CH3CH2ON=O
























 






Nitrogen


Nuclear Quadrupole Coupling Constants


in Ethyl Nitrite


 








 








Calculation of the N nqcc's in cis-trans ethyl nitrite was made here on ropt molecular structures given by MP2/6-311++G(d,p) and MP2/6-311+G(3df,3pd) optimization.











Calculated and experimental nqcc's [1] are compared in Table 1.  Structure parameters are given 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 (degrees) is the angle between its subscripted parameters.  RMS is the root measn square difference between calculated and experimental diagonal nqcc's.  RSD is the residual standard deviation of calibration of the B3PW91/6-311+G(df,pd) model for calculation of the efg's/nqcc's.











 








 








Table 1.  14N nqcc's in Ethyl Nitrite (MHz).  Calculation was made on (1) MP2/6-311++G(d,p) and (2) MP2/6-311+G(3df,3pd) optimized structures.
 










Calc (1)
Calc (2)
Expt. [1]
 








Xaa
1.224
1.155
1.233(2)

Xbb -
 4.705
 -
 4.664
 - 4.682(2) *

Xcc
3.481
3.509
3.449(2) *

|Xab|
2.988
3.066












RMS
0.023 (0.73 %)
0.057 (1.8 %)



RSD
0.030 (1.3 %)
0.030 (1.3 %)












Xxx
2.468
2.472



Xyy
3.481
3.509



Xzz -
 5.949
 -
 5.981



ETA
0.170
0.173



Øz,a
112.61
113.25



Øa,bi
130.46
130.73



Øz,bi**
  17.85
  17.48













 








* Calculated here from Xaa and (Xbb - Xcc) = -8.132(2) MHz [1].

** Angle between z-principal axis and bisector (bi) of the ON=O angle.

 









 







 



Table 2. Ethyl Nitrite: ropt structure parameters (Å and degrees).






 C
 C,1,B1
 H,1,B2,2,A1
 H,1,B3,2,A2,3,D1,0
 H,1,B4,2,A3,3,D2,0
 H,2,B5,1,A4,3,D3,0
 H,2,B6,1,A5,3,D4,0
 O,2,B7,1,A6,3,D5,0
 N,8,B8,2,A7,1,D6,0
 O,9,B9,8,A8,2,D7,0


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




 B1=1.5143058
 B2=1.09197378
 B3=1.09377788
 B4=1.09197378
 B5=1.09481758
 B6=1.09481758
 B7=1.4433935
 B8=1.39284163
 B9=1.19462699
 A1=110.68540726
 A2=109.37669422
 A3=110.68540726
 A4=112.13731319
 A5=112.13731319
 A6=106.25682501
 A7=115.69848693
 A8=114.64774304
 D1=119.60455716
 D2=-120.79088568
 D3=179.46267264
 D4=-58.67178696
 D5=60.39544284
 D6=180.
 D7=0.
  B1=1.50876954
 B2=1.08698441
 B3=1.0882625
 B4=1.08698441
 B5=1.08994777
 B6=1.08994777
 B7=1.43892308
 B8=1.38369149
 B9=1.191854
 A1=110.68167774
 A2=109.51649342
 A3=110.68167774
 A4=112.32566095
 A5=112.32566095
 A6=106.15837396
 A7=115.32817206
 A8=114.45764391
 D1=119.68765518
 D2=-120.62468965
 D3=179.23513456
 D4=-58.61044491
 D5=60.31234482
 D6=180.
 D7=0.



 













Table 3. Ethyl Nitrite:  Rotational Constants (MHz).






MP2/
 6-311++G(d,p) 6-311+G(3df,3pd)   Expt [1]






A
      18029.
         18075.
 18019.929(45)

B
        3031.
           3074.
   3019.9878(70)

C
        2682.
          2716.
   2674.6066(64)



 








 








[1] N.Hansen, F.Temps, H.Mäder, and N.W.Larsen, Phys.Chem.Chem.Phys. 1,3219(1999).

 








Ch.Keussen, U.Andresen, and H,Dreizler, Z.Naturforsch. 43a,469(1988): Xaa = 1.243(10), Xbb = -4.681(11), Xcc = 3.438(11) MHz.

Ch.Keussen and H,Dreizler, Z.Naturforsch. 46a,590(1991).

K.Endo, T.Koshiba, H.Saito, and Y.Kamura, Nippon Kagaku Kaishi 1661(1980).





















Nitrous Acid
 Methyl Nitrite
 tert-Butyl Nitrite



 








 








Table of Contents




Molecules/Nitrogen




 








 













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Last Modified 30 Dec 2015