CH2=C(CH3)-N=O










































Nitrogen


Nuclear Quadrupole Coupling Constants


in syn-2-Nitrosopropene


 








 








 

 





The microwave spectrum of syn-2-nitosopropene was observed and assigned by Sakaizumi et al. [1].

 








Calculation of the 14N nqcc tensors was made here on ropt molecular structures given by B3LYP/6-311+G(3df,3pd) and MP2/6-311+G(3df,3pd) optimization.  These calculated nqcc's are compared with the experimental values [1] in Table 1.  Structure parameters in Z-matrix format are compared in Table 2, rotational constants in Table 3.


 








In Table 1, 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.  Ø is the angle between its subcripted parameters.

RMS is root mean square difference between calculated and experimental nqcc's.  RSD is the calibration residual standard deviation of the B3PW91/6-311+G(df,pd) model for calculation of nitrogen efg's/nqcc's.

 








 








 








Table 1.  14N nqcc's in syn-2-Nitosopropene (MHz).  Calculation was made on the B3LYP/6-311+G(3df,3pd) and MP2/6-311+G(3df,3pd) ropt structures.
 










Calc /B3LYP
Calc /MP2
Expt [1]
 








Xaa
0.942
0.959
0.25(21)

Xbb -
 6.223
 -
 6.180
 -
 7.11(41)

Xcc
5.281
5.221
6.85(61)

|Xab|
1.033
1.103












RMS
1.11 (23.5 %)
1.16 (24.4 %)



RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xxx
1.088
1.126



Xyy
5.281
5.221



Xzz -
 6.369
 -
 6.347



ETA
0.658
0.645



Øz,a
81.95
81.42



Øa,N=O







Øz,N=O

















 








 







 
 


Table 2. syn-2-Nitosopropene.  B3LYP/6-311+G(3df,3pd) and MP2/6-311+G(3df,3pd) ropt structure parameters (Å and degrees).





 C
 C,1,B1
 H,1,B2,2,A1
 H,1,B3,2,A2,3,D1,0
 C,2,B4,1,A3,4,D2,0
 H,5,B5,2,A4,1,D3,0
 H,5,B6,2,A5,1,D4,0
 H,5,B7,2,A6,1,D5,0
 N,2,B8,1,A7,5,D6,0
 O,9,B9,2,A8,1,D7,0



B3LYP/6-311+G(3df,3pd)
 MP2/6-311+G(3df,3pd)





 B1=1.33563076
 B2=1.08057799
 B3=1.08133611
 B4=1.49235242
 B5=1.08743307
 B6=1.09048579
 B7=1.09048579
 B8=1.43943493
 B9=1.21164324
 A1=122.16591933
 A2=119.36487373
 A3=127.25220508
 A4=110.74584888
 A5=110.58387333
 A6=110.58387333
 A7=113.06263077
 A8=114.49797192
 D1=180.
 D2=180.
 D3=0.
 D4=121.15328647
 D5=-121.15328647
 D6=180.
 D7=180.
  B1=1.34115074
 B2=1.08004511
 B3=1.08095998
 B4=1.48906555
 B5=1.08645421
 B6=1.08864826
 B7=1.08864826
 B8=1.43210023
 B9=1.22890277
 A1=121.82970622
 A2=118.89473649
 A3=127.3832175
 A4=110.36484383
 A5=110.35455972
 A6=110.35455972
 A7=112.95509384
 A8=113.41938105
 D1=180.
 D2=180.
 D3=0.
 D4=121.02742501
 D5=-121.02742501
 D6=180.
 D7=180.







 








 



Table 3. syn-2-Nitosopropene.  Rotational Constants (MHz).  B3LYP/6-311+G(3df,3pd) and MP2/6-311+G(3df,3pd) ropt structures.







B3LYP
  MP2
Expt [1]






A
   8777
  8805
8744.09(8)

B
   4871
  4888
 4846.07(2)

C
   3193
  3205
 3178.84(3)


 


















[1] T.Sakaizumi, H.Imajo, R.Yamasaki, T.Usami, S.Kawaji, S.Abe, T.Haraga, H.Morii, N.Kuze, and O.Ohashi, J.Mol.Spectrosc. 204,26(2000).











"Theoretical study of electric field gradients at nitrogen nuclei in HNO, CH3NO, and C3H3NO" R.Polák, and J.Fišer, Chem.Phys. 375,85(2010).

 








 








HN=O CH3N=O



 








 








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Molecules/Nitrogen




 








 













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Last Modified 23 March 2014