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Kinetically stable high-energy isomers of C14H12 and C12H10N2 derived from cis-stilbene and cis-azobenzene.

Baker J, Wolinski K - J Mol Model (2010)

Bottom Line: The isomers were obtained by applying external forces to pairs of carbon atoms from each of the benzene rings in cis-stilbene and cis-azobenzene simultaneously, and are all at least 100 kcal mol(-1) higher in energy than the starting material.Each new structure was characterized as a minimum by vibrational analysis.Despite their high energy, all of the new isomers appear to be kinetically stable with respect to rearrangement back to cis-stilbene or cis-azobenzene, respectively.

View Article: PubMed Central - PubMed

Affiliation: Parallel Quantum Solutions, 2013 Green Acres Road, Fayetteville, AR 72703, USA. baker@pqs-chem.com

ABSTRACT
Following on from our recent enforced geometry optimization (EGO) investigation of isomerization in cis-stilbene (J Comput Chem, in press) we report the discovery of two interesting new, symmetrical "fused sandwich" isomers of both cis-stilbene and the related cis-azobenzene. The isomers were obtained by applying external forces to pairs of carbon atoms from each of the benzene rings in cis-stilbene and cis-azobenzene simultaneously, and are all at least 100 kcal mol(-1) higher in energy than the starting material. Each new structure was characterized as a minimum by vibrational analysis. Despite their high energy, all of the new isomers appear to be kinetically stable with respect to rearrangement back to cis-stilbene or cis-azobenzene, respectively.

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EGO optimization history
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Sch1: EGO optimization history

Mentions: The new isomers, which we call C14H12-Cs, C14H12-C2v, C12H10N2-Cs and C12H10N2-C2v are shown in Fig. 2. They were all obtained by pushing together all symmetry equivalent pairs of carbon atoms from the two phenyl rings in cis-stilbene and cis-azobenzene, respectively. As denoted by the names, the new isomers have either Cs or C2v symmetry. The optimization history for this procedure starting from cis-stilbene using an applied force of 0.1 au is depicted in Scheme 1, below.Fig. 2


Kinetically stable high-energy isomers of C14H12 and C12H10N2 derived from cis-stilbene and cis-azobenzene.

Baker J, Wolinski K - J Mol Model (2010)

EGO optimization history
© Copyright Policy
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC3102204&req=5

Sch1: EGO optimization history
Mentions: The new isomers, which we call C14H12-Cs, C14H12-C2v, C12H10N2-Cs and C12H10N2-C2v are shown in Fig. 2. They were all obtained by pushing together all symmetry equivalent pairs of carbon atoms from the two phenyl rings in cis-stilbene and cis-azobenzene, respectively. As denoted by the names, the new isomers have either Cs or C2v symmetry. The optimization history for this procedure starting from cis-stilbene using an applied force of 0.1 au is depicted in Scheme 1, below.Fig. 2

Bottom Line: The isomers were obtained by applying external forces to pairs of carbon atoms from each of the benzene rings in cis-stilbene and cis-azobenzene simultaneously, and are all at least 100 kcal mol(-1) higher in energy than the starting material.Each new structure was characterized as a minimum by vibrational analysis.Despite their high energy, all of the new isomers appear to be kinetically stable with respect to rearrangement back to cis-stilbene or cis-azobenzene, respectively.

View Article: PubMed Central - PubMed

Affiliation: Parallel Quantum Solutions, 2013 Green Acres Road, Fayetteville, AR 72703, USA. baker@pqs-chem.com

ABSTRACT
Following on from our recent enforced geometry optimization (EGO) investigation of isomerization in cis-stilbene (J Comput Chem, in press) we report the discovery of two interesting new, symmetrical "fused sandwich" isomers of both cis-stilbene and the related cis-azobenzene. The isomers were obtained by applying external forces to pairs of carbon atoms from each of the benzene rings in cis-stilbene and cis-azobenzene simultaneously, and are all at least 100 kcal mol(-1) higher in energy than the starting material. Each new structure was characterized as a minimum by vibrational analysis. Despite their high energy, all of the new isomers appear to be kinetically stable with respect to rearrangement back to cis-stilbene or cis-azobenzene, respectively.

Show MeSH