Vibrational Raman spectra and intramolecular potential function of solid solutions of dimethyl ether- d and dimethyl ether- d 6
Vibrational Raman spectra of dilute solid solutions of dimethyl ether-d0 and dimethyl ether-d6 were recorded at liquid nitrogen temperatures. These data were used to develop a variety of modified internal valence force fields for specifically reflecting intermethyl potential energy coupling terms. A...
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Veröffentlicht in: | The Journal of chemical physics 1978-04, Vol.68 (8), p.3471-3480 |
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Hauptverfasser: | , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
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Zusammenfassung: | Vibrational Raman spectra of dilute solid solutions of dimethyl ether-d0 and dimethyl ether-d6 were recorded at liquid nitrogen temperatures. These data were used to develop a variety of modified internal valence force fields for specifically reflecting intermethyl potential energy coupling terms. A final 18 parameter force field was generated by applying a backward elimination statistical procedure to the least-squares refinement computation for the force constants. This force field emphasizes the importance of a methyl–methyl interaction term between out-of-plane H–C–O bending displacement coordinates. Vibrational assignments for the dimethyl ether-d0, -d3, and -d6 isotopic species were determined from the potential energy distributions calculated from the 18 parameter force field. The effects of both the tilt of the methyl group and inequivalence of the Hin-plane–C–O and Hout-of-plane–C–O angles upon the normal coordinate analysis frequency fits were assessed. |
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ISSN: | 0021-9606 1089-7690 |
DOI: | 10.1063/1.436255 |