CH2=C(H)-C(=O)OD















 








Deuterium


Nuclear Quadrupole Coupling Constants

in Acrylic Acid


 








 








 


 





Calculation of the deuterium nqcc tensors in each of the following conformers of acrylic acid, CH2=C(H)-C(=O)OD, was made here 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 of Calabrese et al. [1] in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.


 








s-cis


s-trans
























 









In Tables 1 and 2, 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.  (degrees) is the angle between its subscripted parameters.  

RMS is the root mean square difference between calculated and experimental nqcc's (percentage of the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation of the B3LYP/6-31G(df,3p) model for calculation of deuterium efg's/nqcc's.

 








 








   








Table 1. D nqcc's in s-cis-CH2=C(H)-C(=O)OD (kHz).  Calculation was made on the (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ ropt molecular structures.
   










Calc (1)
Calc (2)

Expt [1]
   








Xaa
150.9
148.2
148(6)


Xbb
    0.035

  - 0.3

    4(10) *


Xcc -
150.9 -
147.9 -
152(10) *


|Xab|
182.6

178.6




 







RMS
2.9 (2.9 %)
3.4 (3.4 %)
 

RSD
1.1 (0.86 %)
1.1 (0.86 %)


 







Xxx -
122.1 -
119.4



Xyy -
150.9 -
147.9



Xzz
273.0
267.3



ETA
0.105
0.106



z,a

33.78

33.71




a,OD
35.23

35.17




z,OD
  1.45

  1.46




 









 








* Calculated here from experimental Xaa and Xbb - Xcc = 156(18) MHz [1].


 








 









   








Table 2. D nqcc's in s-trans-CH2=C(H)-C(=O)OD (kHz).  Calculation was made on the (1) MP2/6-311+G(3df,3pd) and (2) MP2/aug-cc-pVTZ ropt molecular structures.
   










Calc (1)
Calc (2)

Expt [1]
   








Xaa
247.5
242.1
237(5)


Xbb
- 95.4

- 92.9

- 93(6) *


Xcc -
152.1 -
149.2 -
144(6) *


|Xab|
  99.4

  97.8




 







RMS
7.8 (4.9 %)
4.2 (2.7 %)
 

RSD
1.1 (0.86 %)
1.1 (0.86 %)


 







Xxx -
122.1 -
119.4



Xyy -
152.1 -
149.2



Xzz
274.2
268.6



ETA
0.110
0.111



z,a

15.05

15.14




a,CD
13.54

13.63




z,CD
  1.50

  1.51




 









 









* Calculated here from experimental Xaa and Xbb - Xcc = 51(10) MHz [1].

 








 
 

Table 3.  Acrylic Acid Molecular structure parameters, ropt(1) = MP2/6-311+G(3df,3pd) optimization and ropt(2) = MP2/aug-cc-pVTZ optimization ( and degrees).
 



 C
 C,1,B1
 H,1,B2,2,A1
 H,1,B3,2,A2,3,D1,0
 H,2,B4,1,A3,4,D2,0
 C,2,B5,1,A4,4,D3,0
 O,6,B6,2,A5,1,D4,0
 O,6,B7,2,A6,1,D5,0
 H,8,B8,6,A7,2,D6,0


ropt(1) ropt(2)
 

 B1=1.33382055
 B2=1.08112499
 B3=1.07977579
 B4=1.08025888
 B5=1.47982956
 B6=1.20832748
 B7=1.35307446
 B8=0.96723673
 A1=119.88875799
 A2=121.26339903
 A3=122.40519064
 A4=120.16330761
 A5=126.05066528
 A6=111.01110754
 A7=105.78135469
 D1=180.
 D2=0.
 D3=180.
 D4=0.
 D5=180.
 D6=180.
 B1=1.33477959
 B2=1.08157725
 B3=1.08002298
 B4=1.08029604
 B5=1.47919677
 B6=1.2116912
 B7=1.35625616
 B8=0.97017584
 A1=119.87907813
 A2=121.21817552
 A3=122.42152707
 A4=120.12528693
 A5=126.14032893
 A6=110.90774106
 A7=105.8134703
 D1=180.
 D2=0.
 D3=180.
 D4=0.
 D5=180.
 D6=180.
 


------------------------------------------------
 



 C
 C,1,B1
 H,1,B2,2,A1
 H,1,B3,2,A2,3,D1,0
 H,2,B4,1,A3,4,D2,0
 C,2,B5,1,A4,4,D3,0
 O,6,B6,2,A5,1,D4,0
 O,6,B7,2,A6,1,D5,0
 H,8,B8,6,A7,2,D6,0


ropt(1) ropt(2)


 B1=1.33498513
 B2=1.07981636
 B3=1.0803836
 B4=1.08043691
 B5=1.47564788
 B6=1.21034116
 B7=1.35254432
 B8=0.96655149
 A1=120.9661356
 A2=120.73766143
 A3=122.02883985
 A4=123.60721657
 A5=123.96817192
 A6=113.3826748
 A7=105.36897138
 D1=180.
 D2=0.
 D3=180.
 D4=180.
 D5=0.
 D6=180.
 B1=1.33589285
 B2=1.08020111
 B3=1.08053657
 B4=1.08048346
 B5=1.47508576
 B6=1.21361731
 B7=1.35594906
 B8=0.9694637
 A1=120.93662525
 A2=120.68336421
 A3=122.07085707
 A4=123.6564383
 A5=123.99767896
 A6=113.34376151
 A7=105.37971909
 D1=180.
 D2=0.
 D3=180.
 D4=180.
 D5=0.
 D6=180.






 














Table 4.  CH2=C(H)-C(=O)OD.  Rotational Constants (MHz).  ropt(1) = MP2/6-311+G(3df,3pd),  ropt(2) = MP2/aug-cc-pVTZ optimized structures.
 





 
 ropt(1)  ropt(2)       Expt [1]






s-cis A
11062.3
11007.8
11068.1926(29)


B
  4100.1
  4096.8
  4075.5354(12)


C
  2991.4
  2985.6
  2979.5056(10)


 



s-trans
A
10304.0
10263.0
10242.1235(20)


B
  4324.3
  4317.6
  4307.8658(16)


C
  3046.0
  3039.2
  3033.3858(10)


 








 








[1] C.Calabrese, A.Vigorito, G.Feng, L.B.Favero, A.Maris, S.Melandri, W.D.Geppert, and W.Caminati, J.Mol.Spectrosc. 295,37(2014).


 








 








HC(=O)OH
Propiolic Acid
CF3C(=O)OH
Salicylaldehyde

 








 








Table of Contents




Molecules/Deuterium




 








 













CH2CHCOOD.html






Last Modified 19 July 2014