Cl(CH3)CN2


















 





 





Chlorine and Nitrogen


Nuclear Quadrupole Coupling Constants


in Chloromethyldiazirine



 








 








The rotational spectra of Cl(CH3)NH2 was assigned by Wollrab et al. [1].  Chlorine nuclear quadrupole coiupling constants were measured.


 









Calculation of Cl and 14N nqcc's was made here on molecular structures given by MP2/6-311+G(3df,3pd) and MP2/aug-cc-pVTZ optimization.  These are compared with the experimental values in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.












In Tables 1 and 2, RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percentage of the average of the magnitudes of the experimental nqcc's).  In Table 1, RSD is the calibration residual standard deviation of the B1LYP/TZV(3df,2p) model for calculation of chlorine efg's/nqcc's; and in Table 2, of the B3PW91/6-311+G(df,pd) model for nitrogen.






















   









Table 1.  Chlorine nqcc's in Cl(CH3)CN2 (MHz).  Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized molecular structures.

   












Calc (1)

Calc (2)
Expt [1]
   









35Cl Xaa -
65.66
-
65.92
-
66.51



Xbb
33.29

33.35

32.91



Xcc
32.38

32.57

33.60



Xab -
22.27
-
22.46















RMS
0.89 (2.0 %)
0.73 (1.6 %)





RSD
0.49 (1.1 %)
0.49 (1.1 %)



 








37Cl Xaa -
52.02
-
52.22
-
53.07



Xbb
26.50

26.55

26.40



Xcc
25.52

25.67

26.67



Xab -
16.95
-
17.10















RMS

0.90 (2.5 %)

0.76 (2.2 %)





RSD

0.44 (1.1 %)
0.44 (1.1 %)














 








 









   









Table 2.  Nitrogen nqcc's in 35Cl (CH3)CN2 (MHz).  Calculation was made on (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized molecular structures.

   












Calc (1)

Calc (2)
Expt.

   









14N Xaa
1.782

1.795





Xbb
0.441

0.430





Xcc -
2.224
-
2.225





Xab
2.513

2.502





Xac -/+
0.430
-/+
0.429





Xbc +/-
0.488
+/-
0.489















RSD
0.030 (1.3 %)
0.030 (1.3 %)



 









 









 


Table 3.  Cl(CH3)CN2:  ropt(1) = MP2/6-311+G(3df,3pd) and ropt(2) = MP2/aug-cc-pVTZ optimized molecular structure parameters ( and degrees).
 



 C
 N,1,B1
 N,2,B2,1,A1
 C,1,B3,2,A2,3,D1,0
 H,4,B4,1,A3,2,D2,0
 H,4,B5,1,A4,2,D3,0
 H,4,B6,1,A5,2,D4,0
 Cl,1,B7,2,A6,3,D5,0






     ropt(1)      ropt(2)
 




 B1=1.45407517
 B2=1.26181305
 B3=1.49162183
 B4=1.08823919
 B5=1.08823919
 B6=1.08780462
 B7=1.74015014
 A1=64.28541006
 A2=121.02230609
 A3=110.17458247
 A4=110.17458247
 A5=109.48186944
 A6=116.08450873
 D1=-106.83511092
 D2=150.44770768
 D3=-89.61136066
 D4=30.41817351
 D5=103.63658801
 B1=1.45653261
 B2=1.26329523
 B3=1.49137015
 B4=1.08902516
 B5=1.08902516
 B6=1.08851917
 B7=1.74843639
 A1=64.29960631
 A2=121.26577592
 A3=110.18789835
 A4=110.18789835
 A5=109.44082827
 A6=115.88427544
 D1=-106.99131626
 D2=150.55227788
 D3=-89.5776036
 D4=30.48733714
 D5=103.50509589



 








 








 



Table 4.  35Cl(CH3)CN2:  ropt(1) = MP2/6-311+G(3df,3pd) and ropt(2) = MP2/aug-cc-pVTZ  rotational constants (MHz).
 





 ropt(1) ropt(2) Expt [1]






A
 6626.
 6601.


B
 3926.
 3907.


C
 2814.
 2801.



 








 








[1]  J.E.Wollrab and L.H.Scharpen, J.Chem.Phys. 51(4),1584(1969).


 








 








Diazirine
Methyldiazirine
Dimethyldiazirine






















Table of Contents




Molecules/Nitrogen




 








 













ClCH3CN2.html






Last Modified 9 Jan 2017