|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
g-HCCCH2-CH2Cl
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Chlorine |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in gauche-Chlorobutyne
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of the chlorine nqcc's in g-chlorobutyne
was made on a structure given by MP2/aug-cc-pVTZ(G03) optimization with empirical correction for the CCl, C-C, and the acetylenic CC bond lengths (~ re).
These are compared with the experimental nqcc's of Keske et al.
[1] in Tables 1 - 2. Structure parameters are given in
Table 3; rotational constants in Table 4. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 - 2,
subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor. Øz,CCl (degrees) is the angle between the z-principal axes of the nqcc tensor and the CCl bond direction. ETA = (Xxx - Xyy)/Xzz. |
|
|
RSD is the
calibration residual standard deviation of
the B1LYP/TZV(3df,2p) model for calculation of the chlorine nqcc's,
which may be taken as an estimate of the uncertainty in the
calculated Xij. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 and 2, the experimental Xbb and Xcc were calculated here from the experimental Xaa and Xbb - Xcc.
The principal values of the nqcc tensors were calculated here
from the experimental data using Z. Kisiel's QDIAG.f. (See http://info.ifpan.edu.pl/~kisiel/prospe.htm.) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 1. Chlorine
nqcc's in gauche-chlorobutyne (MHz). Calculation was made on the ~ re structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
35Cl |
Xaa |
|
9.53 |
|
8.161(10) |
|
|
Xbb - Xcc |
- |
60.79 |
- |
59.422(36) |
|
|
|
Xbb |
- |
35.16 |
- |
33.7915 |
|
|
Xcc |
|
25.63 |
|
25.6305 |
|
|
Xab* |
- |
44.49 |
|
44.83(86) |
|
|
|
Xac* |
- |
16.26 |
- |
17.2(15) |
|
|
|
Xbc* |
- |
27.59 |
|
26.79(64) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
1.12 (5.0 %) |
|
|
|
|
|
RSD |
0.49 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
35.72 |
|
35.92 |
|
|
|
Xyy |
|
37.27 |
|
36.70 |
|
|
|
Xzz |
- |
73.00 |
- |
72.62 |
|
|
|
ETA |
|
0.021 |
|
0.011 |
|
|
|
Øz,CCl |
|
0.64 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* The algebraic signs of the off-diagonal Xij depend on the
orientation of the molecule with respect to positive/negative sense of
the a, b, and c axes. However, the algebraic sign of the product XabXacXbc is independent of axes polarity. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
Table 2. Chlorine
nqcc's in gauche-chlorobutyne (MHz). Calculation was made on the ~ re structure. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc. |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
37Cl |
Xaa |
|
6.77 |
|
5.714(17) |
|
|
Xbb - Xcc |
- |
47.38 |
- |
46.3256(58) |
|
|
|
Xbb |
- |
27.07 |
- |
26.0198 |
|
|
Xcc |
|
20.30 |
|
20.3058 |
|
|
Xab* |
- |
35.46 |
|
35.4(19) |
|
|
|
Xac* |
- |
12.96 |
- |
13.5(20) |
|
|
|
Xbc* |
- |
20.30 |
|
21.12(5) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.86 (5.0 %) |
|
|
|
|
|
RSD |
0.44 (1.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
|
28.16 |
|
28.36 |
|
|
|
Xyy |
|
29.37 |
|
28.71 |
|
|
|
Xzz |
- |
57.53 |
- |
57.07 |
|
|
|
ETA |
|
0.021 |
|
0.006 |
|
|
|
Øz,CCl |
|
0.64 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* The algebraic signs of the off-diagonal Xij depend on the
orientation of the molecule with respect to positive/negative sense of
the a, b, and c axes. However, the algebraic sign of the product XabXacXbc is independent of axes polarity. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 3. g-Chlorobutyne (C1). Selected structure parameters, ~ re (Å
and degrees). Complete structure is given here in Z-matrix format. |
| |
|
|
|
|
ClC(2) |
1.7809 |
|
| C(2)C(3) |
1.5195 |
|
| C(3)C(8) |
1.4585 |
|
| C(8)C(9) |
1.2043 |
|
| C(9)H(10) |
1.0619 |
|
| ClC(2)C(3) |
111.17 |
|
| C(2)C(3)C(8) |
112.57 |
|
| C(3)C(8)C(9) |
178.91 |
|
| C(8)C(9)H(10) |
179.57 |
|
| Click on image to enlarge. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 4. g-Chlorobutyne. Rotational constants, 35Cl species (MHz). |
| |
|
|
|
|
|
~ re |
expt. [1] |
| |
|
|
|
|
A |
7866.6 |
7933.9061(25) |
|
B |
2378.5 |
2326.77773(76) |
|
C |
1950.9 |
1919.42152(75) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] J.C.Keske, F.S.Rees, R.D.Suenram, and B.H.Pate, PCCP 5,1599(2003). The
experimental nqcc's and rotational constants given above were
obtained from B.H.Pate via personal communication.
These differ, mainly with respect to algebraic sign of some
nqcc components, from those published in this paper. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
trans-HCCCH2-CH2Cl |
Chloroethanes
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Chlorine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
gHCCCH2CH2Cl.html |
|
|
|
|
|
|
Last
Modified 8 Feb 08 |
|
|
|
|
|
|
|
|
|
|