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Quantum Chemical Exploration of Intermolecular Reactions
of Acetylene
Koichi Ohno ,*[a,b] Takuto Oki,[c] and Hideo Yamakado[c]
Quantum chemical explorations of potential energy surfaces
showed that acetylene produces various products starting from
molecular arrays in short distances of 1.3–2.5 Å. Arrays of
(C2H2)2 gave cyclobutadiene, tetrahedrane, and acetylene
dimers. Arrays of (C2H2)3 gave benzene, prismane, benzvalene,
Dewar benzene, and acetylene trimers. Arrays of (C2H2)4 gave
cubane, cyclooctatetranene, and acetylene tetramers. Different
Introduction
Many chemical reactions are kinetically too slow unless activa-
tion energies are supplied to go beyond the energy barriers
(transition states) toward reaction products. These situations are
due to usual experimental conditions, in which the reactants
are located in their ground states without sufficient thermal
energies. In order to overcome the obstacles against the reac-
tions, heats and catalysts have been conventionally used in syn-
thetic chemistry, and photochemical reactions also have been
employed in some cases. Besides these traditional methods for
chemical reactions, there may be some other types of tech-
niques for promoting new sorts of chemical reactions.
In recent decades, effects of mechanical forces to induce
chemical reactions have been studied.[1] More specifically, theo-
retical energy minimizations on potential energy surfaces (PES)
revealed that new types of chemical reactions are expected to
occur, when the reactants are forced to be placed at high energy
points of the PES.[2–5] By computational searches at the level of
MP2/6-311G(d,p), two parallel benzenes closely placed were
found to give some energy minima in the interaction energy
curve at short interplane distances of ca. 0.16 nm, which corre-
spond to five types of cyclodimers of benzenes of (CH)12.[2] More
thorough computational surveys showed 12 benzene dimers by
geometry optimization starting from close contacts of 2 benzene
molecules.[3] Recently, polycyclic aromatic hydrocarbons, such as
naphthalene, perylene, and coronene, can also give dimers with
many CC covalent bonds between the monomers, when geome-
try optimization was started from the short interplane distances
of ca. 0.14–0.15 nm.[4,5] The short distances for the initial struc-
tures for geometry optimizations were estimated to be attained
by external forces under ultrahigh pressures.[3–5]
Interring covalent interactions between aromatic molecules
can be ascribed to their unsaturated chemical bonds, which
may undergo addition reactions. Based on this supposition, fur-
ther possibilities of mechanochemical reactions between unsat-
urated molecules can be suggested. As an acetylene molecule
has a triple CC bond, one may expect that mechanochemical
Wiley Online Library
forms of initial arrays yielded different sets of products; a paral-
lel array of two monomers gave cyclobutadiene, whereas a
cross array gave tetrahedrane. Initial molecular arrays with
unusually close contacts were estimated to require local forces
of 1–9 × 10−8 N. © 2019 Wiley Periodicals, Inc.
DOI: 10.1002/jcc.26120
polymerization can also happen for acetylene molecules. In this
study, intermolecular reactions between acetylene molecules
were studied by quantum chemical calculations, in order to elu-
cidate how initial conditions of geometries and energies lead to
various chemical products of (C2H2)2, (C2H2)3, and (C2H2)4.
Computational Methods
All electronic-state calculations were performed for the ground
singlet states, by using the Gaussian 09 (G09) program.[6] Density
functional theory (DFT)[7,8] was used with the ultrafine grid and
the D3 dispersion corrections.[9,10] Optimization and exploration
were done by the GRRM program (GRRM14).[11] Some examples
of the input data for Global Reaction Route Mapping (GRRM) cal-
culations were contained in the Supporting Information Appendix
S1 together with some results of calculations. Details of various
calculation types were described separately as follows.
Geometry optimization
The initial structure of each acetylene molecule was set to have
the bond lengths of 0.121 nm for CC and 0.107 nm for CH and
the bond angles of 180 . Initial arrangements of acetylene mol-
ecules were presumed for dimer (C2H2)2 to be parallel (D2h) in
Figure 1 and cross (D2d) in Figure 2, for trimer (C2H2)3 to be tri-
angle (D3h) in Figure 3, prism (D3h) in Figure 4, and ladder (D2h)
[a] K. Ohno
Institute for Quantum Chemical Exploration, Konan 1-9-36, Minato-ku,
Tokyo 108-0075, Japan
E-mail: ohnok@tohoku.ac.jp
[b] K. Ohno
Tohoku University, Graduate School of Science, Aramaki Aza-Aoba 6-3,
Aoba-ku, Sendai, Miyagi, 980-8578, Japan
[c] T. Oki, H. Yamakado
Faculty of Systems Engineering, Wakayama University, Sakaedani
930, Wakayama, Wakayama 640-8510, Japan
Contract Grant sponsor: Japan Society for the Promotion of Science;
Contract Grant sponsor: JSPS KAKENHI; Contract Grant number:
JP17KT0100
© 2019 Wiley Periodicals, Inc.
Journal of Computational Chemistry 2019 1
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Figure 1. Potential energy curve (B3LYP-D3/cc-pVDZ) for parallel array dimer

Figure 4. Potential energy curve (B3LYP-D3/cc-pVDZ) for prism array trimer
(D2h). The distance R is defined at the top right. Optimized structures after
(D3h). The distance R is defined at the top right. Optimized structures after
minimization are indicated by dashed red arrows. [Color figure can be
minimization are indicated by dashed red arrows. [Color figure can be
viewed at wileyonlinelibrary.com]
viewed at wileyonlinelibrary.com]

chemical bonds and intermolecular interactions effectively.[12]

Refinement reoptimization calculations were performed for every
polymerized structure of (C2H2)n (n = 2–4) at the level of B3LYP-
D3/aug-cc-pVTZ, because this level gave nearly comparable
results[12] with the benchmark calculations of formaldehyde
dimers by CCSD(T) at the complete basis-set limit.[13]

