CH3CH2CH2Cl

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Chlorine


Nuclear Quadrupole Coupling Constants


in trans-1-Chloropropane


 







 
 
Calculation of the chlorine nqcc's in t-1-chloropropane was made on a molecular structure derived ab initio, as described below. These nqcc's are compared in Table 1 with the experimental values of de Luis, et al. [1]. Structure parameters are given in Z-matrix format in Table 2.  Rotational constants are given in Table 3.
 
In Table 1, 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 nqcc's. 
 
Subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  The nqcc y-axis is chosen coincident with the inertia c-axis, these are perpendicular to the molecular symmetry plane.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

 







 
 
   






Table 1. Chlorine nqcc's in t-1-Chloropropane (MHz).
   









Calc.
Expt. [1]
   





35Cl Xaa - 54.98 - 54.7357(57)
Xbb 19.00 19.062(21)
Xcc 35.98 35.674(21)
|Xab| 38.49 37.83(15)
 
RMS 0.23 (0.63 %)
RSD 0.49 (1.1 %)
 
Xxx 35.39 35.01(11)
Xyy 35.98 35.674(21)
Xzz - 71.37 - 70.68(11)
ETA 0.0083 0.0094(19)
Øz,a 23.07 22.85
Øa,CCl 22.09 22.09 *
Øz,CCl   0.98   0.76 *
   
37Cl Xaa - 43.40 - 43.2170(60)
Xbb 15.05 15.100(15)
Xcc 28.36 28.117(15)
|Xab| 30.26 32.0(16)
 
RMS 0.18 (0.62 %)
RSD 0.44 (1.1 %)
 

 
* Calculated here corresponding to the structure given below.
 
 
Molecular Structure
 
The molecular structure was optimized at the MP2/6-311+G(d,p) level of theory assuming Cs symmetry.  The optimized CC bond lengths were then corrected using the equation obtained from linear regression analysis of the data given in Table IX of Ref.[2].  For the CCl bond, 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.[3].  The CH bond lengths were corrected using r = 1.001 ropt, where ropt is obtained by MP2/6-31G(d,p) optimization [4].  Interatomic angles used in the calculation are those given by MP2/6-311+G(d,p) optimization.
 
Table 2.  Z-Matrix (Å and degrees).
 
C
C 1 R1
C 2 R2 1 A3
H 2 R3 1 A4 3 -D3
H 2 R3 1 A4 3 D3
H 1 R4 2 A1 3 180.
H 1 R5 2 A2 3 -D1
H 1 R5 2 A2 3 D1
Cl 3 R6 2 A6 6 180.
H 3 R7 2 A7 6 -D2
H 3 R7 2 A7 6 D2
 
R1 = 1.521 A4 = 110.22
R2 = 1.511 A1 = 110.71
R3 = 1.091 A2 = 111.08
R4 = 1.090 A6 = 111.37
R5 = 1.091 A7 = 110.93
R6 = 1.785 D1 = - 60.14
R7 = 1.089 D2 = - 60.28
A3 = 111.09 D3 = 120.96

 
 
Table 3.  Rotational Constants (MHz).  35Cl species.
 
Calc. ropt      Expt. [1]
A 26 129.5 25 753.367(11)
B   2 402.1   2 379.68851(23)
C   2 293.7   2 271.67602(25)
 
 

[1] A.de Luis, M.E.Sanz, F.J.Lorenzo, J.C.López, and J.L.Alonso, J.Mol.Spectrosc. 184,60(1997).
[2] J.Demaison, J.Cosléou, R.Bocquet, and A.G.Lesarri, J.Mol.Spectrosc. 167,400(1994).
[3] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).
[4] J.Demaison and G.Wlodarczak, Structural Chem. 5,57(1994).

 








 








2,2-Chlorofluoropropane 2,2-Dichloropropane
2-Chloropropane Ethyl Chloride
 

 








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Molecules/Chlorine



 

 













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Last Modified 15 June 2004