Electron spin resonance investigation of carbon-13 hyperfine interactions in nitrobenzene anion radical

Swartz, Grace L.; Gulick, Wilson M.

doi:10.1080/00268977500102411

Cited by 22 publications

(14 citation statements)

References 19 publications

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“…In addition, an analysis of atomic spin density for the ,B, state predicts a spin population on nitrogen and on the C,, C,, and C, atoms (Fig. 3) in agreement with the electron spin resonance results (33). Additional geometry optimizations carried out in the ROHF formalism provide an unreliable spin density population on the whole molecule, predicting a high value on nitrogen, but a negligible spin density on the benzene ring.…”

Section: Molecular Structuressupporting

confidence: 60%

Abinitio study on radical anions of nitro compounds

Ramondo¹

1992

Can. J. Chem.

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This paper is dedirnted to Professor Sigeru Huzinaga on the occasion of his 65th birthdayFABIO RAMONDO. Can. J. Chem. 70, 3 14 (1992).The results of ab itritio molecular orbital calculations on some nitro compounds, RN02 (R = CH,, CF,, CH,F, BH,, BF,, BHF, C6H5) and on the corresponding radical anions are reported. The geometries of the neutral and charged species were optimized at the SCF and MP2 levels of theory employing the 6-31G* and the 6-3 1 +G* basis sets. The rotation about the CN and BN bonds reveals distinct conformations for each molecule and vibrational frequencies were determined for such structures. All the employed levels of theory predict structural differences between neutral and charged molecules. The major geometrical changes occurring by electron adding to R N 0 2 consist in the lengthening of the NO bonds and in the shortening of the CN and BN bonds. The radical anions are calculated to be pyramidal at nitrogen in the stable conformers of CH,NO,-, CF3N02-, CH,FNO,-, while, for the T-electron-accepting substituents (BH,, BHF, BF,, C6H5), the anion is planar. Electron correlation energy corrections in the framework of Moiler-Plesset perturbation theory were included to determine relative stabilities between different conformations. At the MP4/6-3 1G*//MP2/ 6-31G* level, an easy rotation of the NO, group is predicted for all the radical anions and neutral molecules with the exception of BH?NO,-, BF2N02-, and BHFN0,-, which show high torsional barriers about the BN bond.

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Section: Molecular Structuressupporting

confidence: 60%

Abinitio study on radical anions of nitro compounds

Ramondo¹

1992

Can. J. Chem.

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“…This result confirms our expectations that the excess electron should be localized on the -NO 2 moiety of the molecule. Furthermore, according to the experiments in the gas-phase, 31 in solution, 32 and in the crystal, 33 both the neutral 31 nitrobenzene and its radical anion 32,33 have planar geometry due to the conjugation of the p-orbitals of oxygen atoms with the -electron orbital of the aromatic ring. Be- cause of this restriction in the degrees of freedom for -NO 2 moiety, the primary effect of the excess electron is to lengthen the N-O bonds in the anion.…”

Section: B Photoelectron "Photodetachment… Spectramentioning

confidence: 99%

Electron binding to valence and multipole states of molecules: Nitrobenzene, para- and meta-dinitrobenzenes

Desfrançois

Périquet

Lyapustina

et al. 1999

The Journal of Chemical Physics

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Low-energy photoelectron imaging spectroscopy of nitromethane anions: Electron affinity, vibrational features, anisotropies, and the dipole-bound state J. Chem. Phys. 130, 074307 (2009); 10.1063/1.3076892Effect of excess electron and one water molecule on relative stability of the canonical and zwitterionic tautomers of glycine Nitrobenzene anions (NB Ϫ ) in both valence and dipole bound states are examined using laser ͑photodetachment͒ photoelectron and Rydberg electron transfer ͑RET͒ spectroscopies. Photoelectron spectroscopy of the valence NB Ϫ anion yields a valence ͑adiabatic͒ electron affinity of 1.00Ϯ0.01 eV. The reaction rates for charge transfer between atoms of cesium and xenon in high Rydberg states ͓Cs(ns,nd) and Xe(n f )͔ and NB exhibit a prominent peak in their n-dependencies consistent with the formation of a dipole bound anion having an electron affinity of 28 meV. Para-dinitrobenzene ͑pDNB͒ has a zero dipole moment and a large quadrupole moment. RET studies with pDNB show a complex n-dependence. The rate of formation of pDNB Ϫ ions exhibits a broad peak at low n-values and a second very broad feature extending to large n-values. The peak at low n is tentatively attributed to charge exchange into a quadrupole bound state (EA qb ϭ25 meV). The absence of field-detachment for these ions suggests that if these are in a quadrupole bound state they are strongly coupled to the valence state. Meta-dinitrobenzene ͑mDNB͒ has a large dipole moment and a small quadrupole moment. The observation of a weak but narrow peak at a low n-value in the RET measurement is consistent with electron attachment into a primarily dipole bound state (EA db ϭ68 meV) which is also strongly coupled to the valence state.

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“…This was attempted by Miller and Gulick [19] who studied hydrogen-bonded complexes between 1 ~ and water by means of INDO calculations. Investigation of the solvent dependence of aci, however, indicated that the radical remained planar [13]. Investigation of the solvent dependence of aci, however, indicated that the radical remained planar [13].…”

Section: Introductionmentioning

confidence: 94%

“…Few radicals have attracted the attention of ESR spectroscopists and theoreticians as nitrobenzene radical anions [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]34]. A main reason for the continuing interest in these species is the unusually large sensitivity of the measured hyperfine couplings to structural and solvational perturbations.…”

Section: Introductionmentioning

confidence: 99%

“…Later experimental investigations [10][11][12][13][14][15], in particular by Gulick and Geske and their coworkers, have made available several 170 and 13C coupling constants for the nitrobenzene and 1,4-dinitrobenzene radical anions 1 ~ and 2 ~ and their derivatives. The 170 constants show a significant trend; in the case of 1 ~ and 2= the magnitude increases slightly by increasing solvent polarity, but the trend is reversed in the pentamethyl derivative of 1 ~ where the nitro group is strongly hindered.…”

Section: Introductionmentioning

confidence: 99%

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Structure and solvation of nitrobenzene and 1,4-dinitrobenzene radical anions

Spanget‐Larsen

1979

Theoret. Chim. Acta

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An INDO method extended to include a contribution from the solvent by means of an effective solvent field (INDO-ESF) and based on properly optimized geometries is applied to the nitrobenzene and 1,4-dinitrobenzene radical anions. The hyperfine couplings and their solvent sensitivities are reproduced within a planar structure of the radicals. The behaviour of 14N and lvO splittings in derivatives with twisted nitro groups is accounted for with no difficulty.Key words: INDO method with inclusion of an effective solvent field-Nitrobenzene and 1,4-dinitrobenzene radical anions, spin distribution and geometries of

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Electron spin resonance investigation of carbon-13 hyperfine interactions in nitrobenzene anion radical

Cited by 22 publications

References 19 publications

Abinitio study on radical anions of nitro compounds

Abinitio study on radical anions of nitro compounds

Electron binding to valence and multipole states of molecules: Nitrobenzene, para- and meta-dinitrobenzenes

Structure and solvation of nitrobenzene and 1,4-dinitrobenzene radical anions

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