Vibrational spectra and normal coordinate analysis of crystalline H$sub 2$$O$$sub 2$, D$sub 2$$O$$sub 2$, and HDO$sub 2$
A systematic investigation was carried out of the vibrational spectra of the hydrogen peroxide crystal and its deuterated analogue, using both ir and Raman spectroscopy, over the range 4000 to 50 cm/sup -1/. Mixtures of the two isotopic species up to approximately 95% deuteration were also studied to identify the fundamentals of the hybrid molecule, HDO/sub 2/. Single crystals of hydrogen peroxide oriented along two of the three crystallographic axes were examined in the Raman effect with polarized laser light. The O-H stretching bands are remarkably narrow in the Raman spectra: DELTA nu (1/2) = 20 cm/sup -1/ at -- 193 deg C compared with about 50 cm/sup in the ir. Nearly all the O-H stretching components predicted by the factor group analysis were observed but a satisfactory identification of all components of the OOH deformation modes could not be achieved. The O-O stretching frequency in D/sub 2/O/sub 2/ (872 cm/sup -1/ ) is slightly higher than in H/sub 2/O/sub 2/ (871 cm/sup -1/) co ntrary to expectations. The hydrogen bonds in the H/sub 2/O/sub 2/ crystal appear somewhat less strong (by about 10 to 15%) than those in ice. A normal coordinate analysis of the unit cell modes proved to be of considerable value in the assignment of observed frequencies. The values of the eleven principal force constants and the twenty interaction constants used to fit the 59 assigned frequencies appear reasonable and are comparable with values found for other hydrogen bonded systems. (auth)
- Research Organization:
- Laval Univ., Quebec
- NSA Number:
- NSA-29-029085
- OSTI ID:
- 4329202
- Journal Information:
- Spectrochim. Acta, v. 30, no. 3, pp. 777-796, Other Information: Orig. Receipt Date: 30-JUN-74; Bib. Info. Source: UK (United Kingdom (sent to DOE from))
- Country of Publication:
- United Kingdom
- Language:
- English
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