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C6H5CCH-d1
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Deuterium |
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Nuclear
Quadrupole Coupling Constants |
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in Phenylacetylene-d1 |
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Deuterium nqcc's were measured in phenylacetylene-d1
by Dreizler et al. [1], who also determined a number of experimental and
theoretical molecular structures. |
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Calculation was made here of the deuterium
nqcc's on the experimental rm(2) and
theoretical CCSD(T)/cc-pVTZ molecular structures of Ref. [1], and
on a structure determined here by B3P86/6-31G(3d,3p)
optimization. In
Tables 1 - 3, calculated nqcc's are compared with the experimental
values.
In Table 4, the principal values of the nqcc tensors calculated on the
B3P86 ropt structure are collected for easy comparison. Structure parameters
are compared in Table 5. |
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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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RMS is the root mean square
difference between calculated and experimental inertia axes nqcc's (percentage
of the average of the magnitudes of the experimental nqcc's). RSD
is the calibration residual standard deviation for the B3LYP/6-31G(df,3p)
model for calculation of the nqcc's. |
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Table 1. Deuterium
nqcc's in C6H5CCH-d1 (kHz). Calculation was made on
the rm(2) structure [1].
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Calc. |
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Expt. [1] |
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2H(4) |
Xaa |
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194.8 |
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188.9(10) |
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Xbb |
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- 92.1 |
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- 92.2(35) |
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Xcc |
- |
102.8 |
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- 96.7(35) |
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RMS |
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4.9 (3.9 %) |
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2H(3) |
Xaa |
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- 15.8 |
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- 28.7(21) |
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Xbb |
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117.6 |
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117.9(32) |
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Xcc |
- |
101.7 |
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- 89.2(32) |
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|Xab| |
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125.3 |
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RMS |
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10.4 (13.2 %) |
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2H(2) |
Xaa |
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- 19.3 |
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- 31.7(15) |
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Xbb |
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123.1 |
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125.1(21) |
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Xcc |
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103.8 |
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- 93.5(21) |
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|Xab| |
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125.6 |
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RMS |
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9.4 (11.2 %) |
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2H(8) * |
Xaa |
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226.4 |
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207.6(10) |
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Xbb |
- |
112.7 |
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103.9(30) |
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Xcc |
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113.7 |
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103.7(30) |
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RMS |
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13.3 (9.6 %) |
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RSD |
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1.1 (0.9 %) |
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* Acetylenic. |
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Table 2. Deuterium
nqcc's in C6H5CCH-d1 (kHz). Calculation was made on the CCSD(T)/cc-pVTZ structure [1].
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Calc. |
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Expt. [1] |
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2H(4) |
Xaa |
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191.2 |
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188.9(10) |
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Xbb |
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- 90.2 |
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- 92.2(35) |
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Xcc |
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100.9 |
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- 96.7(35) |
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RMS |
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3.0 (2.4 %) |
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2H(3) |
Xaa |
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- 16.0 |
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- 28.7(21) |
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Xbb |
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116.9 |
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117.9(32) |
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Xcc |
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100.9 |
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- 89.2(32) |
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|Xab| |
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123.9 |
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RMS |
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10.0 (12.7 %) |
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2H(2) |
Xaa |
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- 17.6 |
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- 31.7(15) |
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Xbb |
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118.2 |
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125.1(21) |
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Xcc |
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100.6 |
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- 93.5(21) |
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|Xab| |
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122.1 |
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RMS |
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9.9 (11.9 %) |
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2H(8) |
Xaa |
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214.7 |
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207.6(10) |
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Xbb |
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106.8 |
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103.9(30) |
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Xcc |
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107.8 |
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103.7(30) |
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RMS |
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5.0 (3.6 %) |
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RSD |
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1.1 (0.9 %) |
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Table 3. Deuterium
nqcc's in C6H5CCH-d1 (kHz). Calculation was made on
the B3P86/6-31G(3d,3p) ropt structure.