Exploration by scaled hypersphere search method combined

with the ADDF technique
Figure 2. Potential energy curve (B3LYP-D3/cc-pVDZ) for cross array dimer Explorations of structures and reaction pathways were made by
(D2d). The distance R is defined at the top right. Optimized structures after the scaled-hypersphere-search (SHS) method combined with
minimization are indicated by dashed red arrows. [Color figure can be
viewed at wileyonlinelibrary.com]
the anharmonic downward distortion following (ADDF) tech-
nique (SHS-ADDF).[14,15] SHS-ADDF makes it possible to trace on
PES to obtain all of the reaction pathways connecting equilib-
in Figure 5, and for tetramer (C2H2)4 to be box (D4h) in Figure 6.
rium points (EQs) and transition structures (TSs). It uses scaled
Initial distances between monomers were taken to be shorter
hyperspheres on which energy minima indicate directions of
than the typical van der Waals CC distance of 0.34 nm as listed
reaction pathways, and this allows to make uphill tracing by
in Tables 1–3.
following a reaction pathway directed from a bottom EQ
The level of the electronic-state calculations was chosen to
toward a saddle point TS. Once a TS is found, intrinsic reaction
be B3LYP-D3/cc-pVDZ, since in a previous study of formalde-
hyde clusters (H2CO)n (n = 1–4) D3-corrected DFT calculations
were found to be appropriate for describing both intramolecular

Figure 3. Potential energy curve (B3LYP-D3/cc-pVDZ) for triangle array Figure 5. Potential energy curve (B3LYP-D3/cc-pVDZ) for ladder array trimer
trimer (D3h). The distance R is defined at the top right. Optimized structures (D2h). The distance R is defined at the top right. Optimized structures after
after minimization are indicated by dashed red arrows. [Color figure can be minimization are indicated by dashed red arrows. [Color figure can be
viewed at wileyonlinelibrary.com] viewed at wileyonlinelibrary.com]

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Results and Discussions

Energy minimization from parallel array of (C2H2)2
Potential energy curve at the level of B3LYP-D3/cc-pVDZ for
parallel arrays (D2h) of two acetylene molecules is shown in
Figure 1. Relative energy with respect to the dissociated struc-
ture at infinite separation is shown in the unit of kJ/mol. The
intermolecular distance R defined at the top right in Figure 1
was varied from 1.5 to 3.0 Å with keeping the monomer struc-
ture fixed at the initial geometry. The energy value of the curve
is only 24.1 kJ/mol at R = 3.0 Å, but it rapidly increases and
becomes larger than typical bond energies of CC (377 kJ/mol)
Figure 6. Potential energy curve (B3LYP-D3/cc-pVDZ) for box array tetramer
and CH (411 kJ/mol) at around 2 Å.
(D4h). The distance R is defined at the top right. Optimized structures after
minimization are indicated by dashed red arrows. [Color figure can be Energy minimization calculations with no constraint for all
viewed at wileyonlinelibrary.com] atoms were performed for six initial geometries of R = 1.5, 1.8,
1.9, 2.0, 2.5, and 3.0 Å at the level of B3LYP-D3/cc-pVDZ. All
coordinates (IRCs) are confirmed by downhill tracing from the cases were optimized to minima with no imaginary frequencies.
TS to two directions using a conventional technique, such as Results of optimized data together with the initial ones are
the steepest decent method, and EQ or dissociation channel listed in Table 1. Optimized structures are divided into two
(DC) is deduced. When a new EQ is found, the same procedure types, cyclobutadiene 1 (D2h) and van der Waals cluster of a
of SHS-ADDF is carried out. A reaction channel network com- slipped parallel-form 2 (C2h). The shorter initial distances of
posed of EQ-TS-EQ and EQ-TS-DC pathways is obtained for a R = 1.5 and 1.8 Å gave 1, whereas the longer initial distances of
given atomic composition by repeating this procedure.[14,15] R ≥ 1.9 Å yielded 2. The boundary is located at ca. 1.9 Å near
SHS-ADDF is implemented as one of the representative func- the knee joint point of the potential energy curve, where the
tions of GRRM14.[11] We used SHS-ADDF in three different ways upper and the lower curves are considered to cross each other,
in this study: (1) local exploration of reaction channels and their as indicated by dashed blue arrows in Figure 1. Cyclobutadiene
barrier heights around a certain EQ, (2) limited exploration ini- 1 is a typical unsaturated cyclic hydrocarbon with two double
tially around randomly generated molecular arrays and further bonds on the four-membered ring. Correlations of molecular
around newly found molecular clusters with no bond orbitals of 1 with orbitals of acetylene were discussed in the
rearrangements, (3) full exploration for a given atomic composi- Supporting Information Appendix S1. The acetylene cluster
tion specified with a molecular formula. 2 will be discussed below in connection with other forms of
acetylene clusters.
Vibrational frequency and free energy calculation
Energy minimization from cross array of (C2H2)2
Calculations of vibrational frequencies and free energies were
made by GRRM14. Harmonic frequencies were used for evalua- Potential energy curve at the level of B3LYP-D3/cc-pVDZ for
tion of zero-point vibrational energy (ZPVE) corrections and free cross arrays (D2d) of three acetylene molecules is shown in
energies. Figure 2. Relative energy with respect to the dissociated struc-
ture at infinite separation is shown as in the case of Figure 1.
The intermolecular distance R defined at the top right in
Table 1. Optimization of acetylene dimers starting from Parallel or Cross
geometries.[a] Figure 2 was varied from 1.5 to 3.0 Å with keeping the mono-
mer structure fixed at the initial geometry. Energy minimization
Initial Initial Optimized
geometry[b] energy[c] energy Optimized structure
calculations were done for initial geometries of R = 1.5, 2.0, 2.5,
and 3.0 Å at the level of B3LYP-D3/cc-pVDZ. All cases were opti-
Parallel (D2h)
1.500 712.166 −59.386 D2h cyclobutadiene 1
mized to minima with no imaginary frequencies. Results of opti-
1.800 650.407 −59.386 D2h cyclobutadiene 1 mized data together with the initial ones are added in the
1.900 647.142 −10.242 C2h slipped parallel-form cluster 2 lower part of Table 1. Four different types of optimized struc-
2.000 490.788 −10.242 C2h slipped parallel-form cluster 2 tures were obtained from cross arrays; the shortest initial dis-
2.500 117.401 −10.242 C2h slipped parallel-form cluster 2
3.000 24.106 −10.242 C2h slipped parallel-form cluster 2 tance of R = 1.5 Å gave a highly symmetrical compound of
Cross (D2d) tetrahedrane 3 (Td) and the longer initial distances gave three
1.500 609.266 44.851 Td tetrahedrane 3 types of van der Waals clusters, slipped parallel-form 2 (C2h) for
2.000 310.085 −10.242 C2h slipped parallel-form cluster 2
R = 2.0 Å, X-form 4 (D2d) for R = 2.5 Å, and T-form 5 (C2v)
2.500 78.133 −2.922 D2d X-form cluster 4
3.000 13.260 −11.000 C2v T-form cluster 5 for R = 3.0 Å.
Tetrahedrane 3, an isomer of C4H4, was obtained by minimi-
[a] Geometry optimization calculations were made at the level of B3LYP-D3/cc-pVDZ.
[b] Initial distance (R), defined in Figure 1 (parallel) or in Figure 2 (cross), is shown in Å. zation from the initial structure at R = 1.5 Å with a large energy
[c] Initial and optimized energies are listed in kJ/mol with respect to the dissociated of ca. 600 kJ/mol, which is much larger than the bond energies
structure at infinite separation.
of CC (377 kJ/mol) and CH (411 kJ/mol). Van der Waals clusters

