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HOONO
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Nitrogen
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Nuclear
Quadrupole Coupling Constants |
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in cis-cis Peroxynitrous Acid |
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Calculation of the nitrogen nqcc's in the cis-cis
conformer of peroxynitrous acid was made on a molecular structure given
by CCSD(T)/cc-pVTZ [1]. These calculated nqcc's are
compared in Tables 1 and 2 with the experimental values of Fry, et al.
[2].
Structure parameters are given in Table 3. |
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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. Ø (degrees)
is the angle between its subscripted parameters. ETA = (Xxx
- Xyy)/Xzz. |
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RMS is the root mean square
difference between calculated and experimental nqcc's (percentage of
average experimental nqcc). RSD is the residual standard deviation
of calibration of the B3PW91/6-311+G(df,pd) model for calculation of
the nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's. |
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Table 1.
Nitrogen nqcc's in cis-cis HOONO (MHz). |
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Calc. |
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Expt. [2] |
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14N |
Xaa |
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1.542 |
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1.4907(25) |
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Xbb |
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4.601 |
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4.5990(59) |
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Xcc |
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3.058 |
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3.1082(32) * |
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|Xab| |
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2.688 |
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3.17(147) |
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RMS |
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0.041 (1.3 %) |
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RSD |
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0.030 (1.3 %) |
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Xxx |
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2.552 |
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Xyy |
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3.058 |
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Xzz |
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5.610 |
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ETA |
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0.090 |
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Øz,a |
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110.60 |
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Øa,bi |
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129.97 |
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Øz,bi** |
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19.38 |
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* Calculated here from the experimental 1.5 Xaa = 2.2361(37) MHz and 0.25 (Xbb - Xcc) = -1.9268(15) MHz using Kisiel's QDIAG.f program. |
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** The z-principal axis makes an angle of 19.38o with the external bisector ("bi") of the O(3)NO(5) angle (atomic numbering, see figure below) and tilts toward O(3). |
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Table 2.
Nitrogen nqcc's in cis-cis DOONO (MHz). |
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Calc. |
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Expt. [2] |
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14N |
Xaa |
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1.454 |
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0.999(189) * |
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Xbb |
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4.513 |
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4.332(109) * |
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Xcc |
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3.058 |
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3.333(109) * |
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|Xab| |
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2.785 |
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RMS |
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0.325 (11.2 %) |
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RSD |
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0.030 (1.3 %) |
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* Calculated here from the experimental 1.5 Xaa = 1.498(283) MHz and 0.25 (Xbb - Xcc) = -1.9163(277) MHz using Kisiel's QDIAG.f program. |
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| Table 3. cis-cis HOONO. CCSD(T)/cc-pVTZ molecular structure parameters [1] (Å
and degrees). |
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HO(2) |
0.9823 |
| O(2)O(3) |
1.4332 |
| O(3)N |
1.3845 |
| NO(5) |
1.1917 |
| HO(2)O(3) |
99.80 |
| O(2)O(3)N |
112.98 |
| O(3)NO(5) |
114.39 |
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[1] J.Fry, S.A.Nizkorodov, M.Okumura. C.M.Roehl, J.S.Francisco, and P.O.Wennberg, J.Chem.Phys. 121,1432(2004). |
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[2] J.Fry, B.J.Drouin, and C.E.Miller, J.Chem.Phys. 124,084304(2006). |
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Table of Contents |
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Molecules/Nitrogen |
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HOONO.html |
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Last
Modified 26 Jan 2008 |
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