Density functional studies of molecular polarizabilities Part 4: the C<sub>10</sub>H<sub>8</sub> molecules azulene, fulvalene and napthalene

Hinchliffe, Alan; Pérez, Juan J.; Machado, Humberto J. Soscún

doi:10.1002/ejtc.63

Cited by 14 publications

(17 citation statements)

References 8 publications

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“…Therefore, the heterocycles that contained phosphorus and sulphur have a major molecular volume (V mol ), which induces a major polarisation (larger nucleus and electron cloud) of the C-P and C-S bonds with respect to the C-N and C-O bonds, explaining perfectly the effect of heterosubstituent (X or Y) found for this property. In addition, the direct relationship found between the polarisability and the C-heteroatom bond length (that determines V mol ) is completely in agreement to the empirical definition of the polarisability [37]:…”

Section: Static Polarisability (α)supporting

confidence: 74%

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH₂CH₂X: a comparative ab initio, DFT and semi-empirical study

Romero

Squitieri

2016

Molecular Physics

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The influence of heterosubstituent and ring puckering angle (ϕ) on electronic properties (μ, α, β and γ ) of 16 four-membered heterocycles (1-16) were demonstrated theoretically using ab initio (HF and MP2), density functional theory (DFT) (PBE1PBE, SVWN5 and B3LYP) and semi-empirical (PM6 and PM3) treatments. Comparing the DFT and ab initio methods, these showed a similar description of electric dipole moment (μ) and polarisability (α) for each one of the studied heterocycles, with small differences in the prediction of α. The calculated hyperpolarisabilities (β and γ ) are very sensitive to the quality of level theory, especially when the heterocycles contain phosphorus and sulphur. On the other hand, comparing with the rest of methods used, the semi-empirical calculations show significant deviations in the prediction of the different properties, and only are in agreement with the calculations of μ for the heterocycles that do not contain phosphorus or sulphur. In general, β and γ are more sensitive to the molecular geometry than μ and α. The dipole moment is determined by the heteroatom (X) within the ring, where the oxetanes and thietanes exhibit a minimum value of μ at planar conformations, while the azetidines and phosphetanes at axial conformations. All heterocycles show a minimum value of α at planar conformation, and their largest values are associated to conformations highly puckered. β exhibits an implicit relationship with the C = Y bond according to the conformational states. In addition, the X and Y heterosubstituents affect significantly the values of α, β and γ , observing the largest values for the phosphorus-and sulphur-containing heterocycles. Finally, considering the values obtained for α, β and γ , the studied heterocycles can represent an interesting unit for the design of new promising push-pull systems as donor or acceptor group.

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Section: Static Polarisability (α)supporting

confidence: 74%

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH₂CH₂X: a comparative ab initio, DFT and semi-empirical study

Romero

Squitieri

2016

Molecular Physics

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“…We reached similar conclusions for naphthalene [10]. The aim of this paper is to extend our studies to anthracene and phenanthrene.…”

Section: Introductionsupporting

confidence: 76%

Density Functional Studies of Molecular Polarizabilities. 7. Anthracene and Phenanthrene

Hinchliffe

Machado

2000

IJMS

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Abstract:We report accurate Ab Initio studies of the static dipole polarizabilities of anthracene and phenanthrene. Geometries were optimized at the HF/6-311G(3d,2p) level of theory. Dipole polarizabilities were calculated at the HF/6-311++G(3d,2p) and BLYP/6-311++G(3d,2p) levels of theory, using HF/6-311G(3d,2p) geometries. The calculated dipole polarizabilities for anthracene are compared with experiment. Inclusion of electron correlation using the BLYP procedure increases the L and M components of the dipole polarizability, but not the perpendicular (N) component. Examination of corresponding BLYP results for the polyacene series benzene, naphthalene and anthracene shows that the normal component of the dipole polarizability scales linearly with the number of benzene ring units, with an increment of 20.8 au. The medium component also scales linearly with an increment of 42.8 atomic units. The long component does not scale linearly. Semi-emiprical AM1 calculations are also given for comparison; the normal component of the dipole polarizability tensor is poorly represented by such calculations.

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“…The most recent calculations [43,44] on 5 at the HF/6-311G(3d,2p) and BLYP/6-311++G(3d,2p) levels of theory [45] have such planarity and bond alternation as expected (Figure 1). Furthermore, the recent all electron mapping of ring currents by Fowler and Jenneskens and their groups [73] shows 5 and its 2,3-benzo derivative with the expected pattern of paratropic ring currents for the σ electrons.…”

Section: Pentafulvalenes (Fulvalenes)mentioning

confidence: 60%

“…These provided much valuable information but it will be realised that recent ab initio computations provide the most reliable information. [43][44][45] What can be said here is that the early results predicted nonpolar, bond alternating structures for the symmetrical non-alternant (4n + 2) π electron hydrocarbons such as 5, and 7. The unsymmetrical homologues 4, 6 and 8, however, were expected to show some polarisation from the generation of two separate (4n + 2) non-benzenoid aromatic moieties as shown by the polar cyclopropenyl-cyclopentadienyl structure 4b of triapentafulvalene (calicene).…”

Section: In Late 1968 He Transferred To Victoria University Of Wellinmentioning

confidence: 88%

The Fulvalenes

Halton

2005

Eur J Org Chem

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The fulvalenes are the class of hydrocarbons obtained by formally cross‐conjugating two rings through a common exocyclic double bond. Although the first report of such a compound dates to 1915, study of the series began in earnest only in the 1950s, and even today many of the unsubstituted parent hydrocarbons remain unknown. The following report, the first to specifically address this class of molecules, summarises the information available from research published to the end of 2004 and offers some suggestions for future study. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Density functional studies of molecular polarizabilities Part 4: the C₁₀H₈ molecules azulene, fulvalene and napthalene

Cited by 14 publications

References 8 publications

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH₂CH₂X: a comparative ab initio, DFT and semi-empirical study

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH₂CH₂X: a comparative ab initio, DFT and semi-empirical study

Density Functional Studies of Molecular Polarizabilities. 7. Anthracene and Phenanthrene

The Fulvalenes

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Density functional studies of molecular polarizabilities Part 4: the C10H8 molecules azulene, fulvalene and napthalene

Cited by 14 publications

References 8 publications

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH2CH2X: a comparative ab initio, DFT and semi-empirical study

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH2CH2X: a comparative ab initio, DFT and semi-empirical study

Density Functional Studies of Molecular Polarizabilities. 7. Anthracene and Phenanthrene

The Fulvalenes

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Density functional studies of molecular polarizabilities Part 4: the C₁₀H₈ molecules azulene, fulvalene and napthalene

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH₂CH₂X: a comparative ab initio, DFT and semi-empirical study

Effect of heterosubstituent and ring puckering angle on linear and nonlinear properties of exo-insaturated four-membered heterocycles, Y=CCH₂CH₂X: a comparative ab initio, DFT and semi-empirical study