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Table 2. Optimization of acetylene trimers starting from triangle, prism, or ladder geometries.[a]

Initial geometry[b] Initial energy[c] Optimized energy Optimized structure

Triangle (D3h)
2.000 964.885 −704.610 D6h benzene 6
2.100 728.094 −704.610 D6h benzene 6
2.200 544.041 −31.022 C3h cyclic trimer cluster 7
2.500 216.748 −31.022 C3h cyclic trimer cluster 7
3.000 38.426 −31.022 C3h cyclic trimer cluster 7
Prism (D3h)
1.400 2190.366 −196.654 D3h prismane 8
1.500 1902.002 −196.653 D3h prismane 8
1.600 1812.518 −196.653 D3h prismane 8
1.700 1838.248 −352.675 C2v Dewar benzene 9
1.800 1734.399 −364.799 C2v benzvalene 10
1.900 1498.792 −352.677 C2v Dewar benzene 9
2.000 1339.826 −31.022 C3h cyclic trimer cluster 7
2.500 333.110 −31.022 C3h cyclic trimer cluster 7
Ladder (D2h)
1.300 2300.546 −704.610 D6h benzene 6
1.400 2082.467 −704.610 D6h benzene 6
1.420 2006.509 −704.610 D6h benzene 6
1.440 1939.723 −704.610 D6h benzene 6
1.445 1924.368 −704.610 D6h benzene 6
1.450 1909.527 −352.678 C2v Dewar benzene 9
1.455 1895.187 −704.612 D6h benzene 6
1.460 1881.339 −704.612 D6h benzene 6
1.470 1855.072 −704.614 D6h benzene 6
1.480 1830.643 −704.610 D6h benzene 6
1.490 1807.971 −704.610 D6h benzene 6
1.500 1876.126 −72.332 Cs cluster (cyclobutadinene+acetylene)
1.510 1821.739 −29.791 C1 cyclopropadienyl─CH─CH─CH
1.600 1414.793 −29.792 C1 cyclopropadienyl─CH─CH─CH
1.700 1111.197 −72.333 Cs cluster (cyclobutadinene + acetylene)
1.800 923.569 −72.333 Cs cluster (cyclobutadinene + acetylene)
2.000 766.163 −72.333 Cs cluster (cyclobutadinene + acetylene)
2.500 243.011 −31.022 C3h cyclic trimer cluster 7
[a] Geometry optimization calculations were made at the level of B3LYP-D3/cc-pVDZ.
[b] Initial distance (R), defined in Figure 3 (triangle), in Figure 4 (prism) or in Figure 5 (ladder), is shown in Å.
[c] Initial and optimized energies are listed in kJ/mol with respect to the dissociated structure at infinite separation. Energies were obtained at the level of B3LYP-D3/cc-pVDZ.

of 2, 4, and 5 were obtained by minimization from the lower
energy points at ca. 310, 78, and 13 kJ/mol, which are much
smaller than the CC and CH bond energies.
Concerning 2–5, acetylene dimers (2, 4, 5) are weakly bonded
clusters, which will be discussed below based on reoptimization
calculations. Tetrahedrane 3 is a highly symmetric hydrocarbon
with a carbon skeleton of tetrahedron. Although 3 has not yet
been synthesized, a derivative with four t-butyl groups was syn-
thesized.[16] Figure 2 suggests that 3 may be synthesized by plac-
ing two acetylene molecules closely contacting with each other
in a crossed geometry at a short distance of ca. 1.5 Å.
In order to compare energies of optimized structures 1–5,
reoptimization calculations at the higher level of B3LYP-D3/aug-
cc-pVTZ were performed, and the results were listed in Table 4.

Table 3. Optimization of acetylene tetramers starting from box geometry.[a]

Initial geometry[b] Initial energy[c] Optimized energy Optimized structure

Box (D4h)
1.400 3406.903 −408.869 Oh cubane 11
1.500 2852.350 −512.650 C2v tricycle[4,2,0,02,5]oct-3,7-diene 12
1.600 2638.382 −408.869 Oh cubane 11
1.700 2202.140 −736.657 D2d cyclooctatetraene 13
1.800 1940.636 −736.657 D2d cyclooctatetraene 13
1.900 1799.552 −736.657 D2d cyclooctatetraene 13
2.000 1774.308 −67.956 C1 cluster (cyclopropadienyl─CH─CH─CH + acetylene)
2.500 −45.975 −46.049 S4 cyclic tetramer cluster 14
[a] Geometry optimization calculations were made at the level of B3LYP-D3/cc-pVDZ.
[b] Initial distance (R), defined in Figure 6 is shown in Å.
[c] Initial and optimized energies are listed in kJ/mol with respect to the dissociated structure at infinite separation.

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Table 4. Obtained polymerized structures of (C2H2)n n = 2–4.[a]

Energy[b] Relative energy[c]

(C2H2)2
Tetrahedrane (Td) 3 −154.6997 78.805
X-form dimer (D2d) 4 −154.7299 −0.374 Van der Waals cluster at second-order saddle point
Slipped parallel dimer (C2h) 2 −154.7321 −6.176 Saddle point between T-form van der Waals clusters
T-form dimer (C2v) 5 −154.7325 −7.207 Van der Waals cluster
Cyclobutadiene (D2h) 1 −154.7393 −24.922
(C2H2)3
Cyclic trimer (C3h) 7 −232.1300 −21.925 Van der Waals cluster
Prismane (D3h) 8 −232.1409 −121.595
Dewar benzene (C2v) 9 −232.2045 −288.574
Benzvalene (C2v) 10 −232.2091 −300.469
Fulvene (C2v) −232.2848 −499.318
Benzene (D6h) 6 −232.3407 −645.916
(C2H2)4
Cyclic tetramer (S4) 14 −309.47211 −33.0658 Van der Waals cluster
Cyclic tetramer (C4h) −309.47207 −33.0654 Saddle point between mirror image forms of S4
Cubane (Oh) 11 −309.5702 −290.673
Tricycle[4,2,0,02,5]oct-3,7-diene (C2v) 12 −309.6183 −416.760
Cyclooctatetraene (D2d) 13 −309.7116 −661.751
[a] Reoptimized energies at the level of B3LYP-D3/aug-cc-pVTZ.
[b] Absolute energies in atomic unit (Hartree).
[c] Relative energies in kJ/mol with respect to the dissociated structure at infinite separation.

