CHFCl-C(=O)Cl
















 








 









Chlorine


Nuclear Quadrupole Coupling Constants


in Chlorofluoroacetyl Chloride


 








 








A PE Scan of chlorofluoroacetyl chloride at the MP2/6-311+G(d,p) level of theory reveals three stable conformations, as shown below:











G1
G2
G3
























E = 0
E = 0.04 kJ/mol
E = 6.9 kJ/mol

ClCCCl = -78.05o
ClCCCl = 75.26o
ClCCCl = -177.25o











Calculation of chlorine nqcc tensors in each conformer of chlorofluoroacetyl chloride was made on a molecular structure given by MP2/aug-cc-pVTZ optimization with approximate re correction of the bond lengths.  These calculated nqcc's are given in Tables 1 - 4.  Structure parameters are given in Table 5, rotational constants and dipole moments in Table 6, and quartic centrifugal distortion constants in Table 7.

 








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.  Øz,CCl (degrees) is the angle between the z-principal axis and the CCl bond direction.

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

 








  








 








Table 1.  Calculated chlorine nqcc's in CHF35Cl(7)-C(=O)35Cl(1) (MHz). 











Conformer
  G1
  G2
  G3
 








Xaa /35Cl(1)
  8.12
 -
 13.85
 -
 46.57

Xbb
- 9.23
 -
 10.42
23.93

Xcc
  1.11
24.27
22.64

Xab
41.68
 -
 46.72
37.59

Xac
22.06
19.84
 -
 10.00

Xbc -
 31.08
  8.01
- 0.51










RSD
0.49 (1.1 %)
0.49 (1.1 %)
0.49 (1.1 %)










Xxx
22.75
23.37
22.46

Xyy
42.27
40.04
41.32

Xzz -
 65.02
 -
 63.41
 -
 63.79

ETA
0.300
0.263
0.295

Øz,CCl
1.43
0.98
1.40

 







Xaa  /35Cl(7)
- 3.34
13.86
 -
 58.56

Xbb
36.02
 -
 26.48
22.49

Xcc -
 32.67
12.62
36.06

Xab
- 0.69
37.68
30.57

Xac -
 55.04
25.42
 -
 15.00

Xbc
  3.38
 -
 42.76
  3.03

 







RSD
0.49 (1.1 %)
0.49 (1.1 %)
0.49 (1.1 %)

 







Xxx
34.52
36.42
35.27

Xyy
40.49
40.32
40.73

Xzz -
 75.01
 -
 76.74
 -
 76.00

ETA
0.079
0.051
0.072

Øz,CCl
1.64
1.98
1.22










   








 








 








Table 2.  Calculated chlorine nqcc's in CHF37Cl(7)-C(=O)35Cl(1) (MHz). 











Conformer
  G1
  G2
  G3
 








Xaa  /35Cl(1)
  8.37
 -
 11.77
 -
 46.82

Xbb
- 8.01
 -
 12.55
24.21

Xcc
- 0.37
24.32
22.61

Xab
41.01
 -
 46.66
37.32

Xac
22.66
19.80
 -
 10.11

Xbc -
 31.68
  8.54
  0.50










RSD
0.49 (1.1 %)
0.49 (1.1 %)
0.49 (1.1 %)










Xaa  /37Cl(7)
- 3.85
  9.32
 -
 46.35

Xbb
28.30
 -
 19.85
17.96

Xcc -
 24.45
10.53
28.39

Xab
- 0.06
30.68
30.14

Xac -
 43.70
20.63
 -
 11.95

Xbc
  3.19
 -
 32.90
  2.39

 







RSD
0.44 (1.1 %)
0.44 (1.1 %)
0.44 (1.1 %)































 








Table 3.  Calculated chlorine nqcc's in CHF35Cl(7)-C(=O)37Cl(1) (MHz). 











Conformer
  G1
  G2
  G3
 








Xaa  /37Cl(1)
  5.16
 -
 12.27
 -
 36.90

Xbb
- 7.97
- 7.01
19.03

Xcc
  2.81
19.28
17.87

Xab
33.84
 -
 36.82
29.47

Xac
16.65
15.52
- 7.77

Xbc -
 23.61
  5.84
- 0.48










RSD
0.44 (1.1 %)
0.44 (1.1 %)
0.44 (1.1 %)










Xaa  /35Cl(7)
- 2.15
14.92
 -
 58.83

Xbb
36.09
 -
 27.50
22.71

Xcc -
 33.94
12.58
36.12

Xab
- 3.04
37.08
30.35

Xac -
 54.68
24.81
 -
 14.82

Xbc
  0.34
 -
 43.14
  2.92

 







RSD
0.49 (1.1 %)
0.49 (1.1 %)
0.49 (1.1 %)











 








 








 








Table 4.  Calculated chlorine nqcc's in CHF37Cl(7)-C(=O)37Cl(1) (MHz). 











