev. 1988, 88, 563.