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C6H5COOH
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Deuterium
and Oxygen |
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Nuclear
Quadrupole Coupling Constants |
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in
Benzoic Acid |
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Calculation of the nqcc's of the OD
deuterium and the C-O and C=O oxygens in benzoic acid was made on the
B3P86/6-31G(3d,3p) optimized molecular structure. These
calculated coupling constants are given in Tables 1 - 3.
Structure parameters are given in Table 4. |
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In Tables 1 - 3, 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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RSD is the calibration residual
standard deviation of the model for calculation of the nqcc's. |
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Table 1. Deuterium nqcc's
in C6H5COOD (kHz).
Calculation was made on the B3P86/6-31G(3d,3p) ropt
structure. |
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Calc. |
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Expt. |
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2H |
Xaa |
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261.3 |
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Xbb |
- |
110.6 |
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Xcc |
- |
150.7 |
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|Xab| |
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64.6 |
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RSD |
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1.1 (0.9 %) |
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Xxx |
- |
121.5 |
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Xyy |
- |
150.7 |
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Xzz |
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272.2 |
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ETA |
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0.107 |
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Øz,a |
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9.57 |
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Øa,OD |
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11.07 |
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Øz,OD |
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1.49 |
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Table 2. 17O
(C-O) nqcc's in C6H5CO17OH (MHz).
Calculation was made on the B3P86/6-31G(3d,3p) ropt
structure. |
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Calc. [a] B1B95/6-311++G(3df,3p) |
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Calc. [b] B1LYP/6-311++G(3df,3p) |
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Calc. [c] B3LYP/6-311++G(3df,3p) |
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Calc. [a]
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Calc. [b] |
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Calc. [c] |
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Xaa |
- |
6.456 |
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6.511 |
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6.509 |
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Xbb |
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0.176 |
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0.189 |
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0.152 |
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Xcc |
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6.633 |
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6.700 |
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6.661 |
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|Xab| |
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4.252 |
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4.336 |
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4.333 |
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RSD |
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0.039 (1.4 %) |
0.041 (1.4 %) |
0.044 (1.5 %) |
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Xxx |
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1.969 |
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2.016 |
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2.043 |
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Xyy |
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6.633 |
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6.700 |
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6.661 |
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Xzz |
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8.602 |
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8.716 |
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8.704 |
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ETA |
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0.542 |
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0.537 |
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0.530 |
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Øz,a |
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26.78 |
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26.95 |
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26.87 |
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Øa,CO |
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63.89 |
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63.89 |
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63.89 |
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Øz,CO |
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37.11 |
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36.94 |
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37.02 |
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Table 3. 17O
(C=O) nqcc's in C6H5C17OOH (MHz).
Calculation was made on the B3P86/6-31G(3d,3p) ropt
structure. |
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Calc. [a] B1B95/6-311++G(3df,3p) |
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Calc. [b] B1LYP/6-311++G(3df,3p) |
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Calc. [c] B3LYP/6-311++G(3df,3p) |
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Calc. [a]
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Calc. [b] |
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Calc. [c] |
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Xaa |
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5.218 |
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5.224 |
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5.199 |
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Xbb |
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0.179 |
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0.203 |
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0.210 |
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Xcc |
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5.038 |
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5.022 |
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4.989 |
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|Xab| |
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5.718 |
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5.766 |
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5.747 |
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RSD |
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0.039 (1.4 %) |
0.041 (1.4 %) |
0.044 (1.5 %) |
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Xxx |
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3.803 |
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3.861 |
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3.858 |
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Xyy |
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5.038 |
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5.022 |
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4.989 |
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Xzz |
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8.841 |
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8.883 |
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8.846 |
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ETA |
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0.140 |
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0.131 |
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0.128 |
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Øz,a |
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32.37 |
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32.40 |
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32.40 |
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Øa,CO |
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58.05 |
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58.05 |
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58.05 |
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Øz,CO |
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89.58 |
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89.55 |
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89.55 |
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| Table 4. Benzoic Acid.
Molecular structure parameters, ropt (Å and
degrees). |
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| C(1)C(2) |
1.3959 |
C(1)C(2)H(2) |
118.50 |
| C(2)C(3) |
1.3865 |
C(2)C(3)H(3) |
120.00 |
| C(3)C(4) |
1.3922 |
C(3)C(4)H(4) |
119.88 |
| C(4)C(5) |
1.3912 |
C(4)C(5)H(5) |
120.04 |
| C(5)C(6) |
1.3883 |
C(5)C(6)H(6) |
120.63 |
| C(6)C(1) |
1.3959 |
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| C(2)H(2) |
1.0841 |
C(1)C(7) |
1.4797 |
| C(3)H(3) |
1.0846 |
C(7)O(8) |
1.2086 |
| C(4)H(4) |
1.0851 |
C(7)O(9) |
1.3489 |
| C(5)H(5) |
1.0846 |
O(9)H(10) |
0.9674 |
| C(6)H(6) |
1.0833 |
C(6)C(1)C(7) |
121.97 |
| C(6)C(1)C(2) |
120.11 |
C(1)C(7)O(8) |
124.88 |
| C(1)C(2)C(3) |
119.91 |
C(1)C(7)O(9) |
113.17 |
| C(2)C(3)C(4) |
119.93 |
C(7)O(9)H(10) |
105.64 |
| C(3)C(4)C(5) |
120.26 |
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| C(4)C(5)C(6) |
120.03 |
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| C(5)C(6)C(1) |
119.75 |
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HCOOH |
CF3COOH |
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M.Onda, M.Asai, K.Takise, K.Kuwae, K.Hayami,
A.Kuroe, M.Mori, H.Miyazaki, N.Suzuki, and I.Yamaguchi, J.Mol.Struct.
482-483,301(1999). |
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Table of Contents |
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Molecules/Deuterium |
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Molecules/Oxygen |
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C6H5COOH.html |
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Last
Modified 29 Oct 2004 |
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