Structures and Energetics of C9H2 Isomers: An

Ab Initio Study
Aditya P. Pandey, Garima Yadav, Tanmay G. Netke, Saurabh Deshpande, and Venkatesan S.
Thimmakondu
Department of Chemistry, BITS-Pilani, K K Birla Goa Campus, Goa 403 726, India
Introduction

Table 1

I From the time cyclopropenylidene (C3H2) found in the laboratory and in

space (Taurus Molecular Cloud-1) [1], interest in finding their homologous
series of molecules has grown up [2].
I So far, three isomers of C9H2 have been found in the laboratory. Isomer 1,
nona-1,3,6,8-tetrayn-5-ylidene, had been detected by cavity ring-down
spectroscopy [3]. Isomers 2 and 6, 1-(hexa-1,3,5-triynyl)cyclopropenylidene
and nonaoctaenylidene, respectively, were detected by Fourier transform
microwave spectroscopy [4,5].
I Rest of the isomers (3-5 and 7-11) are yet to be detected in the laboratory.
I None of the C9H2 isomers have been detected yet in the interstellar or
cirumstellar gas clouds.
I Quantum chemical calculations may help in identifying the unknown isomers
in the laboratory and also in the interstellar medium.

I Energetics of C9H2 isomers in their ground electronic states at

CCSD/cc-pVDZ level of theory

Scheme 1
I Low-energy Isomers: Relative energies (E) are within 100 kJmol1
compared to the global minimum 1 at CCSD(T)/cc-pVDZ level of theory.

Isomer Point
Group
1
Dh
2
Cs
3
Cs
4
Cs
5
Cs
6
C2v
7
Cs
8
C2v
9
Cs
10
Cs
11
C2v

E
[-342.0] a.u
-0.79862662
-0.79248681
-0.78891068
-0.76852548
-0.76235324
-0.75092822
-0.75372043
-0.75305239
-0.75582855
-0.74033951
-0.73178902

ZPE
kJmol1
149.67
163.63
161.99
154.70
160.94
160.07
160.69
159.09
162.87
163.03
163.59

E+ZPE
[-342.0] a.u
-0.74161950
-0.73016326
-0.72721055
-0.70960425
-0.70105525
-0.68995912
-0.69251533
-0.69245701
-0.69379371
-0.67824552
-0.66947971

E E+ZPE
Stability
Debye kJmol1 kJmol1 E E+ZPE
0.000
0.00
0.00 1
1
3.690
16.12
30.08 2
2
3.872
25.51
37.83 3
3
2.270
79.03
84.06 4
4
5.983
95.24
106.50 5
5
8.335 125.23
135.63 9
9
7.007 117.90
128.92 7
7
6.066 119.66
129.08 8
8
8.552 112.37
125.57 6
6
11.507 153.03
166.39 10
10
14.201 175.48
189.40 11
11

Table 2
I Energetics of C9H2 isomers in their ground electronic states at
CCSD(T)/cc-pVDZ level of theory
Isomer Point
Group
1
Dh
2
Cs
3
Cs
4
Cs
5
Cs
6
C2v
7
Cs
8
C2v
9
Cs
10
Cs
11
C2v

E
[-342.0] a.u
-0.86415244
-0.85378427
-0.84947846
-0.83514922
-0.82994718
-0.82663844
-0.82522184
-0.82044225
-0.81924522
-0.80755840
-0.80335902

ZPE
kJmol1
145.12
159.12
157.44
148.76
156.41
155.77
156.32
154.59
158.57
159.14
160.16

E+ZPE
[-342.0] a.u
-0.80887802
-0.79317685
-0.78951393
-0.77848802
-0.77037232
-0.76730739
-0.76568100
-0.76156178
-0.75885006
-0.74694683
-0.74235739

E E+ZPE
Stability
Debye kJmol1 kJmol1 E E+ZPE
0.000
0.00
0.00 1
1
3.717
27.22
41.22 2
2
3.890
38.53
50.84 3
3
2.130
76.15
79.79 4
4
6.306
89.81
101.10 5
5
8.292
98.49
109.14 6
6
7.199 102.21
113.41 7
7
6.317 114.76
124.23 8
8
8.465 117.90
131.35 9
9
11.178 148.59
162.60 10
10
13.681 159.61
174.65 11
11

Discussion and open questions

Scheme 2
I High-energy Isomers: Relative energies (E) are > 100 kJmol1 than the
global minimum 1 at CCSD(T)/cc-pVDZ level of theory.

I Like CnH2 (n = 5 or 7) [7], the linear triplet geometry (isomer 1) is the

most stable one at both levels.
I Although isomers 3-5 are more stable than isomer 6, they are yet to be
detected.
I We note that our study is not an exhaustive survey. In fact, many more
isomeric structures are possible but only the most important ones (E +
ZPE < 175 kJmol1) are reported here.
I Considering the large dipole moment values of many of these isomers, we
believe that it is possible to detect (trap in an Ar matrix) some of these
unidentified isomers (3-5 and 7-11) with the right precursors at low
temperatures.
I How these molecules are formed in space?
I What is the formation mechanism?
I Can it be studied by ab initio calculations?
Acknowledgment

Computational Methods
I Electronic structure calculations reported in this study were carried out
using CFOUR program [6].
I All calculations were done with a frozen-core approximation employing the
correlation-consistent polarzied valence double -basis set (cc-pVDZ).
I For C9H2 isomers, the cc-pVDZ basis set consists of 136 basis functions.
I For isomer 1, we had used a restricted open-shell Hartree-Fock (ROHF)
wave function as the ground electronic state is triplet. For the rest of the
isomers, the singlet ground state is more stable than the triplet and
therefore we had used an RHF wave function.
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Computational facility provided through the DST-FIST program (Project

No. SR/FST/PSI-142/2009) of the Department of Science and
Technology, New Delhi, India, is gratefully acknowledged. We also thank
the Computer Center and Department of Physics, BITS-Pilani, K K Birla
Goa campus, for providing us the additional computational facilities. VST
thanks BITS-Pilani University for providing financial support in the form of
Research Initiation Grant.
References
1 P. Thaddeus, J. M. Vrtilek, C. A. Gottlieb, Astrophys. J. 299, L63-L66 (1985).
2 M. C. McCarthy, M. J. Travers, A. Kovacs, W. Chen, S. E. Novick, C. A. Gottlieb, and P.
Thaddeus, Science, 275, 518-520 (1997).
3 C. D. Ball, M. C. McCarthy, and P. Thaddeus, J. Chem. Phys. 112, 10149-10155 (2000).
4 M. C. McCarthy, M. J. Travers, W. Chen, C. A. Gottlieb, and P. Thaddeus, Astrophys. J.,
498, L89-L92 (1998).
5 A. J. Apponi, M. C. McCarthy, C. A. Gottlieb, and P. Thaddeus, Astrophys. J., 530,
357-361 (2000).
6 J. F. Stanton, J. Gauss, et al., CFOUR. For the current version, see www.cfour.de (2014).
7 R. A. Seburg, et al., J. Am. Chem. Soc., 119, 10838-10845 (1997).
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