Vinylidene: The final chapter

Journal Article · Wed Nov 21 04:00:00 EST 1990 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00180a011· OSTI ID:5234428

Gallo, M M; Hamilton, T P; Schaefer, H F ^[1]

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1. Univ. of Georgia, Athens (USA)

Ab initio molecular electronic structure theory is used to study the electronic ground state vinylidene-acetylene isomerization. Vinylidene, acetylene, and the transition state connecting them are located at various levels of theory, including correlated levels, and with large basis sets. The highest level and basis set with which geometry optimizations are performed is the CCSD level with the TZ+2P basis set. These structures are characterized by harmonic vibrational analyses as minima or transition states. Single-point energies also are computed at higher levels of theory, the highest being CCSD/QZ+3P, for all three structures. The effects of carbon atom f functions and hydrogen atom d functions are also explicitly considered. A classical barrier to isomerization from vinylidene to acetylene of {approximately}3 kcal/mol is found. The {Delta}E for isomerization is predicted to be {approximately}43 kcal/mol.

• DOE Contract Number: FG09-87ER13811
• OSTI ID: 5234428
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 112:24; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETYLENE
ALKYNES
CALCULATION METHODS
CHEMICAL REACTIONS
DATA
ELECTRONIC STRUCTURE
ENERGY LEVELS
GROUND STATES
HYDROCARBONS
INFORMATION
ISOMERIZATION
NUMERICAL DATA
ORGANIC COMPOUNDS
RADICALS
THEORETICAL DATA
VINYLIDENE RADICALS