H-CC-C(=O)OH
























 





 









Deuterium


Nuclear Quadrupole Coupling Constants

in Propiolic Acid, d1

 








 








 

 





Calculation of the deuterium nqcc tensors in monodeuterated propiolic acid 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 [1] in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.

 








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.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

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 H-CC-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
260.8
255.3
256.5(33) *

Xbb -
 110.7 -
 108.3 -
 112.6(45) *

Xcc -
 150.1 -
 147.0 -
 143.9(45) *

|Xab|
  61.5
  59.7



 







RMS
4.4 (2.6 %)
 3.1 (1.8 %)
  

RSD
1.1 (0.86 %)
 1.1 (0.86 %)


 







Xxx -
 120.6 -
 117.8



Xyy -
 150.1 -
 147.0



Xzz
270.7
264.9



ETA
0.109
0.110



Øz,a
  9.17
  9.10



Øa,OD
10.62
10.56



Øz,OD
  1.45
  1.46



 








 








* Calculated here from experimental 1.5Xaa = 0.3848(49) and 0.25(Xbb - Xcc) = 0.00785(211) MHz [1].

 








 








   







Table 2. D nqcc's in D-CC-C(=O)OH (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
212.9
212.6
205.3(27) *

Xbb -
 108.7 -
 108.5



Xcc -
 104.2 -
 104.1



|Xab|
    5.4
    5.7



 







RMS
7.6 (3.7 %)
 7.3 (3.6 %)
  

RSD
1.1 (0.86 %)
 1.1 (0.86 %)


 







Xxx -
 108.8 -
 108.6



Xyy -
 104.2 -
 104.1



Xzz
213.0
212.7



ETA
0.0213
0.0214



Øz,a
  0.96
  1.014



Øa,CD
  0.96
  1.017



Øz,CD
  0.00
  0.003



 








 








* Calculated here from experimental 1.5Xaa = 0.3080(40) MHz [1].

 







 
 

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



 O
 H,1,B1
 C,1,B2,2,A1
 O,3,B3,1,A2,2,D1,0
 C,3,B4,1,A3,4,D2,0
 C,5,B5,2,A4,4,D3,0
 H,6,B6,4,A5,2,D4,0


ropt(1) ropt(2)
 
 B1=0.96815607
 B2=1.34618353
 B3=1.20674381
 B4=1.44665384
 B5=1.21305172
 B6=1.06234116
 A1=105.75550831
 A2=124.15443066
 A3=111.39565131
 A4=161.14605072
 A5=161.75136421
 D1=0.
 D2=180.
 D3=180.
 D4=180.
  B1=0.97119556
 B2=1.34964818
 B3=1.21003443
 B4=1.44601681
 B5=1.21427027
 B6=1.0625963
 A1=105.73105785
 A2=124.12112095
 A3=111.3002228
 A4=161.1340831
 A5=161.82450926
 D1=0.
 D2=180.
 D3=180.
 D4=180.






 














Table 4.  Propiolic Acid 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]






HCCC(=O)OD A
 11848.4
 11788.7
 11858.44934(132)


B
   4003.1
   3998.0
   4015.71252(41)


C
   2992.2
   2985.5
   2995.59587(48)


 


DCCC(=O)OH
 A
 12100.2
 12040.2
 12110.01758(217)


B
   3805.7
   3801.0
   3819.67859(110)


C
   2895.1
   2889.0
   2899.60416(55)


 








 








[1] M.Sun, B.Sargus, S.J.Carey, and S.G.Kukolich, Abstract RK11, 68th International Symposium on Molecular Spectroscopy, June 17-21, 2013.

 








 








HC(=O)OH
HCCH
 CF3C(=O)OH
 Salicylaldehyde

 








 








Table of Contents




Molecules/Deuterium




 








 













HCCCOOH.html






Last Modified 7 July 2013