CH2Cl-CH2NC


 



















 





 









Chlorine and Nitrogen


Nuclear Quadrupole Coupling Constants

in synclinal 2-Chloroethylisocyanide

 








 








 









Calculation of the chlorine and nitrogen nqcc's in synclinal 2-chloroethylisocyanide was made on structures r(1) =  MP2/6-311+G(3df,3pd) optimization with empirical correction for the C-C and CCl bond lengths, and r(2) =  MP2/aug-cc-pVTZ(G03) optimization with empirical correction for the C-C and CCl bond lengths.  These calculated nqcc's are given in Tables 1 - 4.  Structure parameters are given in Table 5, rotational constants in Table 6.

 








In Tables 1 - 4, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  Ø (degrees) is the angle between its subscript parameters.  ETA = (Xxx - Xyy)/Xzz.

RSD is the calibration residual standard deviation of the B1LYP/TZV(3df,2p) and B3PW91/6-311+G(df,pd) models for calculation resspectively of the chlorine and nitrogen nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's (notwithstanding uncertainities in the optimized molecular structures).

 








 







 
   







Table 1.  35Cl nqcc's in synclinal 2-chloroethylisocyanide (MHz).  Calculation was made on the r(1) and r(2) structures.
   









Calc / r(1)
Calc / r(2)
Expt.
   







Xaa
  4.87
  5.20



Xbb -
 31.55
 -
 31.81



Xcc
26.68
26.61



|Xab|
47.70 *
47.53 *



|Xac|
17.42
17.38



|Xbc|
26.93
27.04



 







RSD
0.49 (1.1 %) 0.49 (1.1 %)


 







Xxx
36.29
36.28



Xyy
38.26
38.23



Xzz -
 74.56
 -
 74.52



ETA
0.0264
0.0261



Øz,CCl
0.60
0.62



 








 








* The algebraic sign of the product XabXacXbc is negative.

 








 








   







Table 2.  37Cl nqcc's in synclinal 2-chloroethylisocyanide (MHz).  Calculation was made on the r(1) and r(2) structures.
   









Calc / r(1)
Calc / r(2)
Expt.
   







Xaa
  3.08
  3.34


Xbb -
 24.22
 -
 24.41


Xcc
21.13
21.07


|Xab|
37.91 *
37.78 *



|Xac|
13.85
13.82



|Xbc|
20.98
21.06



 







RSD
0.44 (1.1 %) 0.44 (1.1 %)


 








 








* The algebraic sign of the product XabXacXbc is negative.

 








 








   







Table 3.  14N nqcc's in the 35Cl species of synclinal 2-chloroethylisocyanide (MHz).  Calculation was made on the r(1) and r(2) structures.
   









Calc / r(1)
Calc / r(2)
Expt.
   







Xaa -
 0.011
 -
 0.008


Xbb
0.226
0.228


Xcc -
 0.216
 -
 0.220


|Xab|
0.423 *
0.431 *



|Xac|
0.123
0.126



|Xbc|
0.145
0.146



 







RSD
0.030 (1.3 %) 0.030 (1.3 %)


 








 








* The algebraic sign of the product XabXacXbc is positive.

 








 








   







Table 4.  14N nqcc's in the 37Cl species of synclinal 2-chloroethylisocyanide (MHz).  Calculation was made on the r(1) and r(2) structures.
   









Calc / r(1)
Calc / r(2)
Expt.
   







Xaa -
 0.018
 -
 0.016


Xbb
0.234
0.236


Xcc -
 0.216
 -
 0.220


|Xab|
0.421 *
0.429 *



|Xac|
0.122
0.125



|Xbc|
0.146
0.147



 







RSD
0.030 (1.3 %) 0.030 (1.3 %)


 








 








* The algebraic sign of the product XabXacXbc is positive.

 








 


Table 5.   Synclinal 2-chloroethylisocyanide.  Heavy atom structure parameters, r(1) and r(2) (Å and degrees).   Complete structures are given here in Z-matrix format.
 




  r(1)   r(2)





ClC(1) 1.7727 1.7739
C(1)C(2) 1.5147 1.5143
C(2)N 1.4182 1.4198
NC(4) 1.1794 1.1809
ClC(1)C(2) 111.32 111.08
C(1)C(2)N 111.31 111.38
C(2)NC(4) 179.10 179.11







 








 













Table 6.   Synclinal 2-chloroethylisocyanide, 35Cl species.  Calculated and experimental rotational constants (MHz).
 





  r(1)
   r(2)
   Expt [1]






A
 8408.1
 8395.8
 8534.417(17)

B
 2509.3
 2509.6
 2463.7378(65)

C
 2071.1
 2071.1
 2040.8006(59)



 








 








[1] H.Møllendal, S.Samdal, and J.-C..Guillemin, J.Phys.Chem. A 115,13474(2011).

 








 








ap CH2Cl-CH2NC
 CH3-CH2Cl CH3-CH2NC


 








 








Table of Contents




Molecules/Chlorine




Molecules/Nitrogen




 








 













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Last Modified 1 Dec 2011