Vibrational spectroscopic studies of the chemical dynamics in charge transfer complexes of the type iodine-pyridine 2. Intermolecular dynamics from far infrared bands.
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| Title: | Vibrational spectroscopic studies of the chemical dynamics in charge transfer complexes of the type iodine-pyridine 2. Intermolecular dynamics from far infrared bands. |
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| Authors: | Tassaing, T., Besnard, M., Yarwood, J. |
| Source: | Molecular Physics. 10/10/97, Vol. 92 Issue 2, p281-292. 12p. |
| Subjects: | Pyridine, Iodine, Vibrational spectra, Electron donor-acceptor complexes |
| Abstract: | Detailed interpretation of the far infrared spectra of the pyridine-I complex (in ternary mixtures with an inert solvent) has been attempted using models for elucidation of intermolecular dynamics between components of a liquid mixture. For the complex very diluted in an inert solvent, in the framework of the Robertson-Yarwood model, it is found that the bandshape of the upsilon mode originates from the phase relaxation of the I-I oscillator due to its I- I anharmonic 'indirect' coupling with the upsilon mode. The frequency shifts and widths of the two bands observed at higher concentrations of pyridine in the mixture are then explored by applying the vibrational relaxation formalism of Kubo with the analytical expression of Fukuda, T., Ikawa, S., and Kimura, M., (1989, Chem. Phys ., 133,137) to treat the 'direct' coupling of the transition dipole of the complex with the dipole moment of the solvent molecule. Both phase and energy relaxation contributions have been considered. It has been found that band intensities are intimately related to the extent of charge transfer between the complex components, and that the frequency shifts and widths are dependent on these intensities and on the signs of the transition dipole. At low concentrations of donor, the harmonic contribution /q totally dominates the bandwidths, but at higher concentrations 2/2 q is needed. In addition, the upsilonband phase relaxation explains the bandwidth perfectly well, but for the (lower frequency) upsilon band there is a significant contribution from energy relaxation processes. A study of the effects of the diffusion coefficients on the bandwidths has shown that the reorientational motion of pyridine lies at the origin of the observed broadening. 2 D- I I- I D- I. [ABSTRACT FROM AUTHOR] |
| Copyright of Molecular Physics is the property of Taylor & Francis Ltd and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 7612931 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Vibrational spectroscopic studies of the chemical dynamics in charge transfer complexes of the type iodine-pyridine 2. Intermolecular dynamics from far infrared bands. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Tassaing%2C+T%2E%22">Tassaing, T.</searchLink><br /><searchLink fieldCode="AR" term="%22Besnard%2C+M%2E%22">Besnard, M.</searchLink><br /><searchLink fieldCode="AR" term="%22Yarwood%2C+J%2E%22">Yarwood, J.</searchLink> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Molecular+Physics%22">Molecular Physics</searchLink>. 10/10/97, Vol. 92 Issue 2, p281-292. 12p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Pyridine%22">Pyridine</searchLink><br /><searchLink fieldCode="DE" term="%22Iodine%22">Iodine</searchLink><br /><searchLink fieldCode="DE" term="%22Vibrational+spectra%22">Vibrational spectra</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+donor-acceptor+complexes%22">Electron donor-acceptor complexes</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Detailed interpretation of the far infrared spectra of the pyridine-I complex (in ternary mixtures with an inert solvent) has been attempted using models for elucidation of intermolecular dynamics between components of a liquid mixture. For the complex very diluted in an inert solvent, in the framework of the Robertson-Yarwood model, it is found that the bandshape of the upsilon mode originates from the phase relaxation of the I-I oscillator due to its I- I anharmonic 'indirect' coupling with the upsilon mode. The frequency shifts and widths of the two bands observed at higher concentrations of pyridine in the mixture are then explored by applying the vibrational relaxation formalism of Kubo with the analytical expression of Fukuda, T., Ikawa, S., and Kimura, M., (1989, Chem. Phys ., 133,137) to treat the 'direct' coupling of the transition dipole of the complex with the dipole moment of the solvent molecule. Both phase and energy relaxation contributions have been considered. It has been found that band intensities are intimately related to the extent of charge transfer between the complex components, and that the frequency shifts and widths are dependent on these intensities and on the signs of the transition dipole. At low concentrations of donor, the harmonic contribution /q totally dominates the bandwidths, but at higher concentrations 2/2 q is needed. In addition, the upsilonband phase relaxation explains the bandwidth perfectly well, but for the (lower frequency) upsilon band there is a significant contribution from energy relaxation processes. A study of the effects of the diffusion coefficients on the bandwidths has shown that the reorientational motion of pyridine lies at the origin of the observed broadening. 2 D- I I- I D- I. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Molecular Physics is the property of Taylor & Francis Ltd and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1080/002689797170473 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 12 StartPage: 281 Subjects: – SubjectFull: Pyridine Type: general – SubjectFull: Iodine Type: general – SubjectFull: Vibrational spectra Type: general – SubjectFull: Electron donor-acceptor complexes Type: general Titles: – TitleFull: Vibrational spectroscopic studies of the chemical dynamics in charge transfer complexes of the type iodine-pyridine 2. Intermolecular dynamics from far infrared bands. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Tassaing, T. – PersonEntity: Name: NameFull: Besnard, M. – PersonEntity: Name: NameFull: Yarwood, J. IsPartOfRelationships: – BibEntity: Dates: – D: 10 M: 10 Text: 10/10/97 Type: published Y: 1997 Identifiers: – Type: issn-print Value: 00268976 Numbering: – Type: volume Value: 92 – Type: issue Value: 2 Titles: – TitleFull: Molecular Physics Type: main |
| ResultId | 1 |
