JOURNAL OF CHEMICAL PHYSICS

VOLUME 108, NUMBER 7

15 FEBRUARY 1998

Measurement of the Raman spectrum of liquid water

David M. Carey
Lockheed Martin Corporation, Schenectady, New York 12301

Gerald M. Korenowski
Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York 12180

Received 24 September 1997; accepted 12 November 1997 The Raman spectrum from water was obtained for a range of conditions from ambient to above the critical point, 256 bar and 400 C. A uorescence-free sapphire high-pressure Raman cell was employed with which the Raman spectra from water were examined between 30 and 4000 cm 1. Computer deconvolution of the Raman OH-stretching contours allowed the hydrogen bond strength to be determined from the integrated component intensity ratios by use of the vant Hoff relationship. This procedure yielded a hydrogen bond enthalpy of 2.53 0.10 kcal/mol which is in excellent agreement with previously reported values. 1998 American Institute of Physics. S0021-9606 98 51307-4

I. INTRODUCTION A. Water structure

Water is the most important and possibly the most complex of all liquids. Its uses are innumerable, ranging from the cooling and neutron moderation of nuclear power plants, to the sustaining of life itself. The extreme versatility of water results from its unusual properties,1,2 which are totally dominated by hydrogen bonding. Such hydrogen bonding tends to be maximized, regardless of which geometrical conguration is adopted, and one feature which tends to be common to many congurations is the ve molecule tetrahedral structure depicted in Fig. 1.25

tied in the spectrum from the liquid, at virtually the same frequency.9,11 A compilation of modes, and their designations based upon specic models is given in Table I.

II. EXPERIMENTAL METHODS AND PROCEDURES

B. Previous work

Raman spectroscopy is probably the most important of the techniques which have been employed to obtain information relating to the intra- and inter-molecular vibrational modes of liquid water.2 Gaussian analysis has indicated that liquid water may have as many as seven fundamental intramolecular vibrational distributions, and as many as nine intermolecular vibrational distributions, depending of course on the specic scheme used for analysis and designation of modes.2,3,69 The use of the term distributions refers to the fact that all modes are inhomogeneously broadened, i.e., the bond lengths and bond angles are widely distributed due to intermolecular interactions. The intramolecular modes include two different 2 bending distributions, and as many as ve 1 stretching distributions. The asymmetric stretching vibration of the isolated H2O molecule, 3 B 1 , is observed at about 3755 cm 1 in the gas phase, but its equivalent has never been convincingly demonstrated to exist in the Raman spectrum of the liquid phase. In contrast, the symmetric stretching vibration of the free molecule, 1 A 1 , is seen at about 3650 cm 1 in the gas phase Raman spectrum,10 and its equivalent, in the form of a nonhydrogen-bonded or dangling OH bond, is readily iden0021-9606/98/108(7)/2669/7/$15.00 2669

The main obstacle in obtaining Raman spectra from liquid water at high temperatures and pressures involves the Raman cell. Ordinary glass Raman cells limit the temperatures to about 95 C at 1 atm.3,8,12 Very high pressures and temperatures demand the use of cells employing sapphire or diamond windows. Numerous workers have used such cells starting in the early 1960s, e.g., sapphire window cells; Allmon et al.,13 Lindner and Franck,14 Walrafen et al.,15 and diamond anvil cells; e.g., Barnett et al.16 and Walfrafen et al.17 More recently, a diamond window cell was used to observe the symmetric stretching region of water up to 500 C and 2000 bar.18 Only one study to date has achieved high temperature and high-pressure conditions using shockwave Raman techniques.19 This study examined water to the conditions of 1437 C and 257 000 bar. A serious problem with ordinary sapphire window Raman cells involves uorescence from impurities in the sapphire. This uorescence problem increases with rising temperature, particularly if low-frequency Raman spectra are required.20 Recently, however, ultra pure 99.9999% pure single crystal sapphire cells have become available from Saphikon Incorporated, Milford, New Hampshire. This ultra pure sapphire was used in the Raman cell employed in this work and was found to be uorescence free. The sapphire cell used was a plugged tube, 15 cm in length, with a wall thickness of 0.15 cm. This cell was held in an aluminum enclosure, which was heated electrically. Temperature control was provided by a PARR Instrument Company model 4842 microprocessor controller. The detailed features of the Raman cell and accompanying apparatus are shown in Fig. 2.
1998 American Institute of Physics

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FIG. 2. Schematic diagram of the high temperature high-pressure Raman apparatus. Individual parts include: a the sapphire cell within the heating enclosure; b the low-pressure water addition cylinder; c rupture disk; d transducer; e the double piston intensier; and f the nitrogen supply inlet. Heating elements and the thermocouples for temperature measurement are not shown. FIG. 1. Diagram of the fully hydrogen-bonded ve-molecule tetrahedral nearest-neighbor structure found in liquid water and in several ices Ref. 3 .

