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)/Xzzz,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


z,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


z,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) ( 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

 




|a|
0.97
0.05
0.05

|b| 0.18
1.33
0.94

|c| 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