|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
HO-C=O |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Deuterium |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in
trans and cis
Hydrocarboxyl Radical |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Deuterium nqcc's in
both the cis
and trans conformers of
DOCO, as well as an ro structure, were determined by
Oyama et al. [1]. |
|
|
|
|
|
|
|
|
|
|
|
|
cis-HOCO |
|
|
trans-HOCO |
|
|
|
|
|
|
|
|
|
|
|
|
 |
|
|
 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculations of the deuterium
nqcc's
in DOCO
were made here on the ro structure of Oyama et
al., on
an approximate re structure derived by Botschwina, and on an
ropt structure derived here by MP2/aug-cc-pVTZ
optimization.
These are compared with the experimental nqcc's in Tables 1 and 2.
Structure parameters are given in Table 3. |
|
|
|
|
|
|
|
|
|
|
|
|
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 of the
B3LYP/6-31G(df,3p) model for
calculation of the nqcc's. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
|
Table 1. D
nqcc's
in cis-DOCO (kHz).
Calculation was made
on the ro [1], re [2], and ropt
structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc/ro |
|
Calc/re |
|
Calc/ropt |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Xaa |
- |
101.0 |
- |
118.3 |
- |
114.7 |
- |
104.(11) |
|
|
Xbb |
|
230.8 |
|
266.8 |
|
259.1 |
|
255.(13) |
|
|
Xcc |
- |
129.8 |
- |
148.5 |
- |
144.4 |
- |
151. * |
|
|
|Xab| |
|
3.6 |
|
3.3 |
|
1.7 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
18. (11 %) |
|
11. (6.4 %) |
|
8. (4.5 %) |
|
|
|
|
RSD |
|
1.1 (0.9 %) |
|
1.1 (0.9 %) |
|
1.1 (0.9 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Calculated here from zero trace
condition. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
|
|
Table 2. D
nqcc's
in trans-DOCO (kHz).
Calculation was made
on the ro [1], re [2], and ropt
structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
|
|
Calc/ro |
|
Calc/re |
|
Calc/ropt |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Xaa |
|
73.4 |
|
82.0 |
|
77.5 |
|
71.2(78) |
|
|
Xbb |
|
72.2 |
|
76.0 |
|
76.0 |
|
|
|
|
Xcc |
- |
145.6 |
- |
158.0 |
- |
153.5 |
|
|
|
|
|Xab| |
|
187.4 |
|
204.9 |
|
198.4 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
| Table 3. Hydrocarboxyl.
Molecular
structure parameters, ro [1], re
[2], ropt (Å and degrees). |
| |
|
|
|
|
| |
cis-HOCO |
ro |
re |
ropt |
|
|
|
|
|
|
HO |
0.991 |
0.971 |
0.9752 |
|
OC |
1.329 |
1.328 |
1.3321 |
|
C=O |
1.184 |
1.181 |
1.1881 |
|
HOC |
107.3 |
108.0 |
108.07 |
|
OC=O |
131.1 |
130.3 |
130.74 |
| |
|
|
|
|
|
trans-HOCO |
|
|
|
|
|
|
|
|
|
HO |
0.974 |
0.962 |
0.9663 |
|
OC
|
1.342 |
1.340 |
1.3438 |
|
C=O |
1.181 |
1.176 |
1.1837 |
|
HOC |
107.4 |
107.8 |
107.40 |
|
OC=O |
127.4 |
127.1 |
127.20 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] Y.Oyama, W.Funato,
Y.Sumiyoshi, and Y.Endo, J.Chem.Phys. 134,174303(2011).
|
|
|
[2] P.Botschwina, Mol.Phys.
103,1441(2005). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Salicylaldehyde |
H2CO3 |
HC(=O)OH |
CF3C(=O)OH |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Deuterium |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
HOCO.html |
|
|
|
|
|
|
Last
Modified 31 Oct 2012 |
|
|
|
|
|
|
|
|
|
|