Fluid addition into the cell was provided by a 500 cc cylinder under nitrogen gas overpressure. The main pressure source for the system was a High Pressure Equipment Company model 4-2578 intensier. By controlling the nitrogen gas pressure to this intensier the internal double piston arrangement provided easy pressure control with a 5 to 1 pressure factor increase to the overall system. The nitrogen gas pressure, to both the addition cylinder and the intensier, was controlled utilizing an Air Products Inc. model E11N115H580 single stage gas regulator. System pressure was measured using a Dresser Industries Inc. model 503542, 0 to 5000 psig pressure transducer. This transducer was calibrated at the factory to an accuracy of 0.1%. A system rupture disk and a relief valve were also installed for overpressure protection. Attachment of this system to the sapphire tube was accomplished using a machined Conax Buffalo Corp. model PG5-500-B-G highpressure tting. The actual sealant used in this tting was graphite. Prior to testing, all parts were cleaned and rinsed with acetone and doubly distilled water. Doubly distilled water was also used for the test sample. The sapphire Raman cell was used with an Instruments SA Inc. Jobin Yvon model T64000 Triple Raman spectrometer. The detector was a 1024 512 pixel liquid nitrogen cooled charge coupled device CCD which provided an average spectral resolution for these experiments of 0.493 wave numbers per pixel. The excitation wavelength was the

514.532 nm line on a Lexel Laser Inc. model 3500 Argon Ion Laser. A laser power of 500 mW was measured at the entrance to the sample cell heating enclosure. Spectral data processing involved the subtraction of the Rayleigh scattering signal, a BoseEinstein thermal correction,1,5,12,20 a two-point baseline correction, and curve tting using GRAMS/386 software. The quality or goodness of t obtained was judged by the reduced 2 value; the standard rms noise calculation. Chi squared values obtained were routinely below 5.0, although above 300 C these values averaged 8.1.

III. RESULTS AND DISCUSSION A. Restricted translational modes

TABLE I. Liquid water intra- and inter-molecular bonding modes. The liquid water vibrational symmetry is provided in terms of the C 2 v structure for the librational and translational vibrations and in terms of the C s structure for the OH bending and stretching vibrations. Mode Librational Librational Librational Translational 4 Translational 2 2 OH Bending 1 OH Stretching Raman shift (cm 1) 430 650 795 162 65 1581, 1641 3051, 3233, 3393, 3511, 3628 Symmetry A2 B2 B1 A 1 , B 1 , and B 2 A1 A A

The Raman peaks related to restricted translation in liquid water are centered in the general vicinity of 65 and 162 cm 1 under ambient conditions of temperature and pressure. The so-called hydrogen bond bending Raman feature at 65 cm 1 involves OOO bending,21 whereas the hydrogen bond stretching feature at 162 cm 1 involves OO stretching along the OHO or hydrogen bond direction.1,21,22 A more general description of the 65 and 162 cm 1 Raman features involves assignment as transverse and longitudinal acoustic, TA and LA, phonons, and this description is in complete accord with the above described OOO bending and hydrogen bond stretching descriptions.23 Figure 3 depicts the nominal 65 and 162 cm 1 Raman features after the corresponding contour has been subjected to Gaussian deconvolution. The three intermolecular librational modes, which are also Raman active, are seen as broad peaks between 300 and 1000 cm 1. Table II indicates the way in which rising temperature affects the central Gaussian frequencies of the normal 65 and 162 cm 1 features. From this table it is evident that the central Gaussian frequency of the 165 cm 1 feature appears to decrease with temperature rise. This apparent decrease in energy with rising temperature suggests weakening of hydrogen bonds with temperature rise. The position of the nominal 65 cm 1 Raman feature, in contrast, appears to remain relatively xed.

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J. Chem. Phys., Vol. 108, No. 7, 15 February 1998

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FIG. 3. The Gaussian deconvoluted vibrational Raman spectrum of the 0 1000 cm 1 region of liquid water at 24 C and 128 bar pressure. The deconvoluted reduced Chi2 value for this t was 4.52. Additional spectra for the temperatures of 200 and 400 C are contained in the Appendix.

FIG. 4. The Gaussian deconvoluted vibrational Raman spectrum of the liquid water OH bending region. Environmental conditions were 24 C and 128 bar pressure. The reduced Chi2 value for this t was 1.41. Additional spectra for the temperatures of 200 and 400 C are contained in the Appendix.

