Ab initio investigation of internal rotation in conjugated molecules and the orientation of NO 2 in nitroaromatics: nitrobenzene, o -monofluoro- and o , o ′-difluoro-nitrobenzenes

Staikova, M.; Csizmadia, Imre G.

doi:10.1016/s0166-1280(99)00094-9

Cited by 26 publications

(16 citation statements)

References 21 publications

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“…1B) determined from neutron and electron diffraction were previously compared with calculation at the B3LYP/6-311 + G** level [28] and is here used as a calibration test compound for mono nitrotriphenylenes. Results for nitrobenzene were found to be in good agreement with experimental data [27,[41][42][43][44][45]. For example, in nitrobenzene the N-O bond distance is 1.2272/1.2234 Å [41] and the calculated value is 1.2245 Å. Nitrobenzene is, and has variously been predicted planar at various levels of theory [29,45,46].…”

Section: Nitrobenzenesupporting

confidence: 69%

Structure–mutagenicity relationships and energies of 1-, and 2-nitrotriphenylenes

Onchoke

2009

Journal of Molecular Structure: THEOCHEM

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Section: Nitrobenzenesupporting

confidence: 69%

Structure–mutagenicity relationships and energies of 1-, and 2-nitrotriphenylenes

Onchoke

2009

Journal of Molecular Structure: THEOCHEM

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“…The structure of nitrobenzene (the molecule depicted in Scheme 2) was determined using neutron and electron diffraction (30)(31)(32)(33)(34). Tables 1-2 compare the present calculations with experimental data, and the agreement is excellent.…”

Section: Nitrobenzenementioning

confidence: 63%

Density Functional Theoretical Study of Mono-Nitrated Fluoranthenes

Onchoke

2008

Polycyclic Aromatic Compounds

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The molecules 1-, 2-, 3-, 7-, and 8-nitrofluoranthenes are well-known mutagens and carcinogens. These environmental pollutants are emitted into the atmosphere via anthropogenic activities including diesel combustion emissions, residential home heating and reactions of nitrogen oxide (NO x ) gases with fluoranthene. The differential mutagenic potency between nitrated fluoranthenes has been proposed to emanate from the orientation of the nitro group relative to the aromatic plane. To establish the validity of the structure-function correlations requires specific crystal structures, which are unavailable. Fortunately, electronic structure calculations can be done. In this report, the structures of fluoranthene and its mono nitrated derivatives were investigated with the density functional theoretical theory at B3LYP/6-311+G** level. The structure-function correlations were examined by comparing reported mutagenicity data with calculated bond lengths, angles and dihedral angles. The relationships between the calculated structures and the reported mutagenicity in the chemical literature are discussed.

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“…Previous quantum chemical calculations of NB [28][29][30][31] were not restricted to the determination of the harmonic force field and equilibrium geometrical parameters. In Refs.…”

Section: Previous Quantum Chemical Calculationsmentioning

confidence: 99%

IR spectra of nitrobenzene and nitrobenzene-15N in the gas phase, ab initio analysis of vibrational spectra and reliable force fields of nitrobenzene and 1,3,5-trinitrobenzene. Investigation of equilibrium geometry and internal rotation in these simplest aromatic nitro compounds with one and three rotors by means of electron diffraction, spectroscopic, and quantum chemistry data

et al. 2015

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The IR spectra of gaseous nitrobenzene (NB) and its 15 N isotopomer have been obtained in the frequency range of 3500-250 cm -1 , and the far-IR spectra of their solutions and the NB neat liquid sample have been recorded in the range of 600-30 cm -1 . A detailed description of the spectra of NB and 1,3,5-trinitrobenzene (sym-TNB) and their isotopomers has been accomplished using the force fields calculated at the MP2(full)/aug-cc-pVTZ and MP2(full)/cc-pVTZ levels. Transferability of the refined scale factors for the calculated force constants obtained by the Pulay technique has been used to provide evidence for validity of both interpreting the NB and sym-TNB spectra and refining the calculated force fields. The direct and inverse spectral problems have been solved by variational technique to determine torsional energy levels and refine the potential function by optimizing the V k coefficients in its Fourier series expansion. The height of the MP2(full) barrier to internal rotation has been reduced from 5.5 to 4.5 kcal/mol due to extension of the used basis set from 6-31(d,p) to aug-cc-pVTZ. The method of joint dynamic structural analysis of the GED, MW, and vibrational spectroscopy, and ab initio data in terms of the PES parameters have been applied to investigation of equilibrium geometry and internal rotation in the nonrigid NB and sym-TNB molecules having one and three coupled internal rotors, respectively. The experimental r e -parameter values of both molecules (C 2v and D 3h point group symmetries) are in agreement with those obtained by ab initio calculations. This paper is dedicated to Professor Magdolna Hargittai on the occasion of her 70th birthday.

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Ab initio investigation of internal rotation in conjugated molecules and the orientation of NO 2 in nitroaromatics: nitrobenzene, o -monofluoro- and o , o ′-difluoro-nitrobenzenes

Cited by 26 publications

References 21 publications

Structure–mutagenicity relationships and energies of 1-, and 2-nitrotriphenylenes

Structure–mutagenicity relationships and energies of 1-, and 2-nitrotriphenylenes

Density Functional Theoretical Study of Mono-Nitrated Fluoranthenes

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