Rehybridized 1,3-butadiene radical cations: How far will a radical cation go to maintain conjugation?

Journal of Physical Chemistry A

Volumn 106, Issue 15, 2002, Pages 3967-3974

  Oxgaard, Jonas ^a   Wiest, Olaf ^a  

^a UNIVERSITY OF NOTRE DAME   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

QUANTUM MECHANICAL METHOD; RADICAL CATIONS; REHYBRIDIZATION; SUBSTITUENT EFFECTS;

CHEMICAL REACTIONS; CHEMISTRY; MOLECULAR DYNAMICS; POSITIVE IONS; PROBABILITY DENSITY FUNCTION; QUANTUM THEORY;

BUTADIENE;

EID: 0037129513     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp020041c     Document Type: Article

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56. The scan was also repeated with the Guassian keyword guess = always, thus creating a new wave function for each step of the optimization. The result remained unchanged. As the computational time required increased by a factor of 10, this was only done for testing purposes.
57. The dihedral angle C1-C2-C3-H7 is defined as the angle between the planes formed by C1-C2-C3 and C2-C3-H7 and will thus measure with what angle the C2-H7 bond bends out of the C1-C2-C3 plane. There are two other possible dihedral angles, C1-C2-H7-C3 and C1-H7-C2-C3, which are nonequal. The difference between the angles is at most 3deg;, and we will thus confined the discussion to the C1-C2-C3-H7 dihedral.
58. 2.33 center.
59. (C4-C3-H8-C2)).
60. The energies obtained by QCISD/6-31Gz.ast; show differences as large as 10 kcal/mol when compared to the B3LYP or QCISD(T)/6-311Gz.ast;z.ast; single-point energies of the QCISD/6-31Gz.ast; geometry. This discrepancy increased dramatically with more pronounced pyramidalization and will be the topic of a forthcoming publication.
61. Compound 4 is not experimentally accessible, as it undergoes a facile tautomerization to the corresponding diacyl species. As the purpose of this study is to establish a substituent effect trend rather than an investigation of individual compounds, it was decided to use 4 instead of the stable 2,3-(MeO, MeO) 1,3-butadiene.
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68. bull;+ (phi;1 = 90deg;, phi;2 = 37.2deg;) as an example, the p-orbitals have a dihedral angle of 63.6deg;.