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Calc. |
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Expt. [1] |
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2H(4) |
Xaa (zz) |
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188.9 |
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188.9(10) |
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Xbb (xx) |
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- 89.1 |
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- 92.2(35) |
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Xcc (yy) |
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- 99.7 |
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- 96.7(35) |
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ETA |
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0.056 |
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RMS |
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2.5 (2.0 %) |
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2H(3) |
Xaa |
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- 15.6 |
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- 28.7(21) |
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Xbb |
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115.3 |
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117.9(32) |
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Xcc |
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- 99.7 |
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- 89.2(32) |
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|Xab| |
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122.5 |
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RMS |
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9.8 (12.5 %) |
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Xxx |
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- 89.0 |
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Xyy |
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- 99.7 |
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Xzz |
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188.8 |
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ETA |
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0.057 |
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Øz,a |
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59.06 |
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Øa,CD |
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59.07 |
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Øz,CD |
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0.01 |
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2H(2) |
Xaa |
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- 17.5 |
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- 31.7(15) |
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Xbb |
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117.3 |
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125.1(21) |
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Xcc |
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- 99.8 |
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- 93.5(21) |
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|Xab| |
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120.9 |
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RMS |
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10.0 (12.0 %) |
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Xxx |
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- 88.6 |
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Xyy |
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- 99.8 |
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Xzz |
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188.3 |
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ETA |
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0.059 |
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Øz,a |
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59.56 |
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Øa,CD |
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59.36 |
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Øz,CD |
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0.20 |
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2H(8) |
Xaa (zz) |
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212.2 |
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207.6(10) |
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Xbb (xx) |
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105.6 |
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103.9(30) |
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Xcc (yy) |
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106.6 |
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103.7(30) |
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ETA |
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0.005 |
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RMS |
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3.3 (2.4 %) |
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RSD |
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1.1 (0.9 %) |
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Table 4. Principal
values of the deuterium nqcc tensor calculated on the B3P86/6-31G(3d,3p)
optimized structures of phenylacetylene (PhA), fluorobenzene (FB), and benzene.
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Xzz |
Xyy |
Xxx |
ETA |
Øz,CD |
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C6H5D |
189.0 |
-99.9 |
-89.1 |
0.057 |
0 |
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PhA D(4) |
188.9 |
-99.7 |
-89.1 |
0.056 |
0 |
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FB D(4) |
190.0 |
-101.1 |
-88.8 |
0.065 |
0 |
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PhA D(3) |
188.8 |
-99.7 |
-89.0 |
0.057 |
0.01 |
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FB D(3) |
188.7 |
-99.6 |
-89.2 |
0.055 |
0.03 |
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PhA D(2) |
188.3 |
-99.8 |
-88.6 |
0.059 |
0.20 |
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FB D(2) |
190.0 |
-100.8 |
-89.2 |
0.061 |
0.29 |
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The "bond bending" seen in D(2) compared with D(3) recalls that seen
in chlorofluorobenzene (CFB). In 1,3-CFB, Øz,CCl
is 0.06o. In 1,2-CFB, it is 1.07o. Otherwise,
the substituent has little - if any - effect on the deuterium coupling. |
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| Table 5. Phenylacetylene. Molecular structure parameters (Å
and degrees). |
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rm(2) * |
ropt ** |
ropt *** |
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C(8)H(8) |
1.0546 |
1.0635 |
1.0654 |
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C(7)C(8) |
1.2074 |
1.2136 |
1.2073 |
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C(1)C(7) |
1.4446 |
1.4372 |
1.4232 |
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C(1)C(2) |
1.3928 |
1.4044 |
1.4011 |
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C(2)C(3) |
1.3953 |
1.3946 |
1.3872 |
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C(3)C(4) |
1.3956 |
1.3976 |
1.3910 |
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C(2)H(2) |
1.0771 |
1.0826 |
1.0840 |
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C(3)H(3) |
1.0814 |
1.0829 |
1.0849 |
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C(4)H(4) |
1.0796 |
1.0828 |
1.0848 |
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C(6)C(1)C(2) |
120.70 |
119.45 |
119.15 |
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C(1)C(2)C(3) |
119.53 |
120.13 |
120.25 |
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C(2)C(3)C(4) |
120.22 |
120.21 |
120.25 |
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C(3)C(4)C(5) |
119.81 |
119.86 |
119.86 |
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C(1)C(2)H(2) |
120.19 |
119.27 |
119.14 |
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C(2)C(3)H(3) |
119.98 |
120.10 |
120.06 |
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* Ref. [1], Table 12. rm(2) mod IRLS. |
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** Ref. [1], Table 17. CCSD(T)/cc-pVTZ
optimized structure. |
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*** B3P86/6-31G(3d,3p) optimized structure. |
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[1] H.Driezler, H.D.Rudolph, and B.Hartke,
J.Mol.Struct. 698,1(2004). |
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"Accurate Determination of the Deformation of the Benzene Ring upon
Substitution: Equilibrium Structures of Benzonitrile and
Phenylacetylene" H.D.Rudolph, J.Demaison, and A.G.Császár,
J.Phys.Chem. A 117(48),12969(2013). |
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Benzene-d1 |
Fluorobenzene-d1 |
Pyridine-4D |
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1,2-Chlorofluorobenzene |
1,3-Chlorofluorobenzene |
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Acetylenes |
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Table of Contents |
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Molecules/Deuterium |
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C6H5CCH.html |
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Last
Modified 17 Jan 2005 |
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