B. Librational modes

The three Raman librational modes from liquid water were examined up to 400 C and 256 bar. All three Raman librational features decrease in frequency with rising tem-

perature. This frequency decrease occurs because the librational force constants decrease as the hydrogen bonding decreases. The hydrogen bonds constitute the restraining force which converts the three rotations, which the free water molecule would have in the gas phase, to the corresponding

TABLE II. Water molecular deconvoluted translational, librational, OH bending, and OH stretching Raman peak centers as a function of temperature at the constant pressure of 256 bar. Temperature C 22 Translational 65 162 Librational 430 650 795 OH bending 1581 1641 OH stretching 3051 3233 3393 3511 3628 1581 1642 3028 3242 3386 3484 3626 1591 1641 3054 3254 3393 3499 3624 1585 1640 3050 3265 3390 3490 3619 1575 1641 3050 3282 3389 3489 3615 1575 1640 3048 3291 3385 3478 3600 1561 1638 3055 3295 3385 3461 3572 3657 1597 1634 3053 3312 3391 3454 3539 3654 1584 1632 3051 3315 3405 3461 3543 3657 1584 1636 1551 1627 1588 1639 425 665 802 370 613 767 334 577 751 302 547 719 271 500 701 249 471 698 243 465 690 246 490 700 243 478 693 261 512 711 240 481 701 66 157 67 149 68 142 69 138 69 134 67 127 69 123 69 119 67 113 67 112 63 105 30 50 70 90 100 150 200 250 300 350 400

3322 3439 3485 3561 3658

3307 3460 3504 3575 3658

3314 3486 3522 3586 3658

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J. Chem. Phys., Vol. 108, No. 7, 15 February 1998

D. M. Carey and G. M. Korenowski

FIG. 5. Gaussian deconvoluted vibrational Raman spectrum of liquid water at 24 C and 128 bar pressure in the 2700 3800 cm 1 region. The reduced Chi2 value for this t was 2.51. Additional spectra at the temperatures of 200 and 400 C are contained in the Appendix.

FIG. 7. Translational and librational Spectra; 256 bar and 200 C. The deconvoluted reduced Chi2 value for this t was 3.32.

three librations in the liquid phase. The frequency decreases of the three librational modes are listed in Table II.
C. Intramolecular OH bending modes

The OH bending Raman feature nominally near 1640 cm 1 for liquid water has been found to be decomposable into two distinct Gaussian components. Such bending components have previously been thought to arise from different levels of hydrogen bonding.24 The Gaussian feature at higher frequency or energy occurs near 1640 cm 1 and

FIG. 6. The vant Hoff enthalpy determination by correlation of the slope of the ratio of the natural log of the vibrational component intensities and the inverse temperature, from 22 to 200 C at the constant pressure of 256 bar. The linear least squares t regression slope was 1.275 with an intercept constant of 3.579.

FIG. 8. Intramolecular OH bending mode Raman spectra; 256 bar and 200 C. The deconvoluted reduced Chi2 value for this t was 1.27.

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J. Chem. Phys., Vol. 108, No. 7, 15 February 1998

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FIG. 9. Intramolecular OH stretching mode Raman spectra; 256 bar and 200 C. The deconvoluted reduced Chi2 value for this t was 2.76.

FIG. 11. Intramolecular OH bending mode Raman spectra; 256 bar and 400 C. The deconvoluted reduced Chi2 value for this t was 1.95.

may correspond to partially hydrogen bonded water, whereas the other Gaussian bending component near 1581 cm 1 presumably corresponds to water molecules engaged in fully hydrogen bonded congurations. The two Gaussian components obtained in the analysis are shown in Fig. 4. The effect of temperature rise on the positions of these two Raman Gaussian features is detailed in Table II.

D. Intramolecular OH-stretching Raman modes of water

FIG. 10. Translational and librational spectra; 256 bar and 400 C. The deconvoluted reduced Chi2 value for this t was 2.72.

The region from 2700 to 3800 cm 1 relates to the OHstretching modes of liquid water. The Raman OH-stretching contour obtained in this frequency range may be deconvoluted into ve Gaussian components, as shown in Fig. 5. However, one of these ve Gaussian components could not be detected above about 300 C, and its intensity was found to decrease with rising temperature below 300 C. The various Gaussian Raman OH-stretching components are thought to arise from various amounts of hydrogen bonding, and their intensities thus change with rising temperature, as the tetrahedral hydrogen bonded structure of water is broken down. The effects of temperature on the ve Gaussian components is indicated in tabular form by Table II. However, unlike the librational component frequencies which decrease with rising temperature, it is evident from Table II that the OH-stretching Gaussian component central frequencies are relatively independent of temperature.

