Generalized resonating valence bond description of cyclobutadiene

Journal Article · Wed May 28 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00271a008· OSTI ID:5658745

Voter, A F; Goddard, III, W A

The low-lying electronic states of square and rectangular cyclobutadiene (CBD) are calculated by using the generalized resonating valence bond (GRVB) method and compared with the results from Hartree-Fock and configuration interaction wavefunctions. We find that simple valence bond concepts correctly predict the sequence of excited states (including ground-state singlet) and the distortion to a rectangular geometry for the ground state. Contrary to common expectation, we find that the singlet ground state of square CBD has 22 kcal of resonance energy (relative to a single valence bond structure). Thus, CBD is not antiresonant, though it is much less stable than normal conjugated systems.

• Research Organization: California Institute of Technology, Pasadena
• DOE Contract Number: AA03-76SF00767; AT03-80ER10608
• OSTI ID: 5658745
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:11; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
BUTADIENE
CHEMICAL BONDS
CONFIGURATION INTERACTION
CYCLOALKENES
DATA
DIENES
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
GROUND STATES
HARTREE-FOCK METHOD
HYDROCARBONS
INFORMATION
MATHEMATICAL MODELS
MOLECULAR MODELS
MOLECULAR ORBITAL METHOD
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
THEORETICAL DATA
VALENCE