HONO2





























 








  








Deuterium and Nitrogen


Nuclear Quadrupole Coupling Constants


in Nitric Acid


 








 








 








Deuterium and nitrogen nqcc's in normal and isotopic nitric acid have been reported by Ott et al. [1], Fliege et al. [2], and Albinus et al. [3].  Molecular structures were determined by Cox and Riveros [4], Cox et al. [5], Ghosh et al. [6], and Gutle et al. [7].

 








Calculation was made here of the deuterium and nitrogen nqcc's on the equilibrium structure of Gutle et al.  These are compared with the experimental nqcc's in Tables 1 - 7.  Equilibrium structure parameters are given in Table 8.

 








In Tables 1 - 7, subscripts a,b,c refer to the principal axes of the inertia tensor, 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.  (degrees) is the angle between its subscripted parameters. ETA = (Xxx - Xyy)/Xzz.

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 of the model for calculation of the nqcc's:  B3LYP/6-31G(df,3p) for deuterium, and B3PW91/6-311+G(df,pd) for nitrogen.

 








 








   







Table 1.  Deuterium nqcc's in DONO2 (kHz).  Calculation was made on the re structure [7].
   










Calc.
Expt. [1]
   







2H Xaa
  37.5
  35.0(16)


Xbb
118.8
113.6 *


Xcc - 156.3 - 148.6 *


|Xab|
179.4



 






  RMS
5.6 (5.6 %)




RSD
1.1 (0.9 %)



 







Xxx - 105.8




Xyy - 156.3




Xzz
262.1




ETA
0.193




z,a
128.61




a,OD
127.35




z,OD
    1.26



 







 








* Calculated here from Xaa (= - Xbb - Xcc) and Xbb - Xcc = 262.2(60) kHz [1].

 








 








   







Table 2.  Deuterium nqcc's in DO15NO2 (kHz).  Calculation was made on the re structure [7].
   










Calc.
Expt. [2]
   







2H Xaa
  37.2
  31.1(24)


Xbb
119.2
118.5(29)


Xcc - 156.3 - 149.6(29)


|Xab|
179.3



 






  RMS
5.2 (5.3 %)




RSD
1.1 (0.9 %)



 






   








 








   








Table 3.  14N nqcc's in DONO2 (MHz).  Calculation was made on the re structure [7].
   










Calc.
Expt. [1]
Expt. [3]
   








Xaa
0.702
0.7266(36)
0.7311(56)

Xbb - 0.595 - 0.64885 * - 0.6534(81)

Xcc - 0.107 - 0.07775 * - 0.0777(81)

|Xab|
0.873





 







RMS


0.038 (7.8 %)
0.041 (8.4 %)

RSD


0.030 (1.3 %)
0.030 (1.3 %)

 








 








* Calculated here from Xaa (= - Xbb - Xcc) and Xbb - Xcc = - 0.5711(62) MHz [1].

 








 








   








Table 4.  14N nqcc's in HONO2 (MHz).  Calculation was made on the  re structure [7].
   










Calc.
Expt. [1]
Expt. [3]
   








Xaa
0.914
0.9450(51)
0.929(6)

Xbb - 0.807 - 0.86775 * - 0.859(8)

Xcc - 0.107 - 0.07725 * - 0.070(8)

|Xab|
0.665





 







RMS


0.043 (6.8 %)
0.038 (6.1 %)

RSD


0.030 (1.3 %)
0.030 (1.3 %)

 







Xxx - 1.034





Xyy - 0.107





Xzz
1.141





ETA - 0.812





z,a
18.85





a,N-O
17.29





z,N-O
  1.56





 








 








* Calculated here from Xaa (= - Xbb - Xcc) and Xbb - Xcc = - 0.7905(89) MHz [1].

 








 








   







Table 5.  14N nqcc's in H18ONO2 (MHz).  Calculation was made on the re structure [7].
   










Calc.
Expt. [1]
   







14N Xaa
1.085
1.0820(54)


Xbb - 0.978 - 1.0045 *


Xcc - 0.107 - 0.0775 *


|Xab|
0.345



 






  RMS
0.023 (3.2 %)





RSD
0.030 (1.3 %)



 







 








* Calculated here from Xaa (= - Xbb - Xcc) and Xbb - Xcc = - 0.927(11) MHz [1].

 








 








   







Table 6.  14N nqcc's in syn-HONO18O (MHz).  Calculation was made on the re structure [7].  (syn refers to 18O on the same side of the molecule as H.)
   










Calc.
Expt. [1]
   







14N Xaa
0.746
0.8002(55)


Xbb - 0.639 - 0.7121 *


Xcc - 0.107 - 0.0881 *


|Xab|
0.838



 






  RMS
0.053 (10.0 %)




RSD
0.030 (1.3 %)



 







 








* Calculated here from Xaa (= - Xbb - Xcc) and Xbb - Xcc = - 0.6240(91) MHz [1].

 








 








   







Table 7.  14N nqcc's in anti-HONO18O (MHz).  Calculation was made on the re structure [7].  (anti refers to 18O on the opposite side of the molecule as H.)
   










Calc.
Expt.
   







14N Xaa
0.154




Xbb - 0.047




Xcc - 0.107




|Xab|
1.083



 







RSD
0.030 (1.3 %)



 







 








 








 



Table 8.  Molecular structure parameters, semi-experimental re [7] ( and degrees).







HO 0.9683


O-N 1.3968


N=Osyn 1.2085


N=Oanti 1.1944


HON 102.22


OsynNO 115.80


OantiNO 114.15


 








 








[1] M.E.Ott, M.B.Craddock, and K.R.Leopold, J.Mol.Spectrosc. 229,286(2005).

[2] E.Fliege, H.Dreizler, S.Gerber, H.Huber, J.Mol.Spectrosc. 137,24(1989); E.Fliege and H.Dreizler, Z.Naturforsch. 39a,630(1984).

[3] L.Albinus, J.Spieckermann, and D.H.Sutter, J.Mol.Spectrosc. 133,128(1989).

[4] A.P.Cox and J.M.Riveros, J.Chem.Phys. 42,3106(1965)

[5] A.P.Cox, M.C.Ellis, C.J.Attfield, and A.C.Ferris, J.Mol.Struct. 320,91(1994)

[6] P.N.Ghosh, C.E.Blom, and A.Bauder, J.Mol. Spectrosc. 89,159(1981)

[7] C.Gutle, J.Demaison, and H.D.Rudolph, J.Mol.Spectrosc. 254,99(2009)

 








D.J.Millen and J.R.Morton, J.Chem.Soc. 1523(1960).


 









 









ClNO3 CH3NO3 HCOOD CH2NOH

 








 








Table of Contents




Molecules/Deuterium




Molecules/Nitrogen




 








 













DNO3.html






Last Modified 2 Feb 2009