CF3CF2C(=O)Cl



 









Chlorine


Nuclear Quadrupole Coupling Constants


in Perfluoropropionyl Chloride


 







 

 







Calculation of the Cl nqcc tensor in propionyl chloride was made here on structures given by (1)  MP2/6-311+G(3df,3pd) optimization with approximate re bond lengths and (2) MP2/aug-cc-pVTZ optimization with approximate re bond lengths.  Calculated and experimental [1] nqcc's are compared in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.
 
In Tables 1 and 2, 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 c-axis.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.
RMS is the root measn square difference between calculated and experimental diagonal nqcc's (percent of the average of the absolute experimental nqcc's).  RSD is the residual standard deviation of the calibration of the computional model for calculation of the nqcc's.
 
 
 






Table 1.  35Cl nqcc's in CF3CF2C(=O)Cl (MHz).  Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized molecular structures, each with empirically derived approximate equilibrium bond lengths.
 








Calc (1) Calc (2)
  Expt [1]
 





Xaa - 49.14 - 48.90 - 49.7148(61)
Xbb 26.28 26.04 25.4688(90)
Xcc 22.86 22.85 24.2460(66)
|Xab| 38.75 38.96 37.77(21)
 
RMS 0.98 (3.0 %) 0.99 (3.0 %)
RSD 0.49 (1.1 %) 0.49 (1.1 %)
 
Xxx 42.64 42.63 41.17(15)
Xyy 22.86 22.85 24.246(7)
Xzz - 65.50 - 65.48 - 65.41(15)
ETA - 0.302 - 0.302 - 0.2587(24)
Øz,a 22.89 23.06 22.569(81)
Øa,CCl 24.29 24.45
Øz,CCl   1.39   1.39
 
 
 
 






Table 2.  37Cl nqcc's in CF3CF2C(=O)Cl (MHz).  Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized molecular structures, each with empirically derived approximate equilibrium bond lengths.
 








Calc (1) Calc (2)
  Expt [1]
 





Xaa - 38.81 - 38.62 - 39.256(11)
Xbb 20.79 20.61 20.147(16)
Xcc 18.02 18.01 19.109(12)
|Xab| 30.46 30.62 29.84(13)
 
RMS 0.78 (3.0 %) 0.78 (3.0 %)
RSD 0.49 (1.1 %) 0.49 (1.1 %)
 
Xxx 33.61 33.60
Xyy 18.02 18.01
Xzz - 51.62 - 51.61
ETA - 0.302 - 0.302
Øz,a 22.81 22.98
Øa,CCl 24.21 24.37
Øz,CCl   1.39   1.39
 
 
 
 
Table 3.  Perfluoropropionyl Chloride.  Selected structure parameters (Å and degrees).  r(1) =  MP2/6-311+G(3df,3pd) and r(2) = MP2/aug-cc-pVTZ optimized molecular structures, each with empirically derived approximate equilibrium bond lengths.  Complete structures are given here in Z-matrix format.
 
Cs   r(1)   r(2)
ClC(8) 1.7439 1.7450
C(8)O 1.1843 1.1836
C(8)C(1) 1.5388 1.5392
C(1)C(2) 1.5394 1.5397
C(1)C(8)Cl 111.24 111.01
C(1)C(8)O 124.40 124.66
C(2)C(1)C(8) 112.82 112.93


 
 
Table 4.  Perfluoropropionyl Chloride.  Rotational Constants (MHz).  CF3CF2C(=O)35Cl species.  r(1) =  MP2/6-311+G(3df,3pd) and r(2) = MP2/aug-cc-pVTZ optimized molecular structures, each with empirically derived approximate equilibrium bond lengths.
 
  r(1)   r(2)   Expt. [1]
A 2034.8 2036.7 2015.71840(19)
B   852.5   851.9   842.99816(13)
C   763.8   763.1   755.97374(14)
 
 
[1]  G.S.Grubbs II, R.A.Powoski, D.Jojola, and S.A.Cooke, J.Phys.Chem. A 114,8009(2010). 

 








 








HC(=O)Cl CH3C(=O)Cl (CH3)3C-C(=O)Cl FC(=O)Cl

CH3CH2C(=O)Cl BrCH2C(=O)Cl FCH2C(=O)Cl HCCC(=O)Cl
ClCH2C(=O)Cl s-t-CH2=CHC(=O)Cl
 

 








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Molecules/Chlorine
 

 













CF3CF2COCl.html






Last Modified 2 Aug 2010