Molecular structure and conformation of nitrobenzene reinvestigated by combined analysis of gas-phase electron diffraction, rotational constants, and theoretical calculations

Olga V. Dorofeeva, Yuriy V. Vishnevskiy, Natalja Vogt, Jürgen Vogt, Lyudmila V. Khristenko, Sergey V. Krasnoshchekov, Igor F. Shishkov, I. Hargittai, Lev V. Vilkov

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Abstract

The molecular structure and conformation of nitrobenzene has been reinvestigated by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) spectroscopic data, and quantum chemical calculations. The equilibrium re structure of nitrobenzene was determined by a joint analysis of the GED data and rotational constants taken from the literature. The necessary anharmonic vibrational corrections to the internuclear distances (re - ra) and to rotational constants (Be (i) - B0(i)) were calculated from the B3LYP/cc-pVTZ quadratic and cubic force fields. A combined analysis of GED and MW data led to following structural parameters (re) of planar nitrobenzene (the total estimated uncertainties are in parentheses): r(C-C) av = 1.391(3) Å, r(C-N) = 1.468(4) Å, r(N-O) = 1.223(2) Å, r(C-H)av = 1.071(3) Å, 〈 C2-C1-C6 = 123.5(6)°, 〈 C1-C2-C3 = 117.8(3)°, 〈 C2-C3-C4 = 120.3(3)°, 〈 C3-C4-C5 = 120.5(6)°, 〈 C-C-N = 118.2(3)°, 〈 C-N-O = 117.9(2)°, 〈 O-N-O = 124.2(4)°, 〈 (C-C-H)av = 120.6(20)°. These structural parameters reproduce the experimental B 0(i) values within 0.05 MHz. The experimental results are in good agreement with the theoretical calculations. The barrier height to internal rotation of nitro group, 4.1±1.0 kcal/mol, was estimated from the GED analysis using a dynamic model. The equilibrium structure was also calculated using the experimental rotational constants for nitrobenzene isotopomers and theoretical rotation-vibration interaction constants.

Original languageEnglish
Pages (from-to)739-753
Number of pages15
JournalStructural Chemistry
Volume18
Issue number6
DOIs
Publication statusPublished - Dec 2007

Fingerprint

Molecular Conformation
nitrobenzenes
Molecular Structure
Electron diffraction
Molecular structure
Conformations
molecular structure
electron diffraction
Gases
Electrons
vapor phases
Microwaves
microwaves
Vibration
dynamic models
field theory (physics)
Uncertainty
Dynamic models
nitrobenzene
vibration

Keywords

  • Ab initio and DFT calculations
  • Gas-phase electron diffraction
  • Internal rotation
  • Microwave spectroscopy
  • Molecular structure
  • Nitrobenzene

ASJC Scopus subject areas

  • Chemistry(all)
  • Structural Biology

Cite this

Molecular structure and conformation of nitrobenzene reinvestigated by combined analysis of gas-phase electron diffraction, rotational constants, and theoretical calculations. / Dorofeeva, Olga V.; Vishnevskiy, Yuriy V.; Vogt, Natalja; Vogt, Jürgen; Khristenko, Lyudmila V.; Krasnoshchekov, Sergey V.; Shishkov, Igor F.; Hargittai, I.; Vilkov, Lev V.

In: Structural Chemistry, Vol. 18, No. 6, 12.2007, p. 739-753.

Research output: Contribution to journalArticle

Dorofeeva, Olga V. ; Vishnevskiy, Yuriy V. ; Vogt, Natalja ; Vogt, Jürgen ; Khristenko, Lyudmila V. ; Krasnoshchekov, Sergey V. ; Shishkov, Igor F. ; Hargittai, I. ; Vilkov, Lev V. / Molecular structure and conformation of nitrobenzene reinvestigated by combined analysis of gas-phase electron diffraction, rotational constants, and theoretical calculations. In: Structural Chemistry. 2007 ; Vol. 18, No. 6. pp. 739-753.
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title = "Molecular structure and conformation of nitrobenzene reinvestigated by combined analysis of gas-phase electron diffraction, rotational constants, and theoretical calculations",
abstract = "The molecular structure and conformation of nitrobenzene has been reinvestigated by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) spectroscopic data, and quantum chemical calculations. The equilibrium re structure of nitrobenzene was determined by a joint analysis of the GED data and rotational constants taken from the literature. The necessary anharmonic vibrational corrections to the internuclear distances (re - ra) and to rotational constants (Be (i) - B0(i)) were calculated from the B3LYP/cc-pVTZ quadratic and cubic force fields. A combined analysis of GED and MW data led to following structural parameters (re) of planar nitrobenzene (the total estimated uncertainties are in parentheses): r(C-C) av = 1.391(3) {\AA}, r(C-N) = 1.468(4) {\AA}, r(N-O) = 1.223(2) {\AA}, r(C-H)av = 1.071(3) {\AA}, 〈 C2-C1-C6 = 123.5(6)°, 〈 C1-C2-C3 = 117.8(3)°, 〈 C2-C3-C4 = 120.3(3)°, 〈 C3-C4-C5 = 120.5(6)°, 〈 C-C-N = 118.2(3)°, 〈 C-N-O = 117.9(2)°, 〈 O-N-O = 124.2(4)°, 〈 (C-C-H)av = 120.6(20)°. These structural parameters reproduce the experimental B 0(i) values within 0.05 MHz. The experimental results are in good agreement with the theoretical calculations. The barrier height to internal rotation of nitro group, 4.1±1.0 kcal/mol, was estimated from the GED analysis using a dynamic model. The equilibrium structure was also calculated using the experimental rotational constants for nitrobenzene isotopomers and theoretical rotation-vibration interaction constants.",
keywords = "Ab initio and DFT calculations, Gas-phase electron diffraction, Internal rotation, Microwave spectroscopy, Molecular structure, Nitrobenzene",
author = "Dorofeeva, {Olga V.} and Vishnevskiy, {Yuriy V.} and Natalja Vogt and J{\"u}rgen Vogt and Khristenko, {Lyudmila V.} and Krasnoshchekov, {Sergey V.} and Shishkov, {Igor F.} and I. Hargittai and Vilkov, {Lev V.}",
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T1 - Molecular structure and conformation of nitrobenzene reinvestigated by combined analysis of gas-phase electron diffraction, rotational constants, and theoretical calculations

