g-HCCCH2-CH2Cl



 




 
 
 


Chlorine


Nuclear Quadrupole Coupling Constants

in gauche-Chlorobutyne


 







 
 
Calculation of the chlorine nqcc's in g-chlorobutyne was made on a structure given by MP2/aug-cc-pVTZ(G03) optimization with empirical correction for the CCl, C-C, and the acetylenic CC bond lengths (~ re).  These are compared with the experimental nqcc's of Keske et al. [1] in Tables 1 - 2.  Structure parameters are given in Table 3; rotational constants in Table 4.
 
In Tables 1 - 2, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  Øz,CCl (degrees) is the angle between the z-principal axes of the nqcc tensor and the CCl bond direction.  ETA = (Xxx - Xyy)/Xzz.
RSD is the calibration residual standard deviation of the B1LYP/TZV(3df,2p) model for calculation of the chlorine nqcc's, which may be taken as an estimate of the uncertainty in the calculated Xij.
 
In Tables 1 and 2,  the experimental Xbb and Xcc were calculated here from the experimental Xaa and Xbb -  Xcc.  The principal values of the nqcc tensors were calculated here from the experimental data using Z. Kisiel's QDIAG.f.  (See http://info.ifpan.edu.pl/~kisiel/prospe.htm.)
 
 
 
   







Table 1.  Chlorine nqcc's in gauche-chlorobutyne (MHz).  Calculation was made on the ~ re structure.
   








Calc.
Expt. [1]
   






35Cl Xaa   9.53   8.161(10)
Xbb -  Xcc - 60.79 - 59.422(36)
Xbb - 35.16 - 33.7915
Xcc 25.63 25.6305
Xab* - 44.49 44.83(86)
Xac* - 16.26 - 17.2(15)
Xbc* - 27.59 26.79(64)
 
RMS 1.12 (5.0 %)
RSD 0.49 (1.1 %)
 
Xxx 35.72 35.92
Xyy 37.27 36.70
Xzz - 73.00 - 72.62
ETA 0.021 0.011
Øz,CCl   0.64
 

 
* The algebraic signs of the off-diagonal Xij depend on the orientation of the molecule with respect to positive/negative sense of the a, b, and c axes.  However, the algebraic sign of the product XabXacXbc is independent of axes polarity.
 
 
   







Table 2.  Chlorine nqcc's in gauche-chlorobutyne (MHz).  Calculation was made on the ~ re structure.
   








Calc.
Expt. [1]
   






37Cl Xaa   6.77   5.714(17)
Xbb -  Xcc - 47.38 - 46.3256(58)
Xbb - 27.07 - 26.0198
Xcc 20.30 20.3058
Xab* - 35.46 35.4(19)
Xac* - 12.96 - 13.5(20)
Xbc* - 20.30 21.12(5)
 
RMS 0.86 (5.0 %)
RSD 0.44 (1.1 %)
 
Xxx 28.16 28.36
Xyy 29.37 28.71
Xzz - 57.53 - 57.07
ETA 0.021 0.006
Øz,CCl 0.64
 
 
* The algebraic signs of the off-diagonal Xij depend on the orientation of the molecule with respect to positive/negative sense of the a, b, and c axes.  However, the algebraic sign of the product XabXacXbc is independent of axes polarity.
 
  
Table 3.  g-Chlorobutyne (C1).  Selected structure parameters, ~ re (Å and degrees).   Complete structure is given here in Z-matrix format.
 

ClC(2) 1.7809
C(2)C(3) 1.5195
C(3)C(8) 1.4585
C(8)C(9) 1.2043
C(9)H(10) 1.0619
ClC(2)C(3) 111.17
C(2)C(3)C(8) 112.57
C(3)C(8)C(9) 178.91
C(8)C(9)H(10) 179.57
Click on image to enlarge.

 
Table 4.  g-Chlorobutyne.  Rotational constants, 35Cl species (MHz).
 
  ~ re    expt. [1]
 
A 7866.6 7933.9061(25)
B 2378.5 2326.77773(76)
C 1950.9 1919.42152(75)
 
 
[1] J.C.Keske, F.S.Rees, R.D.Suenram, and B.H.Pate, PCCP 5,1599(2003).   The experimental nqcc's and rotational constants given above were obtained from B.H.Pate via personal communication.  These differ, mainly with respect to algebraic sign of some nqcc  components, from those published in this paper.

 







 
trans-HCCCH2-CH2Cl Chloroethanes
 

 








Table of Contents




Molecules/Chlorine



 

 













gHCCCH2CH2Cl.html






Last Modified 8 Feb 08