Effect of pressure on the charge-transfer band of the [Fe(CN)6]4-·dimethyl viologen ion pair

W. S. Hammack; H. G. Drickamer; D. N. Hendrickson

doi:10.1016/0009-2614(88)85171-6

Effect of pressure on the charge-transfer band of the [Fe(CN)₆]^4-·dimethyl viologen ion pair

W. S. Hammack, H. G. Drickamer, D. N. Hendrickson

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Abstract

The effect of pressure on the optical charge-transfer (CT) band of the ion pair [Fe(CN)₆]^-4·DMV²⁺ (DMV = dimethyl viologen) has been studied in aqueous solution. In the pressure range 0.001 to 10.0 kbar the CT band maximum shifted to higher energy by ≈1700 cm^-1 and the integrated intensity of the CT band increased by ≈35%, with no change in the peak width. These results accord with a vibronic coupling model describe to mixed-valence metal compounds, with a general theory of absorption spectra of ions in solution, as well as with Mulliken's theory of charge transfer. The oscillator strength of the CT band decreased by over a factor of 2 at ambient pressure with increasing concentration of the ion pair (from 1.0 to 50 mM), correlating with the change of the ionic strength over this concentration range.

Original language	English (US)
Pages (from-to)	469-473
Number of pages	5
Journal	Chemical Physics Letters
Volume	151
Issue number	4-5
DOIs	https://doi.org/10.1016/0009-2614(88)85171-6
State	Published - Oct 21 1988

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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@article{1761d7733cc94b4f83855388f08d9aee,

title = "Effect of pressure on the charge-transfer band of the [Fe(CN)6]4-·dimethyl viologen ion pair",

abstract = "The effect of pressure on the optical charge-transfer (CT) band of the ion pair [Fe(CN)6]-4·DMV2+ (DMV = dimethyl viologen) has been studied in aqueous solution. In the pressure range 0.001 to 10.0 kbar the CT band maximum shifted to higher energy by ≈1700 cm-1 and the integrated intensity of the CT band increased by ≈35%, with no change in the peak width. These results accord with a vibronic coupling model describe to mixed-valence metal compounds, with a general theory of absorption spectra of ions in solution, as well as with Mulliken's theory of charge transfer. The oscillator strength of the CT band decreased by over a factor of 2 at ambient pressure with increasing concentration of the ion pair (from 1.0 to 50 mM), correlating with the change of the ionic strength over this concentration range.",

author = "Hammack, {W. S.} and Drickamer, {H. G.} and Hendrickson, {D. N.}",

note = "Funding Information: * This work was supported in part by Materials Science Divi-sion, Department of Energy under Contract DE-ACOZ-76ER02298 and by National Institutes of Health grant HL13652.",

year = "1988",

month = oct,

day = "21",

doi = "10.1016/0009-2614(88)85171-6",

language = "English (US)",

volume = "151",

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journal = "Chemical Physics Letters",

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T1 - Effect of pressure on the charge-transfer band of the [Fe(CN)6]4-·dimethyl viologen ion pair

AU - Hammack, W. S.

AU - Drickamer, H. G.

AU - Hendrickson, D. N.

N1 - Funding Information: * This work was supported in part by Materials Science Divi-sion, Department of Energy under Contract DE-ACOZ-76ER02298 and by National Institutes of Health grant HL13652.

PY - 1988/10/21

Y1 - 1988/10/21

N2 - The effect of pressure on the optical charge-transfer (CT) band of the ion pair [Fe(CN)6]-4·DMV2+ (DMV = dimethyl viologen) has been studied in aqueous solution. In the pressure range 0.001 to 10.0 kbar the CT band maximum shifted to higher energy by ≈1700 cm-1 and the integrated intensity of the CT band increased by ≈35%, with no change in the peak width. These results accord with a vibronic coupling model describe to mixed-valence metal compounds, with a general theory of absorption spectra of ions in solution, as well as with Mulliken's theory of charge transfer. The oscillator strength of the CT band decreased by over a factor of 2 at ambient pressure with increasing concentration of the ion pair (from 1.0 to 50 mM), correlating with the change of the ionic strength over this concentration range.

AB - The effect of pressure on the optical charge-transfer (CT) band of the ion pair [Fe(CN)6]-4·DMV2+ (DMV = dimethyl viologen) has been studied in aqueous solution. In the pressure range 0.001 to 10.0 kbar the CT band maximum shifted to higher energy by ≈1700 cm-1 and the integrated intensity of the CT band increased by ≈35%, with no change in the peak width. These results accord with a vibronic coupling model describe to mixed-valence metal compounds, with a general theory of absorption spectra of ions in solution, as well as with Mulliken's theory of charge transfer. The oscillator strength of the CT band decreased by over a factor of 2 at ambient pressure with increasing concentration of the ion pair (from 1.0 to 50 mM), correlating with the change of the ionic strength over this concentration range.

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