It is found that the slipped parallel-form (C2h) 2 is slightly higher
in energy by 1.03 kJ/mol than T-form (C2v) 5, and it is confirmed
that the slipped parallel-form 2 is a saddle point between two
equivalent T-forms 5 in which two monomers interchanged
their positions by intraplane internal rotation via the C2h struc-
ture. This finding for the relationship between 2 and 5 is consis-
tent with the earlier studies of (C2H2)2 by MP2 calculations[17,18]
and recent more precise calculations by CCSD(T).[19–21] The
most stable acetylene dimer is the T-form 5, whose stability
may be related to CH─π (C─H single and C─C triple bond)
interactions between two acetylene molecules.[22] Experimental
determination of acetylene dimer was made by free-jet infrared
absorption spectroscopy, and the analysis showed that (C2H2)2
is the T form.[23] We found another cluster of X-form (D2d) 4,
which is located much higher in energy by 6.83 kJ/mol than
the most stable T form, though the X form was confirmed to be
a second-order saddle point by refinement calculation at the
level of B3LYP-D3/aug-cc-pVTZ in consistent with the earlier
computational studies.[18,20,21]
Among 1–5 cyclobutadiene 1 is most stable, which is
24.92 kJ/mol lower than the dissociated acetylene molecules.
Van der Waals clusters 2, 4, 5 are located in negative energy
regions with respect to the dissociation limit, 2 (−6.176 kJ/mol),
4 (−0.374 kJ/mol), and 5 (−7.207 kJ/mol). Tetrahedrane 3 on
the other hand exists in the positive energy region at
78.805 kJ/mol. Although 3 is a highly strained molecule, the
lowest energy barrier around its equilibrium structure was esti-
mated to be 127.2 kJ/mol, which is large enough for existing as
a kinetically stable compound.
Energy minimization from triangle array of (C2H2)3
Potential energy curve at the level of B3LYP-D3/cc-pVDZ for tri-
angle arrays (D3h) of three acetylene molecules is shown in
Figure 3. Relative energy with respect to the dissociated
structure at infinite separation is shown as in the cases of
Figures 1 and 2. The intermolecular distance R is defined as the
nearest CC distance between the monomers as displayed at the
top right in Figure 3. R was varied from 2.0 to 3.0 Å with keep-
ing the monomer structure fixed at the initial geometry. Energy
minimization calculations were done for initial geometries of
R = 2.0, 2.1, 2.2, 2.5, and 3.0 Å at the level of B3LYP-D3/cc-pVDZ.
All cases were optimized to minima with no imaginary frequen-
cies. Results of optimized data together with the initial ones are
listed in Table 2. Two types of optimized structures were
obtained from triangle arrays; the short initial distances of
R = 2.0, 2.1 Å in the energy range higher than 600 kJ/mol gave
benzene 6 (D6h) and the longer initial distances in the energy
range lower than 600 kJ/mol gave a cyclic C3h van der Waals
cluster 7.
As shown in Figure 3, triangle arrays of three acetylene mole-
cules may lead to straightforward production of benzene with-
out catalyst. In the cyclic C3h cluster, H atom in one monomer is
attached to C atoms in another monomer, which is due to the
fact that T form involving CH─π interactions is most stable for
dimer.
Energy minimization from prism array of (C2H2)3
Potential energy curve at the level of B3LYP-D3/cc-pVDZ for
prism arrays (D3h) of three acetylene molecules is shown in
Figure 4. Relative energy with respect to the dissociated struc-
ture at infinite separation is shown as in Figures 1–3. R is
defined as the intermolecular distance between the monomers
as displayed at the top right in Figure 4. R was varied from 1.4
to 2.5 Å with keeping the monomer structure fixed at the initial
geometry. Energy minimization calculations were done for ini-
tial geometries of R = 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, and 2.5 Å at
the level of B3LYP-D3/cc-pVDZ. All cases were optimized to
minima with no imaginary frequencies. Results of optimized

