Solvatlon dynamics in N-methylamides

Curtis F. Chapman, Richard S. Fee, Mark Maroncelli

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

Solvation times in three homologous amides, N-methylformamide, N-methylacetamide, and N-methylpropionamide, have been detd. from measurements of the dynamic Stokes shift of the fluorescence spectra of two-probe solutes, prodan and coumarin 102. Single-particle reorientation times have also been measured in one of these solvents, N-methylformamide, by using NMR methods. The solvation dynamics are compared to two theoretical models, the simple continuum model and the dynamic MSA model. Although neither model predicts the time dependence of the response satisfactorily, the average solvation times observed are close to the solvent longitudinal relaxation time (τL) predicted by the simple continuum model. In contrast, the predictions of the dynamical MSA model are approximately 4 times slower than the observed solvation response. The failure of the latter model appears to result from an overestimation of the single-particle reorientation times of these solvents. Esimates of such single-particle times based on the NMR measurements are within a factor of 2 of τL. This similarity seems to account for the near equality of average solvation times to τL in the amides.

Original languageEnglish (US)
Pages (from-to)4929-4935
Number of pages7
JournalJournal of physical chemistry
Volume94
Issue number12
StatePublished - Dec 1 1990

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Solvation
solvation
methylformamide
Amides
amides
retraining
Nuclear magnetic resonance
continuums
nuclear magnetic resonance
dynamic models
Relaxation time
time dependence
Dynamic models
solutes
relaxation time
Fluorescence
fluorescence
probes
shift
predictions

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Chapman, C. F., Fee, R. S., & Maroncelli, M. (1990). Solvatlon dynamics in N-methylamides. Journal of physical chemistry, 94(12), 4929-4935.
Chapman, Curtis F. ; Fee, Richard S. ; Maroncelli, Mark. / Solvatlon dynamics in N-methylamides. In: Journal of physical chemistry. 1990 ; Vol. 94, No. 12. pp. 4929-4935.
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Chapman, CF, Fee, RS & Maroncelli, M 1990, 'Solvatlon dynamics in N-methylamides', Journal of physical chemistry, vol. 94, no. 12, pp. 4929-4935.

Solvatlon dynamics in N-methylamides. / Chapman, Curtis F.; Fee, Richard S.; Maroncelli, Mark.

In: Journal of physical chemistry, Vol. 94, No. 12, 01.12.1990, p. 4929-4935.

Research output: Contribution to journalArticle

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N2 - Solvation times in three homologous amides, N-methylformamide, N-methylacetamide, and N-methylpropionamide, have been detd. from measurements of the dynamic Stokes shift of the fluorescence spectra of two-probe solutes, prodan and coumarin 102. Single-particle reorientation times have also been measured in one of these solvents, N-methylformamide, by using NMR methods. The solvation dynamics are compared to two theoretical models, the simple continuum model and the dynamic MSA model. Although neither model predicts the time dependence of the response satisfactorily, the average solvation times observed are close to the solvent longitudinal relaxation time (τL) predicted by the simple continuum model. In contrast, the predictions of the dynamical MSA model are approximately 4 times slower than the observed solvation response. The failure of the latter model appears to result from an overestimation of the single-particle reorientation times of these solvents. Esimates of such single-particle times based on the NMR measurements are within a factor of 2 of τL. This similarity seems to account for the near equality of average solvation times to τL in the amides.

AB - Solvation times in three homologous amides, N-methylformamide, N-methylacetamide, and N-methylpropionamide, have been detd. from measurements of the dynamic Stokes shift of the fluorescence spectra of two-probe solutes, prodan and coumarin 102. Single-particle reorientation times have also been measured in one of these solvents, N-methylformamide, by using NMR methods. The solvation dynamics are compared to two theoretical models, the simple continuum model and the dynamic MSA model. Although neither model predicts the time dependence of the response satisfactorily, the average solvation times observed are close to the solvent longitudinal relaxation time (τL) predicted by the simple continuum model. In contrast, the predictions of the dynamical MSA model are approximately 4 times slower than the observed solvation response. The failure of the latter model appears to result from an overestimation of the single-particle reorientation times of these solvents. Esimates of such single-particle times based on the NMR measurements are within a factor of 2 of τL. This similarity seems to account for the near equality of average solvation times to τL in the amides.

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