HOCl

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Deuterium and Chlorine


Nuclear Quadrupole Coupling Constants


in Hypochlorous Acid


 







 
 
Chlorine nqcc's in hypochlorous acid were determined first by Lindsey, Lister, and Millen [1], and subsequently by Mirri, Scappini, and Cazzoli [2], Suzuki and Guarnieri [3], Singbeil et al. [4], and Anderson, Gerry and Davis [5].  Effective, substitution, ground state average, and estimated equilibrium structures are presented by Anderson et al. [5].  Deeley [6] and Escribano, Di Lonardo, and Fusina [7] determined equilibrium structures.
 
Deuterium and chlorine nqcc's were calculated here on the equilibrium structure of Escribano, DiLonardo, and Fusina [7]. The deuterium results are presented in Table 1.  In Tables 2 and 3, calculated chlorine nqcc's are compared with the experimental values [4].  The equilibrium structures are compared in Table 3.

 

 




In Tables 1 - 3, subscripts a,b,c refer to the principal axes of the inertia tensor; 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.
 
RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percentage of the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation for the model for calculation of the nqcc's. 
 

 








   






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









Calc.
Expt.
   





2H Xaa - 73.5
Xbb 244.4
Xcc - 170.8
|Xab| 114.3
 
RSD 1.1 (0.9 %)
 
Xxx - 110.4
Xyy - 170.8
Xzz 281.2
ETA 0.215
Øz,a 72.14
Øa,OD 72.75
Øz,OD   0.61
 


 







 
   






Table 2.  Chlorine nqcc's in HOCl (MHz).
   









Calc.
Expt. [4]
   





35Cl Xaa - 122.32 - 121.958(8)
Xbb   59.83   59.519(10)
Xcc   62.48   62.439(10)
|Xab|     3.79
 
  RMS 0.28 (0.34 %)
RSD 0.49 (1.1 %)
 
Xxx   59.91   59.60 *
Xyy   62.48   62.439(10)
Xzz - 122.40 - 122.04
ETA 0.021 0.0233
Øz,a 1.19 1.20
Øa,ClO 2.26 2.26
Øz,ClO 1.07 1.06
 
   
* Calculated here from the experimental diagonal nqcc's and the calculated Xab.
 
 

   






Table 3.  Chlorine nqcc's in HOCl (MHz).
   









Calc.
Expt. [4]
   





37Cl Xaa - 96.40 - 96.233(37)
Xbb 47.16 47.002(44)
Xcc 49.24 49.231(44)
|Xab|   2.97
 
  RMS 0.13 (0.20 %)
RSD 0.44 (1.1 %)
 
Xxx 47.22 47.06 *
Xyy 49.24 49.231(44)
Xzz - 96.46 - 96.29
ETA 0.021 0.0225
Øz,a 1.18 1.19
Øa,ClO 2.25 2.25
Øz,ClO 1.07 1.06
 


 





* Calculated here from the experimental diagonal nqcc's and the calculated Xab.
 
 
Table 5.  Molecular structure parameters (Å and degrees).
re [7] re [6] re [5]
HO 0.96437 0.9643 0.9636
OCl 1.68897 1.6891 1.6908
HOCl 102.965 102.96 102.45
 
 

[1] D.C.Lindsey, D.G.Lister, and D.J.Millen, Chem.Comm. 950(1969).
[2] A.M.Mirri, F.Scappini, and G.Cazzoli, J.Mol.Spectrosc. 38,218(1971).
[3] M.Suzuki and A.Guarnieri, Z.Naturforsch. 30a,497(1975).
[4] H.E.G.Singbeil, W.D.Anderson, R.Wellington Davis, M.C.L.Gerry, E.A.Cohen, H.M.Pickett, F.J.Lovas, and R.D.Suenram, J.Mol. Spectrosc. 103,466(1984).
[5] W.D.Anderson, M.C.L.Gerry, and R.W.Davis, J.Mol. Spectrosc. 115,117(1986).
[6] C.M.Deeley, J.Mol.Spectrosc. 122,481(1987).
[7] R.M.Escribano, G.DiLonardo, and L.Fusina, Chem.Phys.Lett. 259, 614(1996).

 








 







HOBr HOI OBrO OIO

Benzoic Acid HCOOD H2CO OClO
CH3OCl FClO2 FClO3 Cl2O
 

 








Table of Contents



Molecules/Deuterium
Molecules/Chlorine
 

 













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Last Modified 2 June 2003