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data together with the initial ones are added in the middle part
of Table 2. Four types of optimized structures were obtained
from prism arrays; the short initial distances of R = 1.4, 1.5, and
1.6 Å gave prismane 8 (D3h), R = 1.7 and 1.9 Å gave Dewar ben-
zene 9 (C2v), R = 1.8 Å gave benzvalene 10 (C2v), and R = 2.0,
2.5 Å gave a cyclic trimer 7 (C3h).
Three types of isomers of benzene, 8, 9, and 10, were gener-
ated starting from very high energy regions over 1500 kJ/mol.
Selections between 9 and 10 were found to be marginal
reflecting subtle features of PES. The lower energy initial struc-
tures with intermolecular CC distances longer than 2 Å led to a
cyclic C3h cluster 7 involving CH─π intermolecular interactions.
The isomers (8, 9, 10) of benzene are well-known organic
compounds. Prismane 8 was synthesized in 1973.[24] Dewar
benzene 9 is well known as bicycle[2.2.0]hexa-2,5-diene.[25] Ben-
zvalene 10 was synthesized in 1971.[26] Acetylene trimer 7 will
be discussed later in connection with other forms.
Energy minimization from ladder array of (C2H2)3
Potential energy curve at the level of B3LYP-D3/cc-pVDZ for
ladder arrays (D2h) of three acetylene molecules is shown in
Figure 5. Relative energy with respect to the dissociated struc-
ture at infinite separation is shown as in Figures 1–4. The inter-
molecular distance R is defined as displayed at the top right in
Figure 5. The distance R was varied from 1.3 to 2.5 Å with keep-
ing the monomer structure fixed at the initial geometry. Energy
minimization calculations were done for various initial geome-
tries of R = 1.3–2.5 Å at the level of B3LYP-D3/cc-pVDZ. All cases
were optimized to minima with no imaginary frequencies.
Results of optimized data together with the initial ones are
added in the last part of Table 2.
Five types of optimized structures were obtained from ladder
arrays. Very short initial distances of R = 1.30–1.49 Å mostly
gave benzene 6 (D3h), but exceptionally at R = 1.45 Å Dewar
benzene 9 (C2v) was yielded. This singular behavior may be
ascribed to complex features of PES at very high-energy regions
over 1800 kJ/mol. The initial distances between 1.5 and 2.0 Å
also showed complicated features of PES to yield a carbene
(cyclopropadienyl─CH─CH─CH) and a van der Waals cluster
composed of cyclobutadiene and acetylene. At the longer dis-
tance of 2.5 Å a cyclic C3h cluster 7 was obtained.
In order to compare energies of optimized structures 6–10,
reoptimization calculations at the higher level of B3LYP-D3/aug-
cc-pVTZ were performed, and the results were listed in Table 4.
Among 6–10, the most stable one is benzene 6 (−645.916 kJ/
mol), which is much more stable than the second stable-most
isomer of C6H6 (fulvene, −499.318 kJ/mol). Benzvalene 10
(−300.469 kJ/mol) and Dewar benzene 9 (−288.574 kJ/mol) are
also located at much higher energy regions than benzene.
Prismane 8 (−121.595 kJ/mol) is also located in negative energy
regions with respect to three isolated acetylene molecules,
although prismane is known as a highly strained molecule.
These isomers of benzene, 8–10, are located in an energy range
of 345–524 kJ/mol above from the most stable isomer of ben-
zene. In the previous study of global search of benzene iso-
mers, the total energy range of the isomers was found to be up
6 Journal of Computational Chemistry 2019
to ca. 1200 kJ/mol from the lowest isomer of benzene.[27,28]
Thus, prismane 8, the highest energy compound among 6–10,
has a moderate energy among all of the benzene isomers.
Cyclic trimer (C3h) 7 is located at slightly negative energy of
−21.925 kJ/mol as listed in Table 4, which is approximately
three times of the T-form dimer 5 (−7.207 kJ/mol) reflecting
three CH─π interactions in 7 in comparison with the only one
CH─π interaction in 5. Experimental observation of acetylene
trimer 7 was made by Infrared spectroscopy.[29] Many theoreti-
cal computations[17,30–34] made theoretical supports of the
C3h form.
Energy minimization from box array of (C2H2)4
Potential energy curve at the level of B3LYP-D3/cc-pVDZ for
box arrays (D4h) of four acetylene molecules is shown in
Figure 6. Relative energy with respect to the dissociated struc-
ture at infinite separation is shown as in Figures 1–5. The inter-
molecular distance R is defined as displayed at the top right in
Figure 6. The distance R was varied from 1.4 to 2.5 Å with keep-
ing the monomer structure fixed at the initial geometry. Energy
minimization calculations were done for various initial geome-
tries of R = 1.4–2.5 Å at the level of B3LYP-D3/cc-pVDZ. All cases
were optimized to minima with no imaginary frequencies.
Results of optimized data together with the initial ones are
listed in Table 3.
Five types of optimized structures were obtained from box
arrays. At R = 1.4 and 1.6 Å, a highly symmetric compounds of
cubane 11 (Oh) was obtained, whereas at the intermediate dis-
tance of R = 1.5 Å an isomer of C8H8, tricycle[4,2,0,02,5]oct-
3,7-diene 12 (C2v), was obtained. Such a marginal behavior may
be ascribed to complicated features of PES at very high energy
regions over 2600 kJ/mol. At the intermediate distances around
R = 1.7–1.9 Å cyclooctatetraene 13 (D2d) was obtained. The lon-
ger distance of R = 2.0 Å led to a cluster composed of cyclo-
propadienyl─CH─CH─CH and acetylene, much longer distance
of R = 2.5 Å yielded a cyclic tetramer cluster 14 (S4).
Among the reached structures, 11 should be noted as a
highly strained hydrocarbon molecule with a cubic carbon
cage. Cubane 11 was synthesized in 1964[35] earlier than the
synthesis of prismane 8. This is probably related to the big dif-
ference of thermodynamic stability due to their energies that
11 is much lower than 8 as can be seen in Tables 2, 3 (also
refined data of Table 4). Another one to be noted is 12,
