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5
7
4
5
3
6
3
4
6
5
4
1
3
1
2
2
1
2
7
8
6
Cu
+
(C
2v
)
Cu
+
(C
5h
)
Cu
+
(C
2v
)
8
4
6
3
4
6
5
5
3
9
3
2
6
4
1
5
10
1
7
7
2
1
2
8
9
-
Cu
6
(C
2v
)
+
Cu
10
(D
4d
)
Cu
+
(C
2v
)
5
6
4
7
7
5
4
3
5
4
1
3
2
1
1
2
6
3
8
2
7
6
-
-
-
Cu
7
(C
3v
)
Cu
7
(D
5h
)
Cu
8
(C
2v
)
8
4
5
6
7
6
5
4
3
3
3
2
9
9
4
1
1
10
5
1
2
7
8
7
6
8
2
9
-
-
Cu
9
(C
2v
)
-
Cu
10
(D
4d
)
Cu
9
(C
2
)
FIGURE 9.11
Structures. of. the. most. stable. charged. copper. clusters. with. 6-10. atoms..
(Reprinted.from.Jug,.K..et.al.,.
J. Chem. Phys
.,.116(11),.March.15,.4497,.2002..With.permission.)
becomes.linear,.
Cu
6
−
.acquires.a.three-dimensional.structure.like.the.corresponding.
cation,.and.the.
Cu
9
−
.ground.state.represents.a.bond.ring.capping.of.Cu
8
,.which.is.not.
stable.for.the.neutral.nonamer.
For. the. optimized. structures. of. the. neutral. and. ionic. clusters,. binding. energies.
per.atom.were.calculated.at.the.GGA.level..It.was.pointed.out.in.the.literature.that.
basis.set.superposition.errors.(BSSEs).may.be.important.for.a.quantitative.calcula-
tion.of.cluster.binding.energies.[153]..Therefore,.we.have.calculated.the.BSSE.per.
atom.using.the.approximate.correction.of.Jansen.and.Ross.[154]..It.was.shown.[153].
that.the.accuracy.of.this.approximation.is.within.0.2.kcal/mol.per.atom.for.the.basis.
set.used..We.have.also.calculated.the.zero.point.energies.(ZPE).of.the.clusters..The.
values.for.the.neutral.clusters.are.listed.in.Table.4.of.Ref..[144]..The.BSSE.per.atom.
increases. from. 1.4.kcal/mol. for. Cu
2
. to. 5.9.kcal/mol. for. Cu
10
.. The. ZPE. per. atom. is.
much. less. size. dependent. and. considerably. smaller.. For. Cu
2
. and. Cu
3
,. direct. mea-
surements.of.the.atomization.energies.by.luorescence.[155].and.Knudsen.cell.mass.
spectrometry.[156].are.available..The.corrected.binding.energies.(CBE).per.atom.are.
in.good.agreement.with.these.direct.measurements.(see.Table.4.of.Ref..[143])..The.
binding.energies.of.the.larger.neutral.clusters.were.derived.from.CID.experiments.of.
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