ClC(H)=O-O















 









Chlorine


Nuclear Quadrupole Coupling Constants

in the Chlorine Substituted Criegee Intermediate

 


















Chlorine nqcc's in both syn and anti conformations of the chlorine substituted Criegee intermediate were determined by Cabezas et al. [1].





















Syn

Anti


































Calculation of the chlorine nqcc tensors in each conformer shown above was made on ropt molecular structures given by MP2/6-311+G(3df,3pd) and MP2/aug-cc-pVTZ optimization.  These are compared with the experimental nqcc's [1] in Tables 1 - 4.  Structure parameters in Z-matrix format 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.  ETA = (Xxx - Xyy)/Xzz.  Ø (degrees) is the angle between its subscripted parameters.

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).  RSD is the calibration residual standard deviation of the B1LYP/TZV(3df,2p) model for calculation of chlorine efg's/nqcc's.

 








 








 








Table 1.  35Cl nqcc's in syn-ClC(H)=O-O (MHz).  Calculation was made on (1)  MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized structures.
 










Calc (1)
Calc (2)
Expt. [1]
 








Xaa -
 20.52
 -
 20.64
 -
 22.0476(12)

Xbb
- 1.40
- 1.52
- 1.7646(13)

Xcc
21.92
22.16
23.8122(25)

Xab -
 57.49
 -
 57.93
 -
 57.46(15)










RMS
1.42 (8.9 %)
1.26 (7.9 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)












Xxx
47.32
47.64
46.44(15)

Xyy
21.92
22.16
23.8122(25)

Xzz -
 69.24
 -
 69.80
 -
 70.25(15)

ETA -
 0.367
 -
 0.365
 -
 0.322

Øz,a
40.27
40.31
39.995(13)

Øa,CCl
41.13
41.16



Øz,CCl
  0.85
  0.84













 








 








 








Table 2.  37Cl nqcc's in syn-ClC(H)=O-O (MHz).  Calculation was made on (1)  MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized structures.
 










Calc (1)
Calc (2)
Expt. [1]
 








Xaa -
 16.71
 -
 16.81
 -
 17.9281(11)

Xbb
- 0.56
- 0.65
- 0.8376(13)

Xcc
17.28
17.46
18.7657(26)

Xab -
 45.22
 -
 45.56
 -
 44.80(16)










RMS
1.12 (9.0 %)
1.00 (8.0 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)













 








 








 








Table 3.  35Cl nqcc's in anti-ClC(H)=O-O (MHz).  Calculation was made on (1)  MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized structures.
 










Calc (1)
Calc (2)
Expt. [1]
 








Xaa -
 60.22
 -
 60.89
 -
 62.1140(36)

Xbb
32.27
32.85
32.4129(51)

Xcc
27.96
28.04
29.7011(87)

Xab -
 34.91
 -
 34.62
 -
 34.24(89)










RMS
1.22 (2.9 %)
1.22 (2.9 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)












Xxx
43.96
44.25
43.51(52)

Xyy
27.96
28.04
29.7011(87)

Xzz -
 71.92
 -
 72.29
 -
 73.21(52)

ETA -
 0.223
 -
 0.224
 -
 0.189

Øz,a
18.53
18.22
17.96(35)

Øa,CCl
19.08
18.80



Øz,CCl
  0.55
  0.58













 








 








 








Table 4.  37Cl nqcc's in anti-ClC(H)=O-O (MHz).  Calculation was made on (1)  MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ optimized structures.
 










Calc (1)
Calc (2)
Expt. [1]
 








Xaa -
 47.52
 -
 48.05
 -
 48.9948(56)

Xbb
25.49
25.95
25.5726(81)

Xcc
22.03
22.10
23.4222(98) *

Xab -
 27.44
 -
 27.21












RMS
1.17 (3.6 %)
0.97 (3.0 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)













 








* Calculated here from zero trace condition.

 








 



Table 5.  ClC(H)=O-O.  MP2/6-311+G(3df,3pd) and MP2/aug-cc-pVTZ optimized structure parameters (Å and degrees).







Syn ClC(H)=O-O







 O
 O,1,R1
 C,2,R2,1,A1
 H,3,R3,2,A2,1,D1,0
 Cl,3,R4,2,A3,1,D2,0







MP2/6-311+G(3df,3pd)
 MP2/aug-cc-pVTZ







 R1=1.2897815
 R2=1.28337829
 R3=1.07594743
 R4=1.66427715
 A1=120.66471793
 A2=115.64116065
 A3=120.9552215
 D1=180.
 D2=0.
  R1=1.29718147
 R2=1.28628046
 R3=1.07628946
 R4=1.67025281
 A1=120.35287828
 A2=115.69444619
 A3=120.8927569
 D1=180.
 D2=0.












Anti ClC(H)=O-O



 



 O
 O,1,R1
 C,2,R2,1,A1
 H,3,R3,2,A2,1,D1,0
 Cl,3,R4,2,A3,1,D2,0


 


MP2/6-311+G(3df,3pd) MP2/aug-cc-pVTZ







 R1=1.31332033
 R2=1.26634585
 R3=1.08157902
 R4=1.67718052
 A1=118.35575855
 A2=119.58565727
 A3=118.12171069
 D1=0.
 D2=180.
  R1=1.32532984
 R2=1.26762873
 R3=1.08183135
 R4=1.68390368
 A1=117.65455544
 A2=119.65862106
 A3=118.15385063
 D1=0.
 D2=180.







 














Table 6.  35ClC(H)=O-O.  Rotational Constants (MHz).  Calc (1) = MP2/6-311+G(3df,3pd); Calc (2) = MP2/aug-cc-pVTZ optimized structure.








Calc (1)
 Calc (2)
     Expt [1]






Syn
 A
   18025.
   17828.
 17124.40884(61)

B
     4391.
     4381.
   4391.7504(18)

C
     3531.
     3517.
   3491.0687(17)






Anti A
   66163.
   65745.
 64583.2740(14)

B
     2858.
     2838.
   2811.84004(32)

C
     2740.
     2721.
   2693.52510(37)



 








 








[1] C.Cabezas, J.-C.Guillemin, and Y.Endo, J.Chem.Phys. 145,184304(2016).

 








 








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Last Modified 11 Nov 2016