because it is composed of a series of four-membered rings,
which is a dimerized form of cyclobutadiene 1 and also an
extension of Dewar benzene 9 with one more four-
membered ring.
In order to compare energies of optimized structures 11–14
more precisely, reoptimization calculations at the higher level
of B3LYP-D3/aug-cc-pVTZ were performed, and the results were
listed in Table 4. Although cubane 11 is known as a highly
strained molecule, it is located at sufficiently negative energy
region of −290.673 kJ/mol, which is comparable with Dewar
benzene 9 (−288.574 kJ/mol). When two CC bonds in parallel
positions of cubane 11 are opened, the more stable compound
of 12 (−416.760 kJ/mol) is produced. Cyclooctatetraene 12
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(−661.751 kJ/mol) is most stable among 11–14. Cyclic tetramer
14 (S4) (−33.0658 kJ/mol) is a van der Waals cluster, which has
a nonplanar geometry. Planar cyclic tetramer (C4h) was found to
be a saddle point between mirror image forms of 14 (S4). This
saddle point is only 0.0004 kJ/mol higher than 14, and this bar-
rier has no effective meaning because it can be surmounted by
the zero point vibrations of 14. In 14 four acetylene unit con-
tact with adjacent monomers by CH─π interactions like T-form
dimer. The energy of 14 is slightly more negative than the four
times value of T form (−7.207 × 4 = −28.828 kJ/mol), which
may be ascribed to three and four body van der Waals interac-
tions due to very close contact of four monomers.
A rotational analysis for the infrared spectra of the acetylene
tetramer indicated that a puckered ring structure of S4 symme-
try is consistent with the observation.[36] Theoretical calcula-
tions by MP2/3-21G and MP3/6-311G(d.p) showed that a C4h
planar ring structure gives nearly the same energy as the S4
form.[32] A computational study suggesting the C4h ring being
lower than the S4 form was also reported.[37] The present calcula-
tions of acetylene tetramers at the level of B3LYP-D3/aug-cc-pVTZ
showed a little preference of S4 over C4h, but further discussion
will be made below based on free energy calculations.
Energy minimization profile
Energy minimization profiles for various cases listed in Tables 1–3
were essentially energy minimization processes of geometry opti-
mization. Some typical examples were shown in Supporting Infor-
mation Figures S1–S3. Figure S1 shows the energy minimization
profile starting from triangle array at R = 2.1 Å to benzene 6;
numerical data of this process were contained also in
Supporting Information. As can be seen from Supporting Infor-
mation Figure S1, the energies rapidly go down to negative
energy regions with forming new CC bonds between the acet-
ylene monomers. After the hexagonal ring formation, the
molecular shape with distorted directions of CH bonds gradu-
ally converges to the D6h structure of benzene. Supporting
Information Figure S2 shows the energy minimization profile
starting from ladder array at R = 1.49 Å to benzene 6. The
energies decrease with the structural change from a ladder
form like Dewar benzene to hexagonal ring structures finally
reaching D6h benzene. Supporting Information Figure S3
shows the energy minimization profile starting from box array
at R = 1.7 Å to cyclooctatetraene 13. Initially two CC bonds
connecting adjacent acetylene units are broken with rapid
decrease down to ca. 500 kJ/mol where an eight-membered
ring is discernible. Upon going from the positive to the nega-
tive energy regions, directions of CH bonds on the eight-
membered ring are tilted toward less strained directions to
yield finally the D4d form of cyclooctatetraene 13.
Supporting Information Figure S1 the reaction process starts
from very high energy (728 kJ/mol) without catalyst. In order to
elucidate such an interesting reaction process related to ben-
zene and acetylene, a careful inspection of PES for C6H6 should
be made.
Concerning PES of C6H6, a global search by SHS-ADDF was
undertaken in the previous studies[27,28]; the self-consistent
charge density functional tight-binding method[39] was used for
the initial search, and reoptimization calculations were made at
the level of B3LYP/6-311G(d,p) to give satisfactory results as far
as firmly bonded valence isomers are concerned.[28] However, a
subsequent study of H3CNO3[40] and careful searches of formal-
dehyde clusters,[12] showed that (1) the initial search is rec-
ommended to be made by a more suitable level such as
B3LYP/6-31G(d) for reasonable accuracy and efficiency,[40] and
that (2) dispersion corrections such as the D3 method are
essential to describe molecular clusters or weakly bounded sys-
tems.[12] In the previous search of C6H6,[27,28] acetylene trimers
were found to be dissociating due to the lack of dispersion
corrections.
In this study, we made saddle optimization from the initial
triangle trimer structure of R = 2.1 Å at the level of B3LYP-D3/
cc-pVDZ including dispersion corrections, as the triangle struc-
ture in Figure 3 seemed to form new CC bonds among three
monomers. A saddle point (TS) of a planar D3h structure with
one imaginary frequency was found, and IRC pathways from
this TS were traced to confirm benzene 6 and the C3h trimer
7 at the two ends of the IRC pathways. The results of the IRC
traces from the TS (D3h) was shown in Figure 7, in which ener-
gies of TS (869.490 kJ/mol) and the cyclic C3h trimer
(673.588 kJ/mol) were shown with respect to benzene (0 kJ/
mol). In Figure 7, the barrier height from benzene to TS is as
large as ca. 869 kJ/mol, whereas the reverse barrier height from
the cyclic C3h trimer to TS is much smaller to be ca. 196 kJ/mol.
Here, one should note that the energy of the cyclic C3h trimer
is −31.022 kJ/mol with respect to the complete dissociation
into three acetylene monomers. This indicates that the TS in
Figure 7 is at ca. 165 kJ/mol above the dissociation limit of

