Chemistry Reference
In-Depth Information
a
b
c
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120
100
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100
80
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60
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60
6
0
80
100
12
0
14
0
1
6
0
60
80
10
0
1
2
0
140
16
0
6
0
80
100
12
0
1
4
0
1
6
0
d
e
f
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g
h
i
160
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120
100
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100
80
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Fig. 1 Difference densities in the molecular plane,
r
4comp
(
r
)
r
nonrel
(
r
) for (a) Ni(C
2
H
2
), (b)Pd
(C
2
H
2
), (c) Pt(C
2
H
2
);
r
ZORA
(
r
)
r
nonrel
(
r
) for (d) Ni(C
2
H
2
), (e) Pd(C
2
H
2
), (f) Pt(C
2
H
2
); and
r
DKH10
(
r
)
r
nonrel
(
r
) for (g) Ni(C
2
H
2
), (h) Pd(C
2
H
2
), (i) Pt(C
2
H
2
). Values of positive and
negative difference densities are indicated by
solid
and
dashed lines
, respectively. Contour lines
are drawn at
10
n
e
˚
3
with
n
0, 1, 2. Note that the axes labels denote grid
points. (The figure is reprinted with permission from [
64
]. Copyright 2010 American Chemical
Society)
2,
4,
6,
8
¼
concentrations of the valence region of the nickel atom. Moreover, the scalar-
relativistic DKH10 Hamiltonian yields two more contour lines of negative differ-
ence than the Dirac or the ZORA-SO difference densities in the region around the
carbon atoms of the acetylene ligand. From the results of the nickel complex, one
obtains a first indication that the scalar-relativistic DKH10 Hamiltonian recovers
less of the relativistic effects than the ZORA-SO Hamiltonian.
The difference density maps for the palladium complex are depicted in Fig.
1b,
e, h
. Here the situation is very similar to the nickel complex, but the relativistic
effects are more pronounced. The four maxima in the valence region of the metal
