CH3CH2OCl
































 









Chlorine


Nuclear Quadrupole Coupling Constants

in Ethyl Hypochlorite

 








 








 

 





Calculation of the chlorine nuclear quadrupole coupling constant tensors in ethyl hypochlorite was made here on ropt molecular structures given by MP2/cc-pVTZ and MP2/cc-pVQZ optimization.

 








Calculated and experimental [1] nqcc's are compared in Tables 1 and 2, structure parameters in Table 3, rotational constants and electric dipole moments in Table 4.


In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.  Ø (degrees) is the angle between its subscripted parameters.  RMS is the root mean square difference between calculated and experimental diagonal nqcc's.  RSD is the calibration residual standard deviation of the B1LYP/TZV(3df,2p) model for calculation of the efg's/nqcc's. 


 








 








   







Table 1.  35Cl nqcc's in CH3CH2OCl (MHz).  Calculation was made on the (1) MP2/cc-pVTZ and (2) MP2/cc-pVQZ ropt structures.
   









Calc (1)
Calc (2)
Expt [1]
   







Xaa -
 95.28
 -
 95.19
 -
 93.96(62)

Xbb
36.31
36.29
35.76(39)

Xcc
58.97
58.89
58.20(28)

Xab -
 57.63
 -
 57.54



 







RMS
0.94 (1.5 %)
0.87 (1.4 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
57.98
57.92



Xyy
58.97
58.89



Xzz -
 116.95
 -
 116.81



ETA
0.00839
0.00836



Øz,a
20.61
20.60



Øa,OCl
21.05
21.06



Øz,OCl
  0.44
  0.46



 








 








 








   







Table 2.  37Cl nqcc's in CH3CH2OCl (MHz).  Calculation was made on the (1) MP2/cc-pVTZ and (2) MP2/cc-pVQZ ropt structures.
   









Calc (1)
Calc (2)
Expt [1]
   







Xaa -
 75.19
 -
 75.11
 -
 67.4(25)

Xbb
28.71
28.69
24.8(13)

Xcc
46.48
46.42
42.6(12)

Xab -
 45.32
 -
 45.24



 







RMS
5.50 (12.2 %)
5.45 (12.1 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 












Table 3.  CH3CH2OCl  MP2/cc-pVTZ and MP2/cc-pVQZ optimized structure parameters (Å and degrees).





 C
 C,1,B1
 H,1,B2,2,A1
 H,1,B3,2,A2,3,D1,0
 H,1,B4,2,A3,3,D2,0
 H,2,B5,1,A4,3,D3,0
 H,2,B6,1,A5,3,D4,0
 O,2,B7,1,A6,4,D5,0
 Cl,8,B8,2,A7,1,D6,0


MP2/cc-pVTZ MP2/cc-pVQZ




 B1=1.51023721
 B2=1.08707119
 B3=1.08854742
 B4=1.08707119
 B5=1.09109137
 B6=1.09109137
 B7=1.43268007
 B8=1.69583567
 A1=110.57033277
 A2=109.51622346
 A3=110.57033277
 A4=111.65770618
 A5=111.65770618
 A6=105.31789552
 A7=109.61676793
 D1=119.67470924
 D2=-120.65058151
 D3=179.3010946
 D4=-58.65051308
 D5=180.
 D6=180.
  B1=1.50718863
 B2=1.08582159
 B3=1.08733375
 B4=1.08582159
 B5=1.08998778
 B6=1.08998778
 B7=1.43212865
 B8=1.68721461
 A1=110.61188045
 A2=109.43040455
 A3=110.61188045
 A4=111.81240193
 A5=111.81240193
 A6=105.42098194
 A7=109.78083745
 D1=119.63857201
 D2=-120.72285597
 D3=179.18514061
 D4=-58.46228463
 D5=180.
 D6=180.







 







 





Table 4.  CH3CH2OCl. Rotational Constants (MHz) and Dipole Moments * (D).  ropt(1) = MP2/cc-pVTZ, ropt(2) = MP2/cc-pVQZ.

 




ropt(1) ropt(2)   Expt [1]

 



 A
 31752.7
 31895.0
 31582.01(7)

 B
   2708.7
   2720.8
   2691.084(10)

 C
   2576.2
   2588.0
   2560.916(8)

|µa|   1.58
   1.58
   1.632(10)

|µb|   1.15
   1.14
   1.079(3)

 



* Calculated by B1LYP/TZV(3df,2p) method on MP2 ropt structures.



 








 








[1] R.D.Suenram, F.J.Lovas, and D.R.Johnson, J.Mol.Spectrosc. 69,458(1978).

 








 








CH3OCl HOCl
FClO
 ClOOCl

 








 








Table of Contents




Molecules/Chlorine




 








 













CH3CH2OCl.html






Last Modified 29 Dec 2013