CF2Cl-C(=O)-CF2Cl



 









Chlorine


Nuclear Quadrupole Coupling Constants

in 1,3-Dichlorotetrafluoroacetone


 







 
 
Calculations of the chlorine nqcc's in 1,3-dichlorotetrafluoroacetone were made on structures given by MP2/6-311+G(3df) optimization with approximate re C-C, CF, and C=O, and CCl bond lengths and by  MP2/aug-cc-pVTZ optimization with approximate re C-C, CF, and C=O, and CCl bond lengths.  These calculated nqcc's are compared with experimental values in Tables 1 - 3.  Structure parameters are given in Table 4, rotational constants in Table 5.
 
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.  Øz,CCl (degrees) is the angle between the z-principal axis and the CCl axis.  ETA = (Xxx - Xyy)/Xzz.
RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percent of the average of the magnitudes of experimental nqcc's).  RSD is the residual standard deviation of the model for calculation of the nqcc's, which may be taken as an estimate of uncertainty in the calculated nqcc's (not taking into consideration inaccuracies in the structure parameters).
 
 
 
   







Table 1.  35Cl nqcc's in CF235Cl-C(=O)-CF235Cl (MHz).  Calculation was made on structures given by (1) MP2/6-311+G(3df) optimization, and (2) MP2/aug-cc-pVTZ optimization; each with approximate re bond lengths.
   










Calc (1) Calc (2)
  Expt [1]
   






35Cl Xaa - 0.72 - 0.49 - 0.1423(43)
Xbb - 32.40 - 32.56 - 32.2303(53)
Xcc 33.12 33.05 32.3726(31)
Xab - 50.76 - 50.56 - 51.62(45)
Xac ± 15.60 ± 15.57 ± 13.6938(41)
Xbc ± 18.62 ± 18.65 ± 19.44(15)
 
RMS 0.56 (2.6 %) 0.48 (2.2 %)
RSD 0.49 (1.1 %) 0.49 (1.1 %)
 
Xxx 35.80 35.70 36.1(8)
Xyy 39.37 39.30 37.7(1)
Xzz - 75.17 - 75.01 - 73.7(8)
ETA 0.0475 0.0480 0.02(1)
Øz,CCl 1.66 1.72
 

 
 
   





Table 2.  Cl nqcc's in CF235Cl-C(=O)-CF237Cl (MHz).  Calculation was made on structures given by (1) MP2/6-311+G(3df) optimization and (2) MP2/aug-cc-pVTZ optimization, each with approximate re bond lengths.
   






Calc (1)
Calc (2)   Expt
   



35Cl Xaa - 1.71 - 1.47
Xbb - 30.41 - 30.56
Xcc 32.12 32.04
Xab - 50.65 - 50.45
Xac 17.10 17.05
Xbc 20.09 20.12
 
  RMS
RSD 0.49 (1.1 %) 0.49 (1.1 %)
 
37Cl Xaa - 1.54 - 1.36
Xbb - 25.28 - 25.41
Xcc 26.83 26.77
Xab - 40.60 - 40.44
Xac - 11.43 - 11.41
Xbc - 13.21 - 13.24
 
RMS

RSD 0.44 (1.1 %) 0.44 (1.1 %)
 
 
 
   





Table 3.  37Cl nqcc's in CF237Cl-C(=O)-CF237Cl (MHz).  Calculation was made on structures given by (1) MP2/6-311+G(3df) optimization, and (2) MP2/aug-cc-pVTZ optimization; each with approximate re bond lengths.
   






Calc (1)
Calc (2)   Expt
   



37Cl Xaa - 2.31 - 2.13
Xbb - 23.80 - 23.92
Xcc 26.10 26.05
Xab - 40.51 - 40.36
Xac ± 12.61 ± 12.58
Xbc ± 14.40 ± 14.43
 
RMS
RSD 0.44 (1.1 %) 0.44 (1.1 %)
 
Xxx 28.21 28.14
Xyy 31.03 30.98
Xzz - 59.24 - 59.12
ETA 0.0475 0.0480
Øz,CCl 1.66 1.72
 
 
 
Table 4.  CF2Cl-C(=O)-CF2Cl.  Selected structure parameters (Å and degrees).  r(1) =  MP2/6-311+G(3df) optimization, and r(2) = MP2/aug-cc-pVTZ optimization, each with approximate re bond lengths.  Complete structures are given here in Z-matrix format.
 
Point Group C2   r(1)   r(2)

C(1)O 1.1944 1.1944
C(1)C(3) 1.5413 1.5408
C(1)C(4) 1.5413 1.5408
C(3,4)Cl 1.7591 1.7586
C(3)C(1)C(4) 117.10 117.17
C(3)C(1)O 121.45 121.42
C(4)C(1)O 121.45 121.42
C(1)C(3,4)Cl 108.25 108.11
ClC(3,4)C(1)O   93.27   93.38

 
 
Table 5.  CF235Cl-C(=O)-CF235Cl.  Rotational Constants (MHz).  r(1) = MP2/6-311+G(3df) optimization and r(2) = MP2/aug-cc-pVTZ optimization, each with approximate re bond lengths.
 
  r(1)   r(2)     Expt [1]
A 1539.3 1539.8 1535.29390(26)
B   723.1   723.8   713.75756(38)
C   694.9   695.4   687.04713(40)
 
 
[1] G.Kadiwar, C.T.Dewberry, G.S.Grubbs II, and S.A.Cooke, Abstract RH11, 65th OSU International Symposium on Molecular Spectroscopy, 2010.
 
 
CF2Cl-C(=O)-CF3 CH2Cl-C(=O)-CH3 CH2Cl-C(=O)-CH2Cl

 








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Last Modified 10 July 2010