Electron states of benzene…HCl and toluene…HCl hydrogen bonded complexes by ultraviolet photoelectron spectroscopy

Ananthavel, S. P.; Ganguly, Bishwajit; Chandrasekhar, Jayaraman; Hegde, M. S.; Rao, C. N. R.

doi:10.1016/0009-2614(93)e1352-h

Cited by 6 publications

(7 citation statements)

References 15 publications

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“…5 Bromine and benzene obtained commercially are freshly distilled. The samples are taken in glass ampoules.…”

Section: Experiments and Computational Methodsmentioning

confidence: 99%

“…In an attempt to understand the D-A interaction, a series of molecular complexes have been studied in this laboratory by photoelectron spectroscopy and ab initio MO study. 5 Since the ionization energies of g orbitals of I 2 and orbitals of benzene are about the same at 9.3 eV and that of Br 2 and benzene are well separated, a benzenebromine D-A complex is chosen for this study. Here we report the first study of the D-A complex of benzene and bromine by ultraviolet photoelectron spectroscopy and ab initio MO calculations.…”

Section: Introductionmentioning

confidence: 99%

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Electron states of benzene–Br2 donor–acceptor complex: HeI photoelectron spectroscopy and ab initio molecular orbital study

Ananthavel

Hegde

1996

The Journal of Chemical Physics

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HeI photoelectron spectrum of weakly bonded π-donor complex of benzene with Br2 is obtained. Benzene orbitals are shifted to higher binding energy by 0.25 eV and the bromine orbitals to lower binding energy by about 0.5 eV due to the complex formation. Ab initio molecular orbital calculations predicted a weak π→σ* complex between benzene and bromine having a C6v symmetry. The charge transfer is from the benzene π cloud to the bromine orbital. The magnitude of charge transfer computed from natural bond orbital analysis is 0.002.

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“…5 Bromine and benzene obtained commercially are freshly distilled. The samples are taken in glass ampoules.…”

Section: Experiments and Computational Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electron states of benzene–Br2 donor–acceptor complex: HeI photoelectron spectroscopy and ab initio molecular orbital study

Ananthavel

Hegde

1996

The Journal of Chemical Physics

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“…This is the first theoretical report on the benzene···ICl complex, and for the first time electron spectroscopy is used to study a benzene−interhalogen complex. Ultraviolet photoelectron spectroscopy (UVPES) is a powerful tool to study weakly bound complexes in the gas phase, , but none of the investigations reported so far on benzene−halogen complexes, barring a recent report by us on the benzene−bromine complex, have employed this technique. UVPES could give electron states of the complex and monomers, and therefore it could reveal the nature of interactions in the complex at the orbital level.…”

Section: Introductionmentioning

confidence: 99%

Structure of the Benzene···ICl Complex: A UVPES and ab Initio Molecular Orbital Study

et al. 1998

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UVPES studies and ab initio and DFT computations have been done on the benzene‚‚‚ICl complex; electron spectral data and computed orbital energies show that donor orbitals are stabilized and acceptor orbitals are destabilized due to complexation. Calculations predict an oblique structure for the complex in which the interacting site is a CdC bond center in the donor and iodine atom in the acceptor, in full agreement with earlier experimental reports. BSSE-corrected binding energies closely match the enthalpy of complexation reported, and the NBO analysis clearly reveals the involvement of the π orbital of benzene and the σ* orbital of ICl in the complex.

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“…The molecular complexes of amines with halogens that fall under the category of charge-transfer complexes were known well before the charge transfer theory was proposed by Mulliken ultraviolet photoelectron spectroscopy (UVPES), and electron energy loss spectroscopy (EELS). Theoretical methods have also been employed to study them, as they are especially suitable for vapor-phase phenomena.…”

Section: Introductionmentioning

confidence: 99%

UVPES and ab Initio Molecular Orbital Studies on the Electron Donor−Acceptor Complexes of Bromine with Methylamines

et al. 1997

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The He I photoelectron spectra of bromine, methylamine, and their complex have been obtained, and the spectra show that lone-pair orbital energy of nitrogen in methylamine is stabilized by 1.8 eV and the bromine orbital energies are destabilized by about 0.5 eV due to complexation. Ab initio calculations have been performed on the charge-transfer complexes of Br2 with ammonia and methyl-, dimethyl-, and trimethylamines at the 3-21G*, 6-311G, and 6-311G* levels and also with effective core potentials. Calculations predict donor and acceptor orbital energy shifts upon complexation, and there is a reasonable agreement between the calculated and experimental results. Complexation energies have been corrected for BSSE. Frequency analysis has confirmed that ammonia and trimethylamine form complexes with C 3 v symmetry and methylamine and dimethylamine with C s symmetry. Calculations reveal that the lone-pair orbital of nitrogen in amine and the σ* orbital of Br2 are involved in the charge-transfer interaction. LANL1DZ basis seems to be consistent and give a reliable estimate of the complexation energy. The computed complexation energies, orbital energy shifts, and natural bond orbital analysis show that the strength of the complex gradually increases from ammonia to trimethylamine.

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Electron states of benzene…HCl and toluene…HCl hydrogen bonded complexes by ultraviolet photoelectron spectroscopy

Cited by 6 publications

References 15 publications

Electron states of benzene–Br2 donor–acceptor complex: HeI photoelectron spectroscopy and ab initio molecular orbital study

Electron states of benzene–Br2 donor–acceptor complex: HeI photoelectron spectroscopy and ab initio molecular orbital study

Structure of the Benzene···ICl Complex: A UVPES and ab Initio Molecular Orbital Study

UVPES and ab Initio Molecular Orbital Studies on the Electron Donor−Acceptor Complexes of Bromine with Methylamines

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