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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

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Abstract

The IR spectra of gaseous nitrobenzene (NB) and its 15N 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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Notes

  1. Up to a mirror reflection, which is unimportant for us because it does not change the results of the spectroscopic and GED experiments.

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Acknowledgments

The authors are very grateful to Professor Istvan Hargittai, member of Academia Europaea and the Hungarian Academy of Sciences, for providing an opportunity to use high-quality electron scattering intensities for the NB and sym-TNB molecules which were recorded at the Budapest University of Technology and Economics. We thank Mrs. Elizaveta Ogorodnikova for her assistance in preparing this article for publication.

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Authors and Affiliations

  1. Chemistry Department, M. V. Lomonosov Moscow State University, 119991, Moscow, Russia

    Leonid S. Khaikin, Olga E. Grikina & Denis S. Tikhonov

  2. Scientific Research Computer Center, M. V. Lomonosov Moscow State University, 119991, Moscow, Russia

    Igor V. Kochikov

  3. N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991, Moscow, Russia

    Esfir G. Baskir

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  1. Leonid S. Khaikin
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  2. Igor V. Kochikov
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Correspondence to Denis S. Tikhonov.

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Khaikin, L.S., Kochikov, I.V., Grikina, O.E. et al. 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. Struct Chem 26, 1651–1687 (2015). https://doi.org/10.1007/s11224-015-0613-9

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