CF3CCl3


























 






Chlorine


Nuclear Quadrupole Coupling Constants

in 1,1,1-Trichloro-2,2,2-trifluoroethane


 








 


 





Chlorine nqcc's in all four possible chlorine isotopic species of 1,1,1-trichloro-2,2,2-trifluoroethane were determined by Kisiel et al. [1].












Calculation of the chlorine nqcc's was made on an approximate equilibrium molecular structure (~re) derived ab initio (see below), and on an reSE structure derived in Ref. [1].  These are compared with the experimental nqcc's in Tables 1,3 - 7.  Structure parameters are given in Table 2.

 








In Tables 1,3 - 7, suscripts a,b,c refer to principal inertial axes, x,y,z to principal axes of the nqcc tensor.  (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

RMS is the root mean square difference between calculated and experimental diagonal nqcc (percentage of average of absolute experimental nqcc's).  RSD is the residual standard deviation of the calibration of the B1LYP/TZV(3df,2p) computional model for calculation of the nqcc's.

 








 









   








Table 1.  35Cl(1) nqcc's in CF3C35Cl3 (MHz).  Calculation was made on ~re and reSE structures.


 
 







Calc / ~re
Calc / reSE
Expt. [1]


 








Xaa
27.52

27.44
27.55110(58)


Xbb -
69.54
- 69.52 -
69.44020(91)


Xcc
42.02

42.09
41.88910(91)


Xab
37.94

38.16 -
37.760(12) *


 







RSM

0.10 (0.21 %)

0.14 (0.30 %)




RSD

0.49 (1.1 %)

0.49 (1.1 %)












Xxx
40.59

40.65
40.5177(74)


Xyy
42.02
42.09
41.88910(91)


Xzz -
82.61
- 82.74 -
82.4069(74)


ETA

0.017

0.017
0.01664(9)


z,a
70.99

70.90
71.0475(44)


a,CCl
71.40

71.32




z,CCl
  0.41

  0.42




 








 








* Here, and in Tables that follow, differences in algebraic signs of the off-diagonal components are due only to differences in orientation of the moleule with respect to positive/negative sense of the inertial axes.  Only magnitudes of these components are to be compared.


 


















Derivation of Approximate Equilibrium Molecular Structure:  The molecular structure was optimized at the MP2/6-311+G(d,p) level of theory, the optimized CC single bond length then corrected using the equation obtained from linear regression analysis of the data given in Table IX of Ref. [2].  Likewise, the optimized CF bond lengths were corrected by regression analysis of the data given in Table VI of Ref. [3].  For the CCl bonds, the structure was optimized at the MP2/6-311+G(2d,p) level and corrected by linear regression analysis of the data given in Table 4 of Ref. [4].  Interatomic angles used in the calculation are those given by B3P86/6-311+G(3d,3p) partial  optimization (with corrected bond lengths held fixed).

 








 


 
Table 2. Molecular structure parameters ( and degrees), ~re and reSE [1],







  ~re      reSE

CCl 1.7546 1.7586(20)


CC 1.5408 1.5493(12)


CF 1.3254 1.3251(21)


CCF 110.42 110.19(31)


CCCl 108.60 108.68(21)



 


















   








Table 3.  37Cl(1) nqcc's in CF3C37Cl35Cl2 (MHz).  Calculation was made on ~re and reSE structures.


 
 







Calc / ~re
Calc / reSE
Expt. [1]


 








Xaa
18.77

18.72
18.8698(16)


Xbb -
51.88
- 51.89 -
51.8846(17)


Xcc
33.12

33.17
33.0148(17)


Xab
33.30

33.44 -
33.180(44)


 







RSM

0.08  (0.24 %)

0.13 (0.36 %)




RSD

0.49 (1.1 %)

0.49 (1.1 %)












Xxx
31.99

32.04
31.995(30)


Xyy
33.12
33.17
33.0148(17)


Xzz -
65.11
- 65.21 -
65.010(30)


ETA

0.017

0.017
0.0157(5)


z,a
68.34

68.28
68.418(19)


a,CCl
68.75

68.70




z,CCl
  0.41

  0.42




 








 


















   








Table 4.  35Cl(2,3) nqcc's in CF3C37Cl35Cl2 (MHz).  Calculation was made on ~re and reSE structures.