Energy profile going through TS to produce benzene from

(C2H2)3

Production of benzene from three acetylene molecules with

using catalyst is well known as Reppe reaction,[38] but the
energy minimization path yielding benzene in Supporting Infor- Figure 7. Energy profile from the cyclic trimer (C3h) to benzene (D6h) via TS
mation Figure S1 is different from Reppe reaction, because in (D3h). [Color figure can be viewed at wileyonlinelibrary.com]

Wiley Online Library Journal of Computational Chemistry 2019 7

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three acetylene molecules. As can be seen in Table 2, the initial
energies for producing benzene in Table 2 are 728–965 kJ/mol
for triangle arrays and 1808–2301 kJ/mol for ladder array, which
are much higher than the height of TS at ca. 165 kJ/mol from
the C3h cluster to benzene.
Full SHS-ADDF exploration of C4H4
We applied the full SHS-ADDF exploration on the ground singlet
PES at a dispersion-corrected DFT level to C4H4. In order to search
molecular clusters in addition to valence isomers, special treat-
ments for the threshold distance to cut off tracing dissociation
channels were made.[41] First, full SHS-ADDF search for C4H4 was
made at the level of B3LYP-D3/6-31G(d), and 90 EQs and 335 TSs
were obtained. Reoptimization calculations at the level of B3LYP-
D3/cc-pVDZ gave 82 EQs and 262 TSs. Large numbers of TSs dis-
appeared due to insufficient descriptions at the lower level,
whereas for EQs only eight were excluded, because even at the
lower level most EQs can be calculated reliably. Further
reoptimization calculations at the level of B3LYP-D3/aug-cc-pVTZ
gave a little bit smaller numbers of 70 EQs and 239 TSs, in which
less reliable structures were removed during the refinement.
Because we are interested in the lower energy structures, the
low energy part of reaction pathways were extracted and sche-
matically shown in Figure 8. The energies in Figure 8 are
corrected with inclusion of ZPVE. The most stable isomer of C4H4
is vinylacetylene EQ0, and energy values of other structures are
listed with respect to EQ0. All EQs are numbered from EQ0.
Cumulene EQ1 is the second lowest EQ. Cyclobutadiene EQ4 is
the fifth lowest one. T-form acetylene dimer has nearly the same
energy as cyclobutadiene, where ZPVE corrections are important,
since without ZPVE corrections the optimized energy of T-form
dimer in Table 4 is much less stable than cyclobutadiene.
8 Journal of Computational Chemistry 2019
TSs connecting different structures in Figure 8 were found to
be substantially high, and barrier heights are mostly much higher
than 40 kJ/mol, except for the smallest barrier of ca. 7 kJ/mol
from EQ13 to EQ4. EQs in Figure 8 except for EQ13 are well sepa-
rated by high energy barriers. Tetrahedrane EQ15 is not directly
connected with the most stable isomer of EQ0, but many other
EQs in Figure 8 are connected with EQ0 via only one TS.
Only 9 EQs among 70 EQs are contained in Figure 8. Other
61 EQs are carbenes or clusters including small molecules such
as H2 or some combinations of carbene and H2; for example,
the highest energy structures of EQ69 is a cluster of a carbene
of C4 with two H2 molecules. Energies of 70 EQs are from EQ0
(0.0 kJ/mol) to EQ69 (859.1 kJ/mol) with a very wide range of
ca. 860 kJ/mol, whereas for 1–5 obtained in Figures 1 and 2
their energies are from 1 (EQ4: 163.9 kJ/mol) to 3 (EQ15:
263.1 kJ/mol) with a much narrow range of ca. 94 kJ/mol. The
highest energy compound of 3 among 1–5 was found to be
located at the rather lower energy regions of the total energy
distributions of 70 EQs of C4H4. In this study, many unstable
structures with energies higher than 1–5 are not interested. If
such unstable structures are interested, careful treatments
should be further made, especially for diradical channels, by
using open-shell methods or multireference techniques.
Concerning global explorations of the ground singlet PES of
C4H4, we should comment on the earlier pioneering study by a
semi-empirical method of MINDO/3.[42] Totally 50 structures
were reported, but it is much less than the present results of
70 EQs. Moreover, a reaction pathway between tetrahedrane
and cyclobutadiene was proposed to be a two-step channel via
two intermediates, but the present result shows a shorter path-
way via only one intermediate between tetrahedrane and
cyclobutadiene. Reaction channels between cyclobutadiene
and vinylacetylene by MINDO/3 is much lengthy than the
Figure 8. Low-energy part of reaction
pathways of C4H4 on the ground singlet PES.
TSs are shown as blue dots with their
energies in kJ/mol. [Color figure can be
viewed at wileyonlinelibrary.com]
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present result of a direct connection via only one TS. Most of
the chemical structures found by MINDO/3 are compatible with
the present results, but reaction pathways are considerably
different.
The SHS-ADDF explorations have an important advantage to
elucidate the lowest energy barrier around each EQ. The lowest
energy barrier from tetrahedrane 3 (EQ15) is located on the
pathway to EQ13, and its barrier height is 127.2 kJ/mol. This
indicates that 3 (EQ15), still not yet synthesized, will be stable
enough to exist, once it is synthesized. In this connection, the
lowest barrier around a well know compound of cyclobutadiene
1 (EQ4) is rather lower as 77.5 kJ/mol on the pathway to EQ13.
SHS-ADDF search from randomly generated acetylene arrays
Although minimization processes in Figures 1–6 gave various
types of structures, the results are restricted by the assumed ini-
tial acetylene arrays. Furthermore, we tried to explore acetylene
clusters on the ground singlet PES by the SHS-ADDF method.
Starting points on PES were generated randomly by distributing
acetylene molecules. Five hundred independent geometries were
used for the SHS-ADDF searches. Successive SHS-ADDF searches
around the newly explored structures were only done for the
cases with no-bond rearrangements in each acetylene molecule.
In the case of (C2H2)2 SHS-ADDF search at the level of B3LYP-
D3/6-31G(d) gave only two acetylene clusters of the slipped
parallel form (C2h) and T form (C2v). Random generation of ini-
tial arrays at the level of B3LYP-D3/cc-pVDZ also gave the
slipped parallel form and T form as in the case for B3LYP-
D3/6–31G(d). Further reoptimization at the level of B3LYP-D3/
aug-cc-pVTZ only gave T form as EQ, and the slipped parallel
form was found as TS between two equivalent geometries of
T form.
In the case of (C2H2)3, SHS-ADDF search at the level of
B3LYP-D3/6-31G(d) and reoptimization at the level of B3LYP-
D3/aug-cc-pVTZ gave two more clusters (D2d and D2h) with T-
type interactions between monomers in addition to the more
stable cyclic trimers (C3h). As shown in Figure 9, D2d trimer has
Figure 9. Acetylene trimers and tetramers obtained by the SHS-ADDF
method at the level of B3LYP-D3/aug-cc-pVTZ. Relative energies are shown
in kJ/mol with respect to the most stable one.
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a tilted array of three monomers with the vertical axis of T in
the middle place and the lateral top parts at both ends,
whereas D2h trimer is a completely planar array composed of
the lateral top part in the middle and the vertical axes at both
ends. In contrast to the cyclic trimer with three sets of CH─π
interactions, only two sets of CH─π interactions in the linearly
arrayed D2d and D2h trimers to become energetically less stable
by ca. 8 kJ/mol with respect to the cyclic C3h trimer. Two types
of trimers (D2d and D2h) shown in Figure 9 were also reported
by MP2 calculations,[30] but they were not reported in many
other studies.
In the case of (C2H2)4 SHS-ADDF search at the level of B3LYP-
D3/6-31G(d) gave five types of tetramers including the cyclic
cluster (S4). Reoptimization calculations at the level of B3LYP-
D3/cc-pVTZ gave reduced numbers of 3 EQs. Further
reoptimization calculations at the level of B3LYP-D3/aug-cc-
pVTZ gave also three EQs (S4, C2v, Cs), and these structures were
shown in Figure 9. The C2v tetramer has a symmetric planar
array of three monomers, in which T-form dimer locates at the
center with two other monomers constituting a little deformed
cyclic trimers. The Cs tetramer is a nonplanar array composed
of a cyclic trimer and a vertical monomer, where the vertical
monomer and one component of the cyclic trimer nearly con-
