By J. M. Pimbley
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A b o v e 150 C, the isosbestic point flattens out (Luck and Ditter, 1969). This effect can b e described quantitatively in detail up to a b o u t 400 C by a third very b r o a d absorption band with a m a x i m u m at 6850 c m " 1 . This b a n d m a y b e caused by hydrogen b o n d s with unfavored angles a r o u n d the antiparallel orientations H-O ˙ 7200 7000 I ˇ I H H. 6800 6600 6A00 cm"1 6200 Fig. 1 Below: Overtone band HOD in D 20 : 7260-6800 c m -1 region of non-hydrogenbonded or weak hydrogen-bonded OH absorption, 6800-6300 c n r 1 region of hydrogenbonded OH.
SUMMARY In contrast to fundamental IR s p e c t r o s c o p y , the overtone spectra r e p r e s e n t an extremely useful tool for studying the properties of liquid water. T h e s e spectra provide the basis for describing w a t e r and its anom› alous properties u p to a b o u t 400 C. A simplified two-state model of free or n o n - h y d r o g e n - b o n d e d O H groups and hydrogen-bonded O H groups is p r o p o s e d . T h e h y d r o g e n - b o n d e d angles are a s s u m e d to oscillate around the energy m i n i m u m .
A n energy minimum of the h y d r o g e n b o n d arises from the angle β = 0 b e t w e e n the axes of O H and the lone-pair electron orbital. A n estimate of the sharpness of this mini› m u m w a s sought by the matrix spectra of H 2 0 or C H 3 O H in solid A r or N 2 ioo[ 80 1 0 , 1 I , , I I , 50 100 150 200 250 300 350 400 U°C) Fig. 3 Spectroscopically determined content of non-hydrogen-bonded OH ( 0 F) of liq› uid water in equilibrium with vapor. 28 W. A. P. Luck (Hallam 1973; Thiel et al, 1957a, 1957b).
Advanced CMOS process technology by J. M. Pimbley