H2C=C=O  d1 and d2
























 








 









Deuterium


Nuclear Quadrupole Coupling Constants

in Ketene


 








 








 


 





Calculation of the D nuclear quadrupole coupling constant tensors in d2 and d1 Ketene was made here on an re molecular structure derived by Guarnieri et al. [1], and on an approximate equilibrium structure given by MP2/aug-cc-pVTZ optimization with empirically corrected equilibrium C=C and C=O bond lengths.  


 








In Tables 1 and 2, 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.  (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

RSD is the calibration residual standard deviation of the B3LYP/6-31G(df,3p) model for calculation of the nqcc's.

 








 








   








Table 1.  Deuterium nqcc's in D2C=C=O (kHz).  Calculation was made on the (1) re structure of Guarnieri, and (2) the approximate MP2/aug-cc-pVTZ re structure.

   










Calc. (1)

Calc. (2)
Expt [2]

   








Xaa
- 18.4
- 18.9




Xbb - Xcc
250.6

251.3

246(5)


Xbb
134.5
135.1




Xcc -
116.1 -
116.2



|Xac|
126.4
126.1



 







RSD
1.1 (0.86 %)
1.1 (0.86 %)


 







Xxx
- 89.7

- 89.6




Xyy -
116.1 -
116.2



Xzz
205.8
205.8



ETA
0.128
0.129



a,z
60.576
60.71



a,CD
60.885
61.03



z,CD
  0.309
  0.32



 








 








 









   








Table 2.  Deuterium nqcc's in DHC=C=O (kHz).  Calculation was made on the (1) re structure of Guarnieri, and (2) the approximate MP2/aug-cc-pVTZ re structure.

   










Calc. (1)

Calc. (2)
Expt [2]

   








Xaa
  - 9.7

- 10.2




Xbb - Xcc
241.9

242.6

240(15)


Xbb
125.8
126.4




Xcc -
116.1 -
116.2



|Xac|
131.3
131.0



 







RSD
1.1 (0.86 %)
1.1 (0.86 %)


 








 









 








 
 




Table 3.  D2C=C=O Structure parameters ( and degrees): (1) re structure of Guarnieri, (2) the approximate MP2/aug-cc-pVTZ re structure.
 




Point Group: C2V

  re (1)
re (2)








CH
1.0763(1)
1.0763
C=C
1.3122(6)
1.3135
C=O
1.1607(6)
1.1585
CCH
119.115(11)
118.97



 








 








[1] A.Guarnieri, J.Demaison, and H.D.Rudolph, J.Mol.Struct. 969,1(2010).   


[2] V.W.Weiss and W.H.Flygare, J.Chem.Phys. 45,3475(1966).






















H2C=C=17O H2C=O
H2C=S
H2CF2


 









 








Table of Contents




Molecules/Deuterium




 








 













D2CCO.html






Last Modified 25 April 2013