A benchmark vibrational potential surface: ground-state benzene

Goodman, Lionel; Ozkabak, Ali G.; Thakur, Surya N.

doi:10.1021/j100176a008

Cited by 217 publications

(258 citation statements)

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“…These results are in line with the earlier reports on failures of electronic structure methods for the correct description of low-lying out-of-plane vibrational frequencies of benzene, 2,3 several planar arenes, [4][5][6][7][8] and other nonrigid molecules. 9 Similar pitfalls have been recently found by Shabahzian 10 for the challenging ͑B 6 C͒ 2− anion, particularly at the MP2 level of theory.…”

Section: Introductionsupporting

confidence: 92%

Intramolecular basis set superposition error effects on the planarity of benzene and other aromatic molecules: A solution to the problem

Asturiol

Duran

Salvador

2008

The Journal of Chemical Physics

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Recently, the surprising result that ab initio calculations on benzene and other planar arenes at correlated MP2, MP3, configuration interaction with singles and doubles ͑CISD͒, and coupled cluster with singles and doubles levels of theory using standard Pople's basis sets yield nonplanar minima has been reported. The planar optimized structures turn out to be transition states presenting one or more large imaginary frequencies, whereas single-determinant-based methods lead to the expected planar minima and no imaginary frequencies. It has been suggested that such anomalous behavior can be originated by two-electron basis set incompleteness error. In this work, we show that the reported pitfalls can be interpreted in terms of intramolecular basis set superposition error ͑BSSE͒ effects, mostly between the C-H moieties constituting the arenes. We have carried out counterpoise-corrected optimizations and frequency calculations at the Hartree-Fock, B3LYP, MP2, and CISD levels of theory with several basis sets for a number of arenes. In all cases, correcting for intramolecular BSSE fixes the anomalous behavior of the correlated methods, whereas no significant differences are observed in the single-determinant case. Consequently, all systems studied are planar at all levels of theory. The effect of different intramolecular fragment definitions and the particular case of charged species, namely, cyclopentadienyl and indenyl anions, respectively, are also discussed.

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Section: Introductionsupporting

confidence: 92%

Intramolecular basis set superposition error effects on the planarity of benzene and other aromatic molecules: A solution to the problem

Asturiol

Duran

Salvador

2008

The Journal of Chemical Physics

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“…The theoretical calculations take on great significance [110]. Ab initio calculations [111][112][113][114][115][116][117] point to the D 6h structure as that of minimum energy for benzene on the ground state energy surface. The data [111][112][113][114][115][116] are collected in Table 6 and compared with the most important structural results.…”

Section: Benzene: Ground and Lowest Excited Statesmentioning

confidence: 99%

Structures of Annulenes and Model Annulene Systems in the Ground and Lowest Excited States

Gellini

Salvi

2010

Symmetry

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The paper introduces general considerations on structural properties of aromatic, antiaromatic and non-aromatic conjugated systems in terms of potential energy along bond length alternation and distortion coordinates, taking as examples benzene, cyclobutadiene and cyclooctatetraene. Pentalene, formally derived from cyclooctatetraene by cross linking, is also considered as a typical antiaromatic system. The main interest is concerned with [n]annulenes and model [n]annulene molecular systems, n ranging from 10 to 18. The rich variety of conformational and configurational isomers and of dynamical processes among them is described. Specific attention is devoted to bridged [10]-and [14]annulenes in the ground and lowest excited states as well as to s-indacene and biphenylene. Experimental data obtained from vibrational and electronic spectroscopies are discussed and compared with ab initio calculation results. Finally, porphyrin, tetraoxaporphyrin dication and diprotonated porphyrin are presented as annulene structures adopting planar/non-planar geometries depending on the steric hindrance in the inner macrocycle ring. Radiative and non-radiative relaxation processes from excited state levels have been observed by means of time-resolved fluorescence and femtosecond transient absorption spectroscopy. A short account is also given of porphycene, the structural isomer of porphyrin, and of porphycene properties.

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“…An extensive experimental literature exists on the subject (see Refs. [16,45] for reviews): high resolution data are available for many of the fundamentals, and all the assignments can be regarded as conclusive. (An analysis of the B3LYP/cc-pVTZ normal modes of benzene and the azabenzenes in terms of Pulay's redundant internal coordinates can be found in Table 17 of Ref.…”

Section: A Benzenementioning

confidence: 99%

“…The experimental data were taken from the earlier compilation of GOT [45] and from more recent gas-phase measurements [16]. (discounting ν 5 which is severely perturbed by resonances).…”

Section: A Benzenementioning

confidence: 99%

Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields

2003

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Anharmonic force fields and vibrational spectra of the azabenzene series (pyridine, pyridazine, pyrimidine, pyrazine, s-triazine, 1,2,3-triazine, 1,2,4-triazine and s-tetrazine) and benzene are obtained using density functional theory (DFT) with the B97-1 exchange-correlation functional and a triple-zeta plus double polarization (TZ2P) basis set. Overall, the fundamental frequencies computed by second-order rovibrational perturbation theory are in excellent agreement with experiment. The resolution of the presently calculated anharmonic spectra is such that they represent an extremely useful tool for the assignment and interpretation of the experimental spectra, especially where resonances are involved.

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A benchmark vibrational potential surface: ground-state benzene

Cited by 217 publications

References 0 publications

Intramolecular basis set superposition error effects on the planarity of benzene and other aromatic molecules: A solution to the problem

Intramolecular basis set superposition error effects on the planarity of benzene and other aromatic molecules: A solution to the problem

Structures of Annulenes and Model Annulene Systems in the Ground and Lowest Excited States

Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields

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