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The simple form of the vant Hoff expression which refers to the partial derivative of the ln K with respect to the inverse absolute temperature, with pressure held constant was used. This expression is shown as: d ln K d 1/T H . R 1

The three Gaussian Raman components whose central frequencies correspond to about 3051, 3233, and 3393 cm 1 were summed together, as described above, and used to dene the hydrogen bonded concentration. Whereas the remaining two Gaussian components whose frequencies were centered near 3511 and 3628 cm 1 were summed together to give the remaining nonhydrogen bonded concentration. That is, the ratio of the sum of three integrated Gaussian component intensities to the integrated Gaussian component intensities of the remaining two components constitutes the equilibrium constant, K, for the hydrogen bond to nonhydrogen bond reaction of liquid water. The results of the vant Hoff treatment are shown in Fig. 6. The enthalpy change corresponding to the data of Fig. 6 is 2.53 0.10 kcal/mol. This value for the enthalpy change of the hydrogen bond in water is in excellent agreement with values published previously.2,2527
FIG. 12. Intramolecular OH stretching mode Raman spectra; 256 bar and 400 C. The deconvoluted reduced Chi2 value for this t was 3.56.

IV. CONCLUSIONS AND SUMMARY

A new Gaussian component centered near 3657 cm 1 was observed at temperatures above 150 C. This new feature corresponds closely in frequency to the symmetric Raman frequency from water vapor.10 Hence, it is apparent that a small population of free nonhydrogen bonded water molecules may exist even in liquid water under saturation pressure and at elevated temperature.

The Raman spectra from water was obtained using a sapphire high pressure Raman cell. Using this setup, the intra- and inter-molecular vibrations of liquid water were all observed, measured, and deconvoluted for conditions up to and including 400 C and 256 bar pressure. Utilizing the vant Hoff enthalpy relationship, a correlation of the fully four-hydrogen bonded water structure to the three-hydrogen bonded water structure with respect to temperature provided an enthalpy difference of 2.53 0.10 kcal/mol for the energy of a hydrogen bond. This is in agreement with previous studies.
ACKNOWLEDGMENTS

E. Hydrogen bond strength

The determination of the hydrogen bond strength or enthalpy change from Raman intensity data to high temperatures at high pressure constitutes the central feature of the current Raman investigation. In the determination of the hydrogen bond enthalpy change we employed the venerable vant Hoff equation which relates the temperature dependence of an equilibrium constant to the enthalpy change. A ratio of Gaussian component integrated intensities was used to obtain the required equilibrium constant for the vant Hoff approach. More specically, the sum of the three Gaussian integrated component intensities related to hydrogen bonded concentrations was divided by the sum of the two other Gaussian integrated component intensities related to nonhydrogen bonded concentrations. We assumed, of course, that the activities needed for the equilibrium constant expression, were adequately approximated by the Raman integrated component intensities, an approximation which has been used repeatedly in Raman work dealing with liquid water.2,2527

The authors wish to express their gratitude to Dr. Peter L. Andresen of the General Electric Corporate Research and Development Center for his assistance in supporting this work and to Dr. Eric P. Plesko, for his assistance in data manipulation. G.M.K. also acknowledges support from ONR Grant No. N0001490J1537.
APPENDIX

Additional spectra are supplied for information. They include the spectra of 200 and 400 C at 256 bar pressure; Figs. 712.
1

L. Packer, Methods in Enzymology, Volume 127, Biomembranes, Part O, Protons and Water: Structure and Translocation Academic, Orlando, 1986 . 2 F. Franks, Water, a Comprehensive Treatise, Volume I, The Physics and Physical Chemistry of Water Plenum, New York, 1972 . 3 G. E. Walrafen, J. Chem. Phys. 47, 114 1967 . 4 S. A. Rice and M. G. Sceats, J. Phys. Chem. 85, 1108 1981 .

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J. Chem. Phys., Vol. 108, No. 7, 15 February 1998 G. DArrigo, G. Maisano, F. Mallamace, P. Migliardo, and F. Wanderlingh, J. Chem. Phys. 75, 4264 1981 . 6 G. E. Walrafen, J. Chem. Phys. 40, 3249 1964 . 7 G. J. Stafford, P. S. Leung, A. W. Naumann, and P. C. Schaffer, J. Chem. Phys. 50, 4444 1969 . 8 J. R. Scherer, M. K. Go, and S. Kint, J. Phys. Chem. 78, 1304 1974 . 9 G. E. Walrafen, J. Phys. Chem. 100, 10363 1996 . 10 G. Herzberg, Molecular Spectra and Molecular Structure, Volume II Van Nostrand, New York, 1951 . 11 G. E. Walrafen, W.-H. Yang, Y. C. Chu, and M. S. Hokmabadi, J. Phys. Chem. 100, 1381 1996 . 12 K. Mizoguchi, Y. Hori, and Y. Tominaga, J. Chem. Phys. 97, 1961 1992 . 13 W. E. Allmon, W. S. Hurst, W. J. Bowers, Jr., V. E. Bean, and P. J. Millett, 12th International Conference on the Properties of Water and Steam, Orlando, Florida, September 1116, 1994. 14 H. Lindner, Doctoral Dissertation, Univ. of Karlsruhe, 1970. 15 G. E. Walrafen, J. Solution Chem. 2, 159 1973 .
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