Restricted geometry optimization for estimating stabilization energies of polycyclic aromatic hydrocarbons
Bao, Peng; Yu, Zhong-Heng
AbstractAt the B3LYP/6-31G* level, our program of geometry optimization under the restrictions of pi-orbital interactions was applied to five homologous series such as acene-, phenanthrene, triphenylene, chrysene, benzopyrene series, and seven additional molecules such as tri- and tetra-benzanthracene, benzo- and naphtho-pentaphene, dibenzopentacene and tribenzotetracene, providing each of the 35 polycyclic aromatic hydrocarbons (PAHs) with two types of localized reference geometries: (i) the 'GL' geometry where all double bonds are localized and (ii) m different 'GE-m' geometries, where only a specific pair of double bonds are permitted to conjugate and all other bonds are localized.. Each GE-m resulted from the local pi interaction between a pair of double bonds in the GL geometry. The total sum of molecular energy differences, ([E(Ground) - E(GL)] - Sigma[E(GE-m) - E(GL)]), is defined as the extra stabilization energy (ESE) for a PAH. The corrected ESE (CESE) then resulted from considering pi interactions between pairs of nonbonded double bonds. In this work, the position, energy, and GL sextet rules were developed to ensure that the GL geometry chosen from its candidates as well as the GE-m geometries is no longer arbitrary. Therefore, it is the GL and GE-m geometries of the PAH itself, rather than nonaromatic compounds, that serve as reference structures for calculating CESE. As a result, for each of the four homologous series (acene, phenanthrene, triphenylene, and benzopyrene), CESE/pi can be fitted as a linear function of the p band frequency (v) over tilde. For each of the four isomeric series with molecular formulas of C(18)H(12), C(22)H(14), C(26)H(16), and C(30)H(18), CESE/pi can also be fitted as a second-order polynomial function of the p band frequency (v) over tilde as well as of the number of GL sextets. Copyright (C) 2009 John Wiley & Sons, Ltd.
KeywordAromaticity Extra Stabilization Energy Localized Reference Structures Polycyclic Aromatic Hydrocarbons Restricted Geometry Optimization
Indexed BySCI
WOS IDWOS:000273663600002
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Cited Times:2[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Corresponding AuthorYu, Zhong-Heng
AffiliationChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Struct Chem Unstable & Stable Speci, Inst Chem, Beijing 100190, Peoples R China
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GB/T 7714
Bao, Peng,Yu, Zhong-Heng. Restricted geometry optimization for estimating stabilization energies of polycyclic aromatic hydrocarbons[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,2010,23(1):16-29.
APA Bao, Peng,&Yu, Zhong-Heng.(2010).Restricted geometry optimization for estimating stabilization energies of polycyclic aromatic hydrocarbons.JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,23(1),16-29.
MLA Bao, Peng,et al."Restricted geometry optimization for estimating stabilization energies of polycyclic aromatic hydrocarbons".JOURNAL OF PHYSICAL ORGANIC CHEMISTRY 23.1(2010):16-29.
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