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H2CO3 |
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Deuterium |
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Nuclear
Quadrupole Coupling Constants |
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in
cis-trans Carbonic Acid |
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Deuterium nqcc's were measured in cis-trans H2CO3
by Mori et al (2011) [1]. A partial ro structure and
an ab initio CCSD(T)/cc-pVQZ ropt
structure were determined also by Mori et al (2009)
[2]. |
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Calculations of the cis and trans deuterium nqcc's
in HDCO3
were made on these ro and ropt structures.
These are compared with the experimental nqcc's in Tables 1 and 2.
Structure parameters are given in Table 3. |
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In Tables 1 and 2, 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. |
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Table 1. Dcis
nqcc's
in HDCO3 (kHz). Calculation was made
on the ro and ropt structures. |
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Calc/ro |
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Calc/ropt |
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Expt. [1] |
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Xaa |
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193.6 |
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199.7 |
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175.(15) |
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Xbb - Xcc |
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119.8 |
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113.6 |
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79.(35) |
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Xbb |
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- 36.8 |
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- 43.1 |
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- 48. * |
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Xcc |
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156.7 |
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156.6 |
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127. * |
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|Xab| |
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165.8 |
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161.4 |
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RMS |
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21. (18 %) |
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22. (19 %) |
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RSD |
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1.1 (0.9 %) |
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1.1 (0.9 %) |
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* Calculated here from the
experimental Xaa and Xbb - Xcc. |
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Table 2. Dtrans
nqcc's
in HDCO3 (kHz). Calculation was made
on the ro and ropt structures. |
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Calc/ro |
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Calc/ropt |
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Expt. [1] |
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Xaa |
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61.4 |
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72.6 |
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81.(10) |
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Xbb - Xcc |
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256.5
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243.7 |
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239.(14) |
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Xbb |
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97.6 |
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85.6 |
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79. * |
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Xcc |
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159.0 |
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158.2 |
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160. * |
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|Xab| |
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201.0 |
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201.2 |
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RMS |
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16. (15 %) |
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6. (6 %) |
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RSD |
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1.1 (0.9 %) |
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1.1 (0.9 %) |
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* Calculated here from the
experimental Xaa and Xbb - Xcc. |
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| Table 3. Carbonic Acid.
Molecular
structure parameters, ro and CCSD(T)/cc-pVQZ ropt
[2] (Å and degrees). |
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ro |
ropt |
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O(1)C |
1.18788(94) |
1.194 |
| CO(3) |
1.3447(13) |
1.354 |
| CO(5) |
1.3568(17) |
1.336 |
| O(1)CO(3) |
126.78(15) |
125.2 |
| O(1)CO(5) |
122.94(12) |
124.3 |
| O(3)H/D |
0.968/0.963 * |
0.963 |
| CO(3)H/D |
106.1 * |
106.1 |
| O(5)H/D |
0.968/0.963 * |
0.963 |
| CO(5)H/D |
108.6 * |
108.6 |
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* Fixed to the ropt
value. In the ro structure, OH is chosen
0.005 Å
longer than OD, and OD is the ropt value. |
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[1] T.Mori, K.Suma, Y.Sumiyoshi, and
Y.Endo, J.Chem.Phys. 134,044319(2011).
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[2] T.Mori, K.Suma, Y.Sumiyoshi,
and Y.Endo, J.Chem.Phys. 130,204308(2009). |
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HOCN |
H2CO3 |
HC(=O)OH |
CF3C(=O)OH |
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Table of Contents |
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Molecules/Deuterium |
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H2CO3.html |
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Last
Modified 29 Oct 2012 |
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