A priori results for molecular geometry, scaled quantum mechanical (SQM) force field, and vibrational spectra of pyridazine

Attila R. Bérces, P. Szalay, Ildikó Magdó, G. Fogarasi, Gábor Pongor

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Abstract

For the ground electronic state of pyridazine, two kinds of molecular data, the molecular geometry and the harmonic force field, have been determined theoretically at the ab initio Hartree-Fock level using the 4-21G basis set. In order to compensate for the systematic errors of both sets of computed molecular data, empirical corrections were used with the help of a few parameters whose values have been calibrated previously on model molecule(s). Thus, the resulting corrected data are a priori for pyridazine. These a priori molecular data are regarded as good estimates of the "true" values of the corresponding data. The a priori molecular geometry of pyridazine [r(N1N2) = 133.8 pm, r(N2C3) = 132.6 pm, r(C3C4) = 140.4 pm, r(C4C5) = 137.9 pm, r(C3H3) = 107.4 pm, r(C4H4) = 107.5 pm, α(NNC) = 119.8°, α(NCC) = 123.2°, α(CCC) = 117.1°, α(NCH) = 115.7°, and α(C3C4H4) = 120.6°] is presently the best equilibrium structure for the gaseous molecule and shows less aromatic character for this molecule than expected: this is manifested by the significant alternation of bond lengths around the ring. Our results are in excellent agreement with the ring structure of a recent X-ray analysis of pyridazine at 100 K. The a priori scaled quantum mechanical (SQM) force field of pyridazine (transferring all the required scale factors from the benzene molecule) is regarded as physically the most correct and the most accurate harmonic force field of this molecule. On the basis of this force field, the a priori vibrational spectra of pyridazine-h4 and pyridazine-d4 have been determined as if the experimental vibrational spectra of both molecules were completely unknown. Comparison with experimental spectra, after a few reassignments, shows 15.6 and 30 cm-1 for the mean and the maximal individual deviations, respectively. (Only the non-CH/CD stretching frequencies were considered.) Computed IR intensities are generally in agreement with experiments at a qualitative level.

Original languageEnglish
Pages (from-to)1356-1363
Number of pages8
JournalJournal of Physical Chemistry
Volume97
Issue number7
Publication statusPublished - 1993

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Vibrational spectra
vibrational spectra
field theory (physics)
Molecules
Geometry
geometry
molecules
harmonics
Systematic errors
ring structures
X ray analysis
alternations
Bond length
Electronic states
systematic errors
Stretching
pyridazine
Benzene
benzene
deviation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

A priori results for molecular geometry, scaled quantum mechanical (SQM) force field, and vibrational spectra of pyridazine. / Bérces, Attila R.; Szalay, P.; Magdó, Ildikó; Fogarasi, G.; Pongor, Gábor.

In: Journal of Physical Chemistry, Vol. 97, No. 7, 1993, p. 1356-1363.

Research output: Contribution to journalArticle

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title = "A priori results for molecular geometry, scaled quantum mechanical (SQM) force field, and vibrational spectra of pyridazine",
abstract = "For the ground electronic state of pyridazine, two kinds of molecular data, the molecular geometry and the harmonic force field, have been determined theoretically at the ab initio Hartree-Fock level using the 4-21G basis set. In order to compensate for the systematic errors of both sets of computed molecular data, empirical corrections were used with the help of a few parameters whose values have been calibrated previously on model molecule(s). Thus, the resulting corrected data are a priori for pyridazine. These a priori molecular data are regarded as good estimates of the {"}true{"} values of the corresponding data. The a priori molecular geometry of pyridazine [r(N1N2) = 133.8 pm, r(N2C3) = 132.6 pm, r(C3C4) = 140.4 pm, r(C4C5) = 137.9 pm, r(C3H3) = 107.4 pm, r(C4H4) = 107.5 pm, α(NNC) = 119.8°, α(NCC) = 123.2°, α(CCC) = 117.1°, α(NCH) = 115.7°, and α(C3C4H4) = 120.6°] is presently the best equilibrium structure for the gaseous molecule and shows less aromatic character for this molecule than expected: this is manifested by the significant alternation of bond lengths around the ring. Our results are in excellent agreement with the ring structure of a recent X-ray analysis of pyridazine at 100 K. The a priori scaled quantum mechanical (SQM) force field of pyridazine (transferring all the required scale factors from the benzene molecule) is regarded as physically the most correct and the most accurate harmonic force field of this molecule. On the basis of this force field, the a priori vibrational spectra of pyridazine-h4 and pyridazine-d4 have been determined as if the experimental vibrational spectra of both molecules were completely unknown. Comparison with experimental spectra, after a few reassignments, shows 15.6 and 30 cm-1 for the mean and the maximal individual deviations, respectively. (Only the non-CH/CD stretching frequencies were considered.) Computed IR intensities are generally in agreement with experiments at a qualitative level.",
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T1 - A priori results for molecular geometry, scaled quantum mechanical (SQM) force field, and vibrational spectra of pyridazine

AU - Bérces, Attila R.

