HCOOH PDF





 









Deuterium and Oxygen


Nuclear Quadrupole Coupling Constants


in Formic Acid


 







 
 
Deuterium nqcc's were measured in HCOOD by Ruben and Kukolich [1].  An equilibrium structure was determined by Davis, Robiette, and Gerry [2].
 
Calculation of the deuterium nqcc's in HCOOD and DCOOH, and the oxygen nqcc's in HC17O17OH was made on the equilibrium structure.  In Table 1, the calculated and experimental deuterium nqcc's in HCOOD are compared.  In Table 2, calculated deuterium nqcc's in DCOOH are given.  In Tables 3 and 4, calculated oxygen nqcc's are shown.  Structure parameters are given in Table 5.

 

 




In the following Tables, 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 for the model for calculation of the nqcc's. 
 
The subscripts a,b,c refer to the principal axes of the inertia tensor,  the subscripts x,y,z to the principal axes of the nqcc tensor.  The nqcc y-axis is chosen coincident with the inertia c-axis, these are perpendicular to the plane of the molecule.  Ø (degrees) is the angle between its subscripted parameters. ETA = (Xxx - Xyy)/Xzz.
 

 








   






Table 1.  Deuterium nqcc's in HCOOD (kHz).
   









Calc.
Expt. [1]
   





2H Xaa - 119.2 - 119.3(20)
Xbb 267.6 267.5(30)
Xcc - 148.4 - 148.2(20)
|Xab|   25.6
 
RMS 0.2 (0.1 %)
RSD 1.1 (0.9 %)
 
Xxx - 120.8
Xyy - 148.4
Xzz 269.3
ETA 0.102
Øz,a 86.23
Øa,OD 84.85
Øz,OD   1.38
 


 







 
   






Table 2.  Deuterium nqcc's in DCOOH (kHz).
   









Calc.
Expt.
   





2H Xaa - 86.0
Xbb 175.2
Xcc - 89.2
|Xab|     6.8
 
RSD 1.1 (0.9 %)
 
Xxx - 86.1
Xyy - 89.2
Xzz 175.4
ETA 0.018
Øz,a 88.51
Øa,CD 88.59
Øz,CD   0.08
 
   
 

   






Table 3.  17O (C-O-H) nqcc's in HC17O17OH (MHz).
 
Calc. [a] B1B95/6-311++G(3df,3p)
Calc. [b] B1LYP/6-311++G(3df,3p)
Calc. [c] B3LYP/6-311++G(3df,3p)
   







Calc. [a]
Calc. [b]
Calc. [c]
   





Xaa - 0.696 - 0.719 - 0.675
Xbb - 5.556 - 5.604 - 5.597
Xcc 6.252 6.323 6.272
|Xab| 4.645 4.713 4.715
 
RSD 0.039 (1.4 %) 0.041 (1.4 %) 0.044 (1.5 %)
 
Xxx 2.116 2.147 2.183
Xyy 6.252 6.323 6.272
Xzz - 8.368 - 8.470 - 8.454
ETA 0.494 0.493 0.484
Øz,a 58.81 58.70 58.78
Øa,CO 22.04 22.04 22.04
Øz,CO 36.77 36.65 36.74
 








   






Table 4.  17O (C=O) nqcc's in HC17O17OH (MHz).
 
Calc. [a] B1B95/6-311++G(3df,3p)
Calc. [b] B1LYP/6-311++G(3df,3p)
Calc. [c] B3LYP/6-311++G(3df,3p)
   







Calc. [a]
Calc. [b]
Calc. [c]
   





Xaa 0.408 0.428 0.416
Xbb 5.553 5.521 5.498
Xcc - 5.960 - 5.948 - 5.914
|Xab| 5.582 5.590 5.575
 
RSD 0.039 (1.4 %) 0.041 (1.4 %) 0.044 (1.5 %)
 
Xxx - 3.166 - 3.169 - 3.170
Xyy - 5.960 - 5.948 - 5.914
Xzz 9.126 9.117 9.084
ETA 0.306 0.305 0.302
Øz,a 57.37 57.24 57.25
Øa,CO 33.16 33.16 33.16
Øz,CO 89.47 89.60 89.59
 
 
 
Table 5.  Molecular structure parameters, re [2] (Å and degrees).
 
OH 0.969
CH 1.091
C=O 1.201
CO 1.340
OCO 124.80
HC=O 123.26
HCO 111.94
COH 106.61
 
 

[1] D.J.Ruben and S.G.Kukolich, J.Chem.Phys. 60,100(1974);  S.G.Kukolich, J.Chem.Phys. 51,358(1969).
[2] R.Wellington Davis, A.G.Robiette, and M.C.L.Gerry, J.Mol. Spectrosc. 81,93(1980).

 








 








Benzoic Acid H2CO HOCl CF3COOH
 

 








Table of Contents



Molecules/Deuterium
Molecules/Oxygen
 

 













HCOOD.html






Last Modified 31 Oct 2004