Conformer
  G1
  G2
  G3
 








Xaa  /37Cl(1)
  5.39
 -
 10.67
 -
 37.09

Xbb
- 7.20
- 8.65
19.24

Xcc
  1.81
19.32
17.85

Xab
33.36
 -
 36.83
29.26

Xac
17.07
15.50
- 7.86

Xbc -
 24.13
  6.24
- 0.46










RSD
0.44 (1.1 %)
0.44 (1.1 %)
0.44 (1.1 %)










Xaa  /37Cl(7)
- 2.90
10.23 -
 46.55

Xbb
28.42
 -
 20.73
10.12

Xcc -
 25.51
10.50
28.43

Xab
- 2.02
30.23
29.98

Xac -
 43.46
20.14 -
 11.81

Xbc
  0.75
 -
 33.22
  2.30

 







RSD
0.44 (1.1 %)
0.44 (1.1 %)
0.44 (1.1 %)











 








 








 


Table 5.  CHFCl-C(=O)Cl.  Structure parameters, MP2/aug-cc-pVTZ optimization (approximate re bond lengths are given in parentheses) (Å and degrees). 
 




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





   G1
    G2
    G3





 B1=1.75186146  (1.7486)
 B2=1.19429752  (1.1864)
 B3=1.52577738  (1.5235)
 B4=1.08640215
 B5=1.35568569  (1.3493)
 B6=1.76473889  (1.7615)
 A1=123.6740615
 A2=113.21712656
 A3=109.12492793
 A4=111.23971466
 A5=107.85075395
 D1=178.82551465
 D2=164.22376002
 D3=42.87295096
 D4=-78.04950433
  B1=1.76661708  (1.7634)
 B2=1.18882889  (1.1805)
 B3=1.52618114  (1.5239)
 B4=1.08671552
 B5=1.35260323  (1.3463)
 B6=1.76691532  (1.7637)
 A1=123.67297921
 A2=110.8851163
 A3=111.29387592
 A4=109.20314081
 A5=108.01818026
 D1=179.69677145
 D2=-43.47024349
 D3=-165.02747144
 D4=75.25989825
  B1=1.76654802  (1.7633)
 B2=1.1888663    (1.1806)
 B3=1.53510215  (1.5324)
 B4=1.08859995
 B5=1.36262693  (1.3561)
 B6=1.75181958  (1.7486)
 A1=123.11464424
 A2=109.82460788
 A3=109.50443436
 A4=108.75874139
 A5=110.73518187
 D1=-178.27160399
 D2=62.87986271
 D3=-56.06037691
 D4=-177.24787289


 








 













Table 6.  CHF35Cl-C(=O)35Cl.  Rotational Constants (MHz) and Dipole Moments (D).
 



 
 G1
  G2
  G3






A
 3168
 3189
 4542

B
 1654
 1772
 1481

C
 1551
 1305
 1168

 



|µa|
 0.97
 0.05
 0.05

|µb| 0.18
 1.33
 0.94

|µc| 0.51
 1.72
 1.50


 








 
















Table 7.  CHF35Cl-C(=O)35Cl.  B3LYP/cc-pVTZ Quartic Centrifugal Distortion Constants (kHz).
 






 

 G1
 G2
 G3









Delta_J
0.701
0.741
0.299

Delta_JK -
 0.500
 -
 1.93
0.0312

Delta_K
2.54
2.67
1.15

delta_J -
 0.164
0.289
0.104

delta_K
4.87
2.12
3.43

 






D_J
0.604
0.609
0.217

D_JK
0.0826
 -
 1.14
0.528

D_K
2.06
2.01
0.735

d_1
0.164
 -
 0.289
 -
 0.104

d_2 -
 0.0486
 -
 0.0660
 -
 0.0414


 








 








HC(=O)Cl FC(=O)Cl CH3C(=O)Cl CF3C(=O)Cl

CH2ClC(=O)Cl CF2ClC(=O)Cl CH3CH2C(=O)Cl CF3CF2C(=O)Cl











 








Table of Contents




Molecules/Chlorine




 








 













CHFClCOCl.html






Last Modified 20 Feb 2014