H2O



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Deuterium and Oxygen


Nuclear Quadrupole Coupling Constants


in the Water Molecule


 








 








 








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]; Cazzoli, Dore, Puzzarini, and Gauss [2], Fry and Kukolich [3]; Bellet, Lafferty, and Steenbeckeliers [4]; Benedict, Gailar, and Plyler [5], and Cazzoli et al. [6].  These authors report the deuterium nqcc's in D2O, in HDO, the oxygen nqcc's in H2O, and an equilibrium molecular structure.


 








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 - 4.  Molecular structure parameters are given in Table 5.

 


 





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.  (degrees) is the angle between its subscripted parameters. ETA = (Xxx - Xyy)/Xzz.

 








 








   









Table 1.  Deuterium nqcc's in D2O (kHz).
   












Calc.
Expt. [1]
Expt. [2]
   









2H Xaa
149.5
153.92(11)
152.55(88)


Xbb
  24.9
  22.12(11)
  20.24 *


Xcc - 174.4 - 175.037(11) - 172.79 *


Xab 210.3





 









RMS


3.0 (2.6 %)
3.3 (2.9 %)


RSD
1.1 (0.9 %)





 









Xxx - 132.1






Xyy - 174.4






Xzz
306.5






ETA
0.138






z,a
36.75






a,OD
37.74






z,OD
  0.99





 









 








* Derived here from Xaa and Xbb - Xcc = 198.03(76) MHz.

 








 








   









Table 2.  Deuterium nqcc's in HDO (kHz).
   












Calc.
Expt. [6]
Expt. [3]
   









2H Xaa
274.6
277.3(9)

276.45(88)


Xbb - 100.2 -
105.1(20)
- 110.97(146)


Xcc - 174.4 -
172.2(20)
- 165.77(110)


|Xab|
114.0





 









RMS


3.5 (1.9 %)

8.0 (4.4 %)


RSD
1.1 (0.9 %)





 









 








 







 
   







Table 3.  Oxygen nqcc's in H2O (MHz).

 






Calc. = B1LYP/6-311++G(3df,3p).     PDF

 









Calc.
Expt. [4]
   







17O Xaa
- 8.941
- 8.8964


Xbb
- 1.160
- 1.2104


Xcc
10.101
10.1068

 







RMS
0.040 (0.59 %)




RSD
0.041 (1.4 %)



 







 








 








   







Table 4.  Oxygen nqcc's in H2O (MHz).

 






Calc. = MP4(SDQ)/6-311++G(3df,3pd).     PDF

 









Calc.
Expt. [4]
   







17O Xaa
- 8.897
- 8.8964


Xbb
- 1.067
- 1.2104


Xcc
  9.964
10.1068

 







RMS
0.117 (1.7 %)




RSD
0.022 (0.77 %)



 







 








 












Table 5.  Molecular structure parameters, re [5] ( and degrees).
 




OH 0.95721


HOH 104.522


   








 








[1] R.Bhattacharjee, J.S.Muenter, and M.D.Marshall, J.Mol.Spectrosc. 145,302(1991).

[2] G.Cazzoli, L.Dore, C.Puzzarini, and J.Gauss, Mol.Phys. 108,2335(2010).

[3] H.A.Fry and S.G.Kukolich, J.Chem.Phys. 76,4387(1982).

[4] J.Bellet, W.J.Lafferty, and G.Steenbeckeliers, J.Mol.Spectrosc. 47,388(1973). 

[5] W.S.Benedict, N.Gailar, and E.K.Plyler, J.Chem.Phys. 24,1139(1956).

[6] G.Cazzoli, V.Lattanzi, J.L.Alonso, J.Gauss, and C.Puzzarini, ApJ 806,1(2015).


 








"The hyperfine structure in the rotational spectra of D217O and HD17O: Confirmation of the absolute nuclear magnetic shielding scale for oxygen " C.Puzzarini, G.Cazzoli, M.E.Harding, J.Vzquez, and J.Gauss, J.Chem.Phys. 142,124308(2015).

"The rotational spectra of HD17O and D217O:  Experiment and quantum-chemical calculations" C.Puzzarini, G.Cazzoli, and J.Gauss, J.Chem.Phys. 137,154311(2012).

"A new experimental absolute nuclear magnetic shielding scale for oxygen based on the rotational hyperfine structure of H217O" C.Puzzarini, G.Cazzoli, M.E.Harding, J.Vzquez, and J.Gauss, J.Chem.Phys. 131,234304(2009).

"On equilibrium structures of the water molecule" A.G.Csszr, G.Czak, T.Furtenbacher, J.Tennyson, V.Szalay, S.V.Shirin, N.F.Zobov, and O.L.Polyansky, J.Chem.Phys. 122,214305(2005).

"Electric field gradients in water: A systematic investigation of basis set, electron correlation, and rovibrational effects" L.Olsen. O.Christiansen, L.Hemmingsen, S.P.A.Sauer, and K.Mikkelsen, J.Chem.Phys. 116,1424(2002).

F.C.De Lucia and P.Helminger, J.Mol.Spectrosc. 56,138(1975): 1.5Xaa = -13.349 MHz, (Xbb -  Xcc)/4 = -2.860 MHz

R.L.Cook, F.C.DeLucia, and P.Helminger, J.Mol.Spectrosc. 53,62(1974): re(OH) = 0.9587 and re(HOH) = 103.9o

 








 








H2S H2CO H2CS


HCOOD DNO3 H2CCO


 








 








Table of Contents




Molecules/Deuterium




Molecules/Oxygen

 








 













H2O.html






Last Modified 20 Dec 2016