CF2Cl-CCl3



 





 





 





 





 









Chlorine


Nuclear Quadrupole Coupling Constants

in CF2Cl-CCl3

 








 








 









Calculation of the chlorine nqcc tensor in CF2Cl-CCl3 was made on a molecular structure given by MP2/aug-cc-pVTZ optimization (ropt), and on same structure but with approximate equilibrium  (re) CCl, C-C, and CF bond lengths.  (Also, see Calculation of Nuclear Quadrupole Coupling Constants on Approximate Equilibrium Structures: Ethanes.)


 








Calculated nqcc tensors are shown in Tables 1 - 3.  Structure parameters are given in Table 4;  rotational constants and dipole moments in Table 5; quartic centrifugal distortion constants in Table 6.

 








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

RMS is 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 chlorine efg's/nqcc's.

NOTE:  Experimental results shown in Tables 1 - 3 have been derived here from 1.5Xaa  and  (Xbb - Xcc)/4 given in Ref. [1].


 








 








 
   








Table 1.  35Cl(1) nqcc's in CF235Cl-C35Cl3 (MHz).  Cl in CF2Cl group. See figure below for atomic numbering.

   










 ropt

  re
Expt [1]

   








Xaa - 35.53 - 35.67 -
35.0209(43)


Xbb
- 4.05

- 3.71

- 4.1681(53)


Xcc
39.58
39.38
39.1891(53)


|Xab|
55.97
55.54
55.37(12)


 







RMS
0.38 (1.4 %)

0.47 (1.8 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
38.36
38.11
37.88(12)


Xyy
39.58
39.38
39.1891(53)

Xzz - 77.94 - 77.49 -
77.07(12)


ETA
0.0156
0.0165
0.0169(15)


z,a
37.15
36.98
37.216(16)


a,CCl
39.04

38.96




z,CCl
  1.89

  1.98




 








 








 








   








Table 2.  35Cl(4) nqcc's in CF235Cl-C35Cl3 (MHz).  In-plane Cl in CCl3 group. See figure below for atomic numbering.
   










 ropt

  re
Expt [1]

   








Xaa -
25.70
-
25.83
-
24.9797(44)

Xbb -
16.73
-
16.50
-
17.1594(49)

Xcc
42.43

42.33

42.1390(49)

|Xab|
61.82

61.63

61.50(12)


 







RMS
0.52 (1.8 %)

0.63 (2.2 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
40.77

40.64

40.55(12)


Xyy
42.43

42.33

42.1390(49)

Xzz -
83.20
-
82.97
-
82.69(12)


ETA
0.0200

0.0203

0.0192(15)


z,a
42.92

42.84

43.1810(39)


a,CCl
43.51

43.44




z,CCl
  0.59

  0.60




 








 








 








   








Table 3.  35Cl(5,6) nqcc's in CF235Cl-C35Cl3 (MHz).  See figure below for atomic numbering.
   










 ropt

  re
Expt [1]

   








Xaa
40.57

40.49

39.9757(25)

Xbb
  1.94

  1.91

  1.8867(20)

Xcc -
42.51
-
42.40
-
41.8623(20)

Xab
  5.62

  5.55

  6.307(80)


Xac -/+
  6.94
-/+
  6.83

  7.70(19)


Xbc +/-
42.51
+/-
57.72
-
57.4297(43)


 







RMS
0.51 (1.8 %)

0.43 (1.6 %)




RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
40.72

40.61

40.23(13)


Xyy
42.20

42.09

42.01(11)


Xzz -
82.92
-
82.70
-
82.25(3)


ETA
0.0178

0.0180

0.0216(2)


z,CCl
0.40

0.39




 








 









 














Table 4.  CF2Cl-CCl3  MP2/aug-cc-pVTZ ropt structure parameters ( and degrees).  Approximate equilibrium bond lengths are given in parentheses.
 










 Cl
 C,1,B1
 C,2,B2,1,A1
 Cl,3,B3,2,A2,1,D1,0
 Cl,3,B4,2,A3,1,D2,0
 Cl,3,B5,2,A4,1,D3,0
 F,2,B6,3,A5,4,D4,0
 F,2,B7,3,A6,4,D5,0







 B1=1.75514006        (1.7519)
 B2=1.55930863        (1.5555)
 B3=1.76593045        (1.7627)
 B4=1.7599322          (1.7567)
 B5=1.7599322          (1.7567)
 B6=1.33777127        (1.3310)
 B7=1.33777127        (1.3310)
 A1=112.0864681
 A2=107.60919407
 A3=109.25173386
 A4=109.25173386
 A5=109.02251706
 A6=109.02251706
 D1=180.
 D2=-60.62734157
 D3=60.62734157
 D4=-58.79242767
 D5=58.79242767









 













Table 5.  CF235Cl-C35Cl3   Rotational Constants (MHz) and Dipole Moments (D).







  ropt     re      Expt [1]






A 1235.9
1242.3
1236.843683(84)

B   925.2
  929.5
  921.25227(10)

C   882.1
  886.1
  878.23725(10)

 



|a|   0.17
  0.17


|b|   0.63
  0.60



 








 








 





Table 6.  CF235Cl-C35Cl3 Quartic Centrifugal Distortion Constants (Hz).  Calc = B3LYP/cc-pVTZ
 








Calc

Expt [1]









Delta_J
37.5

34.4(27)


Delta_JK
19.6




Delta_K
- 9.4




delta_J
  2.6




delta_K
36.1




 






 








 








Z.Kisiel, E.Białkowska-Jaworska, L.Pszczłkowski, I.Uriarte, P.Ecija, F.J.Basterretxea, and  E.J.Cocinero, Abstract RF11, 70th International Symposium on Molecular Spectroscopy, Champaign-Urbana, 2015.

 








 








CHF2-CHFCl CHF2-CH2Cl CHF2-CF2Cl CH2F-CF2Cl

Calculation of Nuclear Quadrupole Coupling Constants on Approximate Equilibrium Structures: Ethanes

 








 








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Molecules/Chlorine




 








 













CF2ClCCl3.html






Last Modified 25 April 2015