F(O=)C-C(=O)Cl


















 





 





 









Chlorine



Nuclear Quadrupole Coupling Constants


in trans Oxalyl Chlorofluoride



 








 








 








Calculation of the chlorine nqcc tensors in trans oxalyl chlorofluoride was made here on a structure given by MP2/aug-cc-pVTZ optimization with empirically derived approximate equilibrium bond lengths.  These nqcc's are given in Table 1.  Structure parameters are given in Table 2; rotational constants, quartic centrifugal distortion constants, and dipole moments in Table 3.

 








In Table 1, subscripts a,b,c refer to the principal axes of the inertia tensor, subscripts x,y,z to the principal axes of the nqcc tensor.  The nqcc y-axis is chosen coincident with the c-axis.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

RSD is the residual standard deviation of the calibration of the B1LYP/TZV(3df,2p) model for calculation of the nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's.

 








 








   







Table 1.  Chlorine nqcc's in F(O=)C-C(=O)Cl (MHz).
   










Calc.
Expt.
   







35Cl Xaa -
38.54





Xbb
18.10




Xcc
20.44




|Xab|
47.79



 







RSD
0.49 (1.1 %)



 







Xxx
45.34




Xyy
20.44




Xzz - 65.77




ETA -
0.378




Øz,a
29.68




Øa,CCl
31.05




Øz,CCl
  1.37



 






37Cl Xaa -
31.09





Xbb
14.98





Xcc
16.11





|Xab|
37.24





 







RSD

0.44 (1.1 %)





 







 








 


















Table 2.  F(O=)C-C(=O)Cl  Structure parameters (Å and degrees).
 












 Cl
 C,1,R1
 C,2,R2,1,A2
 F,3,R3,2,A3,1,D3,0
 O,2,R4,3,A4,4,D4,0
 O,3,R5,2,A5,1,D5,0
      Variables:
 R1=1.7374
 R2=1.5349
 R3=1.3260
 R4=1.1852
 R5=1.1779
 A2=111.85525657
 A3=109.36136751
 A4=123.6726018
 A5=126.94057861
 D3=180.
 D4=0.
 D5=0.

 











 








 



















Table 3.  F(O=)C-C(=O)35Cl  Equilibrium rotational constants (MHz), B3LYP/cc-pVTZ quartic centrifugal distrotion constants (kHz), and B1LYP/TZV(3df,2p) dipole moments (D).
 











A
5126.4



B
2344.3



C
1608.7




 





Delta_J

0.29




Delta_JK -
0.018




Delta_K
1.29




delta_j
0.097




delta_k
0.62




 






D_J

0.26




D_JK

0.19




D_K

1.12




d_1
-
0.097




d_2
-
0.017




 
 








a|
0.57



b|
0.16



 








 









 








F.Bulat and A.Toro-Labbé,  Chem. Phys. Lett. 354,508(2002).


K.-M.Marstokk and H.Møllendal, Acta Chem. Scand. 49,172(1995).


 









 









H(O=)C-C(=O)Cl
HC(=O)Cl FC(=O)Cl CH3C(=O)Cl

 








 








Table of Contents




Molecules/Chlorine




 








 













FOCCOCl.html






Last Modified 14 March 2013