Abstract
Ethynylvinylidene, an energetically low‐lying isomer of diacetylene, has been studied using ab initio molecular electronic structure theory. Geometries of diacetylene, ethynylvinylidene, and the transition state between them have been optimized using the double‐ζ plus polarization (DZP) and triple‐ζ plus double polarization function (TZ2P) basis sets with the self‐consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double substitutions (CCSD), and CCSD with perturbatively included connected triple substitutions [CCSD(T)] methods. At the TZ2P CCSD(T) level of theory only single point energies have been determined at the TZ2P CCSD geometries. Harmonic vibrational frequencies and infrared (IR) intensities are reported for the three stationary points at the DZP SCF, TZ2P SCF, and DZP CISD levels of theory. For ethynylvinylidene, rotational constants, dipole moments, and dipole moment components along the principal axes are also given. This isomer is found to be an extremely shallow minimum on the C4H2 potential energy surface, and the classical barrier to rearrangement (to diacetylene) is vanishingly small at the highest level of theory.
| Original language | English |
|---|---|
| Pages (from-to) | 317-321 |
| Number of pages | 5 |
| Journal | Israel Journal of Chemistry |
| Volume | 33 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - 1993 |
Fingerprint
All Science Journal Classification (ASJC) codes
- Chemistry(all)
Cite this
}
Ethynylvinylidene. / Collins, Charlene L.; Hu, Ching‐Han ‐H; Yamaguchi, Yukio; Schaefer, Henry F.
In: Israel Journal of Chemistry, Vol. 33, No. 3, 1993, p. 317-321.Research output: Contribution to journal › Article
TY - JOUR
T1 - Ethynylvinylidene
AU - Collins, Charlene L.
AU - Hu, Ching‐Han ‐H
AU - Yamaguchi, Yukio
AU - Schaefer, Henry F.
PY - 1993
Y1 - 1993
N2 - Ethynylvinylidene, an energetically low‐lying isomer of diacetylene, has been studied using ab initio molecular electronic structure theory. Geometries of diacetylene, ethynylvinylidene, and the transition state between them have been optimized using the double‐ζ plus polarization (DZP) and triple‐ζ plus double polarization function (TZ2P) basis sets with the self‐consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double substitutions (CCSD), and CCSD with perturbatively included connected triple substitutions [CCSD(T)] methods. At the TZ2P CCSD(T) level of theory only single point energies have been determined at the TZ2P CCSD geometries. Harmonic vibrational frequencies and infrared (IR) intensities are reported for the three stationary points at the DZP SCF, TZ2P SCF, and DZP CISD levels of theory. For ethynylvinylidene, rotational constants, dipole moments, and dipole moment components along the principal axes are also given. This isomer is found to be an extremely shallow minimum on the C4H2 potential energy surface, and the classical barrier to rearrangement (to diacetylene) is vanishingly small at the highest level of theory.
AB - Ethynylvinylidene, an energetically low‐lying isomer of diacetylene, has been studied using ab initio molecular electronic structure theory. Geometries of diacetylene, ethynylvinylidene, and the transition state between them have been optimized using the double‐ζ plus polarization (DZP) and triple‐ζ plus double polarization function (TZ2P) basis sets with the self‐consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double substitutions (CCSD), and CCSD with perturbatively included connected triple substitutions [CCSD(T)] methods. At the TZ2P CCSD(T) level of theory only single point energies have been determined at the TZ2P CCSD geometries. Harmonic vibrational frequencies and infrared (IR) intensities are reported for the three stationary points at the DZP SCF, TZ2P SCF, and DZP CISD levels of theory. For ethynylvinylidene, rotational constants, dipole moments, and dipole moment components along the principal axes are also given. This isomer is found to be an extremely shallow minimum on the C4H2 potential energy surface, and the classical barrier to rearrangement (to diacetylene) is vanishingly small at the highest level of theory.
UR - http://www.scopus.com/inward/record.url?scp=85005693495&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85005693495&partnerID=8YFLogxK
U2 - 10.1002/ijch.199300038
DO - 10.1002/ijch.199300038
M3 - Article
AN - SCOPUS:85005693495
VL - 33
SP - 317
EP - 321
JO - Israel Journal of Chemistry
JF - Israel Journal of Chemistry
SN - 0021-2148
IS - 3
ER -