CHF2Cl




























 









Chlorine


Nuclear Quadrupole Coupling Constants


in Chlorodifluoromethane


 








 








 








Calculation of the chlorine nqcc's in chlorodifluoromethane was made on the substitution and average molecular structures of Cramb et al. [1], and on ropt = CCSD(T)_AE/wCVQZ and reSE molecular structures of Vogt et al. [2].  These results are compared with the experimental nqcc's of Blanco et al. [3] for 35Cl and Cramb et al. for 37Cl in Tables 1 and 2.  Structure parameters are shown in Table 3.  Earlier investigations of the nqcc's and molecular structure were made by McLay and Mann [4] and Beeson, Weatherly, and Williams [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.  ETA = (Xxx - Xyy)/Xzz.  (degrees) is the angle between its subscripted parameters. 


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


 








 








 
   








Table 1.  35Cl nqcc's in CHF2Cl (MHz).  Calculation was made on the rs and rz molecular structures of Cramb et al. [1].
   










Calc /rs
Calc /rz
Expt. [3]
   








Xaa - 65.91 - 66.50 - 65.0239(65)

Xbb
35.56
35.57
35.467(14)

Xcc
30.34
30.93
29.566(14)

|Xac|
26.37
26.21
24.(5)

 







RMS
0.68 (1.6 %)
1.16 (2.7 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 








 








 








   








Table 2.  35Cl nqcc's in CHF2Cl (MHz).  Calculation was made on the ropt = CCSD(T)_AE/wCVQZ and reSE molecular structures of Vogt et al. [2].
   










Calc /ropt
Calc /reSE
Expt. [3]
   








Xaa - 65.30 - 65.17 - 65.0239(65)

Xbb
35.44
35.46
35.467(14)

Xcc
29.86

29.70
29.566(14)

|Xac|
26.47
26.77
24.(5)

 







RMS
0.23 (0.54 %)
0.11 (0.26 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
36.73
36.74

35.3(25)

Xyy
35.44
35.46
35.467(14)

Xzz - 72.17 -
72.20
- 70.8(25)

ETA -
0.018 -
0.018

0.0024(390)

z,a
14.55
14.72

13.4(25)

a,CCl
14.25
14.34




z,CCl
  0.29

  0.38




 








 









 








   








Table 3.  37Cl nqcc's in CHF2Cl (MHz).  Calculation was made on the rs and rz molecular structures of Cramb et al. [1].
   










Calc /rs
Calc /rz
Expt. [1]
   








Xaa - 51.99 - 52.46 - 51.342(31)

Xbb
28.03
28.03
27.920

Xcc
23.96
24.42
23.422

|Xac|
20.70
20.57



 







RMS
0.49 (1.4 %)
0.87 (2.5 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 








   








Table 4.  37Cl nqcc's in CHF2Cl (MHz).  Calculation was made on the ropt  = CCSD(T)_AE/wCVQZ and reSE molecular structures of Vogt et al. [2].
   










Calc /ropt
Calc /reSE
Expt. [1]
   








Xaa - 51.51 - 51.41 - 51.342(31)

Xbb
27.93
27.95
27.920

Xcc
23.58
23.46
23.422

|Xac|
20.78
21.02



 







RMS
0.13 (0.39 %)

0.04 (0.13 %)




RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 















Table 4.  CHF2Cl Molecular structure parameters  ( and degrees).
 






rs [1] rz [1]ropt [2]
  reSE [2]







CH 1.098 1.0981.0843
1.0850(11)

CCl 1.742 1.7421.7577
1.7560(9)

CF 1.346 1.3541.3352
1.3363(5)

HCF


109.99
109.97(4)

HCCl 110.8 110.7109.30
109.60(6)

ClCF 110.5 111.0109.68
109.62(4)

FCF 107.5 106.7108.20
108.06(6)


 








 








[1] D.T.Cramb, Y.Bos, H.M.Jemson, M.C.L. Gerry, and C.J.Marsden, J.Mol.Struct. 190,387(1988).  For 35Cl; Xaa = 65.119(18), Xbb = 35.468, and Xcc = 29.650 MHz.


[2] N.Vogt, J.Demaison, and H.D.Rudolf, Mol.Phys. 112,2873(2014).


[3] S.Blanco, A.Lesarri, J.C.Lpez, J.L.Alonso, and A.Guarnieri, Z.Naturforsch. 51a,129(1996).

[4] D.B.McLay and C.R.Mann, Canad.J.Phys. 40,61(1962).

[5] E.L.Beeson, T.L.Weatherly, and Q.Williams, J.Chem.Phys. 37,2926(1962).

 








 








CH2FCl CF3Cl CH3Cl CH2Cl2

CF2Cl2 CHCl3 CFCl3 CH2BrCl

CF2BrCl







 








Calculation of Nuclear Quadrupole Coupling Constants on Approximate Equilibrium Structures of Chlorofluoromethanes.

 









 








Table of Contents




Molecules/Chlorine




 








 













CHF2Cl.html






Last Modified 27 Sept 2007