AU - Szalay, P.

AU - Magdó, Ildikó

AU - Fogarasi, G.

AU - Pongor, Gábor

PY - 1993

Y1 - 1993

N2 - For the ground electronic state of pyridazine, two kinds of molecular data, the molecular geometry and the harmonic force field, have been determined theoretically at the ab initio Hartree-Fock level using the 4-21G basis set. In order to compensate for the systematic errors of both sets of computed molecular data, empirical corrections were used with the help of a few parameters whose values have been calibrated previously on model molecule(s). Thus, the resulting corrected data are a priori for pyridazine. These a priori molecular data are regarded as good estimates of the "true" values of the corresponding data. The a priori molecular geometry of pyridazine [r(N1N2) = 133.8 pm, r(N2C3) = 132.6 pm, r(C3C4) = 140.4 pm, r(C4C5) = 137.9 pm, r(C3H3) = 107.4 pm, r(C4H4) = 107.5 pm, α(NNC) = 119.8°, α(NCC) = 123.2°, α(CCC) = 117.1°, α(NCH) = 115.7°, and α(C3C4H4) = 120.6°] is presently the best equilibrium structure for the gaseous molecule and shows less aromatic character for this molecule than expected: this is manifested by the significant alternation of bond lengths around the ring. Our results are in excellent agreement with the ring structure of a recent X-ray analysis of pyridazine at 100 K. The a priori scaled quantum mechanical (SQM) force field of pyridazine (transferring all the required scale factors from the benzene molecule) is regarded as physically the most correct and the most accurate harmonic force field of this molecule. On the basis of this force field, the a priori vibrational spectra of pyridazine-h4 and pyridazine-d4 have been determined as if the experimental vibrational spectra of both molecules were completely unknown. Comparison with experimental spectra, after a few reassignments, shows 15.6 and 30 cm-1 for the mean and the maximal individual deviations, respectively. (Only the non-CH/CD stretching frequencies were considered.) Computed IR intensities are generally in agreement with experiments at a qualitative level.

AB - For the ground electronic state of pyridazine, two kinds of molecular data, the molecular geometry and the harmonic force field, have been determined theoretically at the ab initio Hartree-Fock level using the 4-21G basis set. In order to compensate for the systematic errors of both sets of computed molecular data, empirical corrections were used with the help of a few parameters whose values have been calibrated previously on model molecule(s). Thus, the resulting corrected data are a priori for pyridazine. These a priori molecular data are regarded as good estimates of the "true" values of the corresponding data. The a priori molecular geometry of pyridazine [r(N1N2) = 133.8 pm, r(N2C3) = 132.6 pm, r(C3C4) = 140.4 pm, r(C4C5) = 137.9 pm, r(C3H3) = 107.4 pm, r(C4H4) = 107.5 pm, α(NNC) = 119.8°, α(NCC) = 123.2°, α(CCC) = 117.1°, α(NCH) = 115.7°, and α(C3C4H4) = 120.6°] is presently the best equilibrium structure for the gaseous molecule and shows less aromatic character for this molecule than expected: this is manifested by the significant alternation of bond lengths around the ring. Our results are in excellent agreement with the ring structure of a recent X-ray analysis of pyridazine at 100 K. The a priori scaled quantum mechanical (SQM) force field of pyridazine (transferring all the required scale factors from the benzene molecule) is regarded as physically the most correct and the most accurate harmonic force field of this molecule. On the basis of this force field, the a priori vibrational spectra of pyridazine-h4 and pyridazine-d4 have been determined as if the experimental vibrational spectra of both molecules were completely unknown. Comparison with experimental spectra, after a few reassignments, shows 15.6 and 30 cm-1 for the mean and the maximal individual deviations, respectively. (Only the non-CH/CD stretching frequencies were considered.) Computed IR intensities are generally in agreement with experiments at a qualitative level.

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