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.  Ø (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)

Øz,a
37.15
36.98
37.216(16)

Øa,CCl
39.04
38.96



Øz,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)

Øz,a
42.92
42.84
43.1810(39)

Øa,CCl
43.51
43.44



Øz,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)

Øz,CCl
0.40
0.39



 








 








 













Table 4.  CF2Cl-CCl3  MP2/aug-cc-pVTZ ropt structure parameters (Å 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)

 



|µa|   0.17
   0.17

|µb|   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.Pszczółkowski, 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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Last Modified 25 April 2015