Cyanovinylidene: An observable unsaturated carbene and a possible interstellar molecule

Ching-Han Hu, Henry F. Schaefer

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Ab initio quantum mechanical methods, including the self-consistent field (SCF), single and double excitation configuration interaction (CISD), the single and double excitation coupled cluster (CCSD), and the single, double, and perturbative triple excitation coupled cluster [CCSD(T)] have been applied to study the ground-state cyanovinylidene-cyanoacetyleneisomerization reaction. The classical barrier for the isomerization from cyanovinylidene to cyanoacetylene is found to be 4.3 kcal/mol and is 2.2 kcal/mol when the zero-point vibrational energy corrections are included. Cyanovinylidene is predicted to lie 47 kcal/mol higher in energy than cyanoacetylene. Some comparisons of cyanovinylidene with vinylidene and fluorovinylidene are presented and suggest that cyanovinylidene is a genuine minimum on the potential energy hypersurface. Thus, the probability of observing cyanovinylidene spectroscopically is substantial, particularly via negative ion photodetachment spectroscopy. Two low-lying triplet states ã3A′ and b̃3A″ of cyanovinylidene have also been studied.

Original languageEnglish
Pages (from-to)10681-10686
Number of pages6
JournalJournal of Physical Chemistry
Volume97
Issue number41
DOIs
Publication statusPublished - 1993 Jan 1

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carbenes
Isomerization
Potential energy
cyanoacetylene
Ground state
Negative ions
Spectroscopy
Molecules
excitation
molecules
photodetachment
vinylidene
negative ions
isomerization
configuration interaction
atomic energy levels
self consistent fields
potential energy
ground state
energy

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

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abstract = "Ab initio quantum mechanical methods, including the self-consistent field (SCF), single and double excitation configuration interaction (CISD), the single and double excitation coupled cluster (CCSD), and the single, double, and perturbative triple excitation coupled cluster [CCSD(T)] have been applied to study the ground-state cyanovinylidene-cyanoacetyleneisomerization reaction. The classical barrier for the isomerization from cyanovinylidene to cyanoacetylene is found to be 4.3 kcal/mol and is 2.2 kcal/mol when the zero-point vibrational energy corrections are included. Cyanovinylidene is predicted to lie 47 kcal/mol higher in energy than cyanoacetylene. Some comparisons of cyanovinylidene with vinylidene and fluorovinylidene are presented and suggest that cyanovinylidene is a genuine minimum on the potential energy hypersurface. Thus, the probability of observing cyanovinylidene spectroscopically is substantial, particularly via negative ion photodetachment spectroscopy. Two low-lying triplet states {\~a}3A′ and b̃3A″ of cyanovinylidene have also been studied.",
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Cyanovinylidene : An observable unsaturated carbene and a possible interstellar molecule. / Hu, Ching-Han; Schaefer, Henry F.

In: Journal of Physical Chemistry, Vol. 97, No. 41, 01.01.1993, p. 10681-10686.

Research output: Contribution to journalArticle

TY - JOUR

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T2 - An observable unsaturated carbene and a possible interstellar molecule

AU - Hu, Ching-Han

AU - Schaefer, Henry F.

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