AU - Dorofeeva, Olga V.

AU - Vishnevskiy, Yuriy V.

AU - Vogt, Natalja

AU - Vogt, Jürgen

AU - Khristenko, Lyudmila V.

AU - Krasnoshchekov, Sergey V.

AU - Shishkov, Igor F.

AU - Hargittai, I.

AU - Vilkov, Lev V.

PY - 2007/12

Y1 - 2007/12

N2 - The molecular structure and conformation of nitrobenzene has been reinvestigated by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) spectroscopic data, and quantum chemical calculations. The equilibrium re structure of nitrobenzene was determined by a joint analysis of the GED data and rotational constants taken from the literature. The necessary anharmonic vibrational corrections to the internuclear distances (re - ra) and to rotational constants (Be (i) - B0(i)) were calculated from the B3LYP/cc-pVTZ quadratic and cubic force fields. A combined analysis of GED and MW data led to following structural parameters (re) of planar nitrobenzene (the total estimated uncertainties are in parentheses): r(C-C) av = 1.391(3) Å, r(C-N) = 1.468(4) Å, r(N-O) = 1.223(2) Å, r(C-H)av = 1.071(3) Å, 〈 C2-C1-C6 = 123.5(6)°, 〈 C1-C2-C3 = 117.8(3)°, 〈 C2-C3-C4 = 120.3(3)°, 〈 C3-C4-C5 = 120.5(6)°, 〈 C-C-N = 118.2(3)°, 〈 C-N-O = 117.9(2)°, 〈 O-N-O = 124.2(4)°, 〈 (C-C-H)av = 120.6(20)°. These structural parameters reproduce the experimental B 0(i) values within 0.05 MHz. The experimental results are in good agreement with the theoretical calculations. The barrier height to internal rotation of nitro group, 4.1±1.0 kcal/mol, was estimated from the GED analysis using a dynamic model. The equilibrium structure was also calculated using the experimental rotational constants for nitrobenzene isotopomers and theoretical rotation-vibration interaction constants.

AB - The molecular structure and conformation of nitrobenzene has been reinvestigated by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) spectroscopic data, and quantum chemical calculations. The equilibrium re structure of nitrobenzene was determined by a joint analysis of the GED data and rotational constants taken from the literature. The necessary anharmonic vibrational corrections to the internuclear distances (re - ra) and to rotational constants (Be (i) - B0(i)) were calculated from the B3LYP/cc-pVTZ quadratic and cubic force fields. A combined analysis of GED and MW data led to following structural parameters (re) of planar nitrobenzene (the total estimated uncertainties are in parentheses): r(C-C) av = 1.391(3) Å, r(C-N) = 1.468(4) Å, r(N-O) = 1.223(2) Å, r(C-H)av = 1.071(3) Å, 〈 C2-C1-C6 = 123.5(6)°, 〈 C1-C2-C3 = 117.8(3)°, 〈 C2-C3-C4 = 120.3(3)°, 〈 C3-C4-C5 = 120.5(6)°, 〈 C-C-N = 118.2(3)°, 〈 C-N-O = 117.9(2)°, 〈 O-N-O = 124.2(4)°, 〈 (C-C-H)av = 120.6(20)°. These structural parameters reproduce the experimental B 0(i) values within 0.05 MHz. The experimental results are in good agreement with the theoretical calculations. The barrier height to internal rotation of nitro group, 4.1±1.0 kcal/mol, was estimated from the GED analysis using a dynamic model. The equilibrium structure was also calculated using the experimental rotational constants for nitrobenzene isotopomers and theoretical rotation-vibration interaction constants.

KW - Ab initio and DFT calculations

KW - Gas-phase electron diffraction

KW - Internal rotation

KW - Microwave spectroscopy

KW - Molecular structure

KW - Nitrobenzene

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