Density Functional Calculations of Metal Clusters: Structure, Dynamics, and Reactivity - Metallic Systems: A Quantum Chemist's Perspective - page 313

TABLE 9.1
Peak Positions, Assignment, and Relative Intensity,
Given as v ion

neutral , of the Simulated Nb 3 O − → Nb 3 O +
e − Photoelectron Spectrum at 300 K
Our Notation
(Neutral)

Spacing from
Origin (cm −1 ) Assignment Relative Intensity

3 3 0 −310.(−295) 0.017.(0.036)

0 1

0 0

3 1 3 316.(320) 0.135.(0.164)

3 3 2 631.(635) 0.001.(0.001)

6 1 1 738.(710) 0.037.(0.033)

1 1

1 3
0

1054.(1025) 0.077.(0.012)

0

Source: . Reprinted. from. Calaminici,. P.. et. al.,. J. Chem. Phys .,. 121(8),.
August.22,.3558,.2004..With.permission.
Note: . Experimental.data.from.Ref..[128].are.given.in.parentheses.

Ref..[108]..This.is.probably.due.to.the.difference.in.bond.lengths.calculated.for.the.
neutral.Nb 3 O.system.(see.Figure.9.20.of.this.work.and.Figure.9.4.of.Ref..[108])..We.
account.this.to.the.improved.accuracy.of.the.numerical.integration.of.the.exchange-
correlation.potential.in.deMon2k.
In.Ref..[185],.we.have.compared.the.calculated.spacing.from.the.origin.and.the.
relative.intensities.for.the.most.relevant.peaks.with.experiment..We.list.in.Table.9.1.
the.peak.positions,.the.assignment,.and.relative.intensity.of.the.simulated.photoelec-
tron.spectrum.at.300.K.together.with.the.experimental.data..For.easy.comparison,.
we.have.used.the.