stitute a T-form dimer. These two tetramers, C2v and Cs, are only
slightly (1.0 and 3.3 kJ/mol) higher than the S4 tetramer.
Relative energies of acetylene clusters
In order to compare relative energies of clusters carefully, ZPVE
corrections and free energies should be considered. Relative
energies of acetylene clusters (C2H2)n (n = 2–4) at the level of
B3LYP-D3/aug-cc-pVTZ and relative Gibbs free energies are
listed in Table 5; relative energies were evaluated with respect
to the most stable one for each size. Gibbs free energies were
calculated at 300 K and 1 atm. ZPVE-corrected values are shown
in parentheses.
The most stable form of acetylene dimer is T form (C2v). Infra-
red spectroscopy showed that T form is in good agreement
with the observation, though two monomers are easily rotat-
able with each other in the experimental condition.[23] In our
results, the slipped parallel form (C2h) was confirmed to be a
saddle point between two equivalent T forms with two mono-
mer arrangements interchanged. The energy barrier height
from C2v to C2h is only 1.030 J/mol, and it reduces to 0.606 kJ/
mol after ZPVE corrections. In free energies, the corresponding
barrier height becomes 4.656 kJ/mol (4.232 kJ/mol with ZPVE
corrections). These small barrier heights can be surmounted
easily at ca. 300 K. X form (D2d) is a second-order saddle point
located at much higher energies, and hence X form is not
important in experiments.
The lowest energy acetylene trimer is a cyclic form (C3h).
Spectroscopic studies indicated that the cyclic C3h form is
responsible for experimental data.[29] As long as the relative
energies are considered, other forms of trimers, D2d and D2h,
seem to be much less important. However, free energies of D2d
and D2h trimers become much lower than the cyclic C3h form.
Although generation of clusters is not necessarily preferable for
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 FULL PAPER
Table 5. Relative energies of acetylene clusters (C2H2)n n = 2–4.[a]
Relative energy[b]
Dimer (C2H2)2
T-form (C2v) 5 0.000 (0.000)
Slipped parallel (C2h) 2 1.030 (0.606)
X-form (D2d) 4 6.833 (4.232)
Trimer (C2H2)3
Cyclic (C3h) 7 0.000 (0.000)
Tilted array (D2d)[d] 7.863 (8.805)
Planar array (D2h)[d] 8.258 (6.703)
Tetramer (C2H2)4
Nonplanar cyclic (S4) 14 0.000 (0.000)
Planar cyclic (C4h) 0.101 (0.029)
Planar array (C2v)[d] 1.021 (0.666)
Nonplanar array (Cs)[d] 3.334 (2.639)
[a] Energies were obtained at the level of B3LYP-D3/aug-cc-pVTZ.
[b] Relative energies in kJ/mol with respect to the most stable cluster. ZPVE-corrected values are in parentheses.
[c] Relative free energies in kJ/mol with respect to the most stable cluster. ZPVE-corrected values are in parentheses.
[d] Structural figures are shown in Figure 9.
lower energy ones, careful analyses should be made in experi-
mental studies.
Spectroscopic study of acetylene tetramer indicated the pres-
ence of cyclic S4 tetramer.[36] In our calculations, the most sta-
ble tetramer was found to be the cyclic S4 form. Our
computational studies also showed that a planar cyclic tetramer
(C4h) exists as a saddle point on the PES. The barrier height to
this C4h form from the nonplanar S4 form was found to be very
small as 0.101 kJ/mol (84.4 cm−1) and 0.029 kJ/mol (2.4 cm−1)
after ZPVE corrections, so that the vibrational potential may be
a very shallow double well including two mirror images of the
S4 forms. Although in such double-well cases the potential
curve is more or less deformed from the harmonic model, our
free energy calculations at 300 K and 1 atm gave a sufficiently
high barrier height of 11.133 kJ/mol (930.6 cm−1) and
11.061 kJ/mol (924.6 cm−1) after ZPVE corrections. When the S4
cluster exists at one minimum of the double-well, it will have a
chirality.
Two other forms of tetramers, a planar array of C2v and a
nonplanar array of Cs, may also exist, although spectroscopic
observation was limited to the S4 form.[36] Although the C2v tet-
ramer was claimed to be most stable at the levels of
DFT(M06-2X) and MP2/aug-cc-pVDZ, the S4 tetramer is margin-
ally a little bit lower than the C2v form at the level of CCSD(T)/
aug-cc-pVDZ.[19] The Cs-form tetramer is interesting, because it
has negative free energy with respect to the S4 form as shown
in Table 5. Our results for acetylene tetramers (S4, C2v, Cs) were
found to be very similar to a recent DFT calculations at the level
of ω897X-V/aug-cc-pVTZ.[34]
Chemical reactions starting from a high-energy place of PES
As shown in Figures 1–6 and Supporting Information
Figures S1–S3, assemblies of acetylene molecules placed artificially
at a high-energy area of PES may undergo new types of chemical
reactions. A possibility of synthesizing tetrahedrane from two
acetylene molecules is suggested in Figure 2. Even without cata-
lysts three acetylene molecules are to be transformed into a
10 Journal of Computational Chemistry 2019
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Relative free energy[c]
0.000 (0.000)
4.656 (4.232) Saddle point between T forms
9.331 (7.633) Second-order saddle point
0.000 (0.000)
−7.852 (−6.913)
−6.609 (−8.164)
0.000 (0.000)
11.133(11.061) Saddle point between S4 forms
0.831 (0.475)
−5.440 (−6.135)
benzene molecules as shown in Figures 3 and 5 and Supporting
Information Figures S1 and S2.
We need to know how to initiate such kinds of new chemis-
try in real experiments. There may be many difficulties, but we
may expect that mechanochemistry will develop novel tech-
niques how to put molecules at certain places on PES.
Based on our studies on acetylene arrays shown in Figures 1–6
and Supporting Information Figure S1–S3, we may roughly esti-
mate required forces pressing acetylene molecules. Slopes of the
potential energy curves in Figure 1–6 give forces exerting on
acetylene monomers to put them apart from each other. For
example, from Figure 1 the range of R = 2.0–2.5 Å yields a force
of 1.24 × 10−8 N. Repulsive forces acting on the acetylene mole-
cules can thus be estimated as 1–9 × 10−8 N for Figures 1–6.
Although very strong forces may be attainable by recent ultra-
high pressure techniques,[43] the forces to be required for reac-
tions between acetylene molecules in this study should not be
static under equilibrium thermodynamic conditions, because
static forces gradually introduced may arouse some other reac-
tions before the aimed reactions. Thus, the forces between acety-
lene molecules need to be exerted locally in an instant condition
without arousing other reactions. For this purpose, mechanical
forces in nanotechnologies to manipulate molecules may be
employed to realize artificial placements of molecules at certain
parts of PES.
Conclusions
Placing acetylene molecules at distances much shorter than
van der Waals contacts on PES, various structures were easily
obtained by simple minimization procedures. Although con-
tacts at short distances need to be attained by mechanical
forces of 1–9 × 10−8 N, mechanochemistry will open new fields
where uncultivated sorts of chemical reactions await technical
developments.
As coordinate spaces of PES are generally too huge, finding
new chemistry on PES is a challenging problem. We found vari-
ous new reaction routes and various structures on PES by
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conventional geometry optimization starting from series of
molecular arrays for (C2H2)2, (C2H2)3, and (C2H2)4. Similar com-
putational studies for other molecules may also provide novel
structures and reaction pathways. Also in more general cases,
one may expect new types of chemical reactions, by placing
molecules at high-energy places on their PES.
Acknowledgments
K.O. acknowledges Tohoku University for using Electronic Journals
and research utilities of some electronic computers, Gaussian pro-
gram G09, and GaussView 5.09. H.Y. was supported by a Grant-in-
Aid (JSPS KAKENHI Grant No. JP17KT0100) from the Japan Society
for the Promotion of Science.
Keywords: potential energy surface
acetylene
reaction
route
mechanochemistry
How to cite this article: K. Ohno, T. Oki, H. Yamakado. J. Comput.
Chem. 2019, 9999, 1–11. DOI: 10.1002/jcc.26120
Additional Supporting Information may be found in the
online version of this article.
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Received: 23 August 2019
Revised: 12 November 2019
Accepted: 12 November 2019
Journal of Computational Chemistry 2019 11