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H2O |
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Deuterium and Oxygen |
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Nuclear
Quadrupole Coupling Constants |
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in the Water Molecule |
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The water molecule has been the subject of numerous experimental
and theoretical investigations. Relevant to this work are the publications
of Bhattacharjee, Muenter, and Marshall [1], Bellet, Lafferty, and Steenbeckeliers
[2], and Benedict, Gailar, and Plyler [3]. These authors report
respectively the deuterium nqcc's in D2O, the oxygen nqcc's
in H2O, and an equilibrium molecular structure. |
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Calculation of the deuterium and oxygen
nqcc's was made on the equilibrium structure. These results are
compared with the experimental values in Tables 1 - 3. Molecular
structure parameters are given in Table 4. |
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Subscripts a,b,c refer to the
principal axes of the inertia tensor, subscripts x,y,z to
the principal axes of the nqcc tensor. The nqcc y-axis is chosen
coincident with the inertia c-axis, these are perpendicular to the plane
of the molecule. Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
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Table 1. Deuterium nqcc's
in D2O (kHz). |
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Calc. |
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Expt. [1] |
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2H |
Xaa |
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149.5 |
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153.92(11) |
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Xbb |
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24.9 |
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22.12(11) |
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Xcc |
- |
174.4 |
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175.037(11) |
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Xab |
± |
210.3 |
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RMS |
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3.0 (2.6 %) |
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RSD |
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1.1 (0.9 %) |
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Xxx |
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132.1 |
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Xyy |
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174.4 |
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Xzz |
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306.5 |
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ETA |
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0.138 |
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Øz,a |
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36.75 |
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Øa,OD |
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37.74 |
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Øz,OD |
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0.99 |
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Table 2. Oxygen nqcc's
in H2O (MHz). |
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Calc. = B1LYP/6-311++G(3df,3p). PDF |
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Calc. |
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Expt. [1] |
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17O |
Xaa |
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- 8.941 |
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- 8.8964 |
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Xbb |
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- 1.160 |
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- 1.2104 |
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Xcc |
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10.101 |
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10.1068 |
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RMS |
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0.040 (0.59 %) |
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RSD |
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0.041 (1.4 %) |
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Table 3. Oxygen nqcc's
in H2O (MHz). |
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Calc. = MP4(SDQ)/6-311++G(3df,3pd). PDF |
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Calc. |
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Expt. [1] |
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17O |
Xaa |
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- 8.897 |
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- 8.8964 |
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Xbb |
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- 1.067 |
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- 1.2104 |
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Xcc |
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9.964 |
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10.1068 |
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RMS |
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0.117 (1.7 %) |
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RSD |
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0.022 (0.77 %) |
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| Table 4. Molecular structure parameters, re [3] (Å
and degrees). |
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OH |
0.95721 |
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HOH |
104.522 |
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[1] R.Bhattacharjee, J.S.Muenter, and M.D.Marshall, J.Mol.Spectrosc.
145,302(1991). |
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[2] J.Bellet, W.J.Lafferty, and G.Steenbeckeliers, J.Mol.Spectrosc.
47,388(1973). |
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[3] W.S.Benedict, N.Gailar, and E.K.Plyler, J.Chem.Phys. 24,1139(1956). |
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H2S |
H2CO |
H2CS |
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HCOOD |
DNO3 |
H2CCO |
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Table of Contents |
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Molecules/Deuterium |
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Molecules/Oxygen |
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H2O.html |
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Last
Modified 21 Nov 2005 |
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