 
 







Calc / ~re
Calc / reSE
Expt. [1]


 








Xaa
29.24

29.15
29.2276(9)


Xbb
12.41

12.47
12.3792(15)


Xcc -
41.65
-
41.62 -
41.6068(15)


Xab -
18.27
-
18.39
18.130(35)


Xac -/+
30.59
-/+
30.80
-/+
30.459(24)


Xbc -/+
49.77
-/+
49.79
+/-
49.6361(24)


 







RSM

0.03  (0.11 %)

0.07 (0.24 %)




RSD

0.49 (1.1 %)

0.49 (1.1 %)












Xxx
40.59

40.65
40.486(16)


Xyy
42.02
42.09
41.8875(25)


Xzz -
82.61
- 82.74 -
82.373(16)


ETA

0.017

0.017
0.0170(10)


z,CCl
0.41

0.42




 




























   








Table 5.  35Cl(1) nqcc's in CF3C35Cl37Cl2 (MHz).  Calculation was made on ~re and reSE structures.


 
 







Calc / ~re
Calc / reSE
Expt. [1]


 








Xaa
30.58

30.50
30.5494(41)


Xbb
42.02

42.09
41.8697(85)


Xcc -
72.60
-
72.59 -
72.4191(85)


Xac
33.65

33.91 -
33.72(19)


 







RSM

0.14  (0.29 %)

0.16 (0.33 %)




RSD

0.49 (1.1 %)

0.49 (1.1 %)












Xxx
40.59

40.65
40.61(10)


Xyy
42.02
42.09
41.8697(85)

Xzz -
82.61
- 82.74 -
82.48(10)


ETA

0.017

0.017
0.0153(13)


z,a
73.44

73.33
73.389(75)


a,CCl
73.85

73.75




z,CCl
  0.41

  0.42




 








 









 









   








Table 6.  37Cl(2,3) nqcc's in CF3C35Cl37Cl2 (MHz).  Calculation was made on ~re and reSE structures.


 
 







Calc / ~re
Calc / reSE
Expt. [1]


 








Xaa
20.39

20.33
20.4401(27)


Xbb -
32.82
-
32.80 -
32.7801(48)


Xcc
12.43

12.47
12.3399(48)


Xab -/+
27.50
-/+
27.64 -/+
27.06(17)


Xac -
15.35
-
15.43

15.33(20)


Xbc -/+
36.93
-/+
36.95
+/-
36.860(17)


 







RSM

0.07  (0.31 %)

0.10 (0.46 %)




RSD

0.49 (1.1 %)

0.49 (1.1 %)












Xxx
31.99

32.04
31.77(11)


Xyy
33.12
33.17
33.011(43)

Xzz -
65.11
- 65.21 -
64.79(11)


ETA

0.017

0.017
0.0191(19)


z,CCl
0.41

0.42




 








 









 









   








Table 7.  37Cl(1) nqcc's in CF3C37Cl3 (MHz).  Calculation was made on ~re and reSE structures.


 
 







Calc / ~re
Calc / reSE
Expt. [1]


 








Xaa
21.68

21.62
21.7161(30)


Xbb -
54.80
- 54.79 -
54.7179(13)


Xcc
33.12

33.17
33.0035(13)


Xab
29.90

30.07 -
29.60(13)


 







RSM

0.08 (0.23 %)

0.12 (0.32 %)




RSD

0.49 (1.1 %)

0.49 (1.1 %)












Xxx
31.99

32.04
31.838(74)


Xyy
33.12
33.17
33.0035(13)


Xzz -
65.11
- 65.21 -
64.839(74)


ETA

0.017

0.017
0.0180(12)


z,a
70.99

70.90
71.123(61)


a,CCl
71.40

71.32




z,CCl
  0.41

  0.42




 


















 









[1] Z.Kisiel, L.Pszczłkowski, E.Białkowska-Jaworska, M.Jaworski, I.Uriarte, F.J.Basterretxea, and E.J.Cocinero, J.Mol.Spectrosc. 352,1(2018).


[2] J.Demaison, J.Coslou, R.Bocquet, and A.G.Lesarri, J.Mol. Spectrosc. 167,400(1994).

[3] R.M.Villamaan, W.D.Chen, G.Wlodarczak, J.Demaison, A.G.Lesarri, J.C.Lpez, and J.L.Alonso, J.Mol.Spectrosc. 171,223(1995).

[4] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).

 








 








CFCl3 SiHCl3 CH3CCl3 OPCl3

NCl3 PCl3 AsCl3 SPCl3

CH3Cl CH2Cl2 CHCl3


 








 








Table of Contents




Molecules/Chlorine




 








 













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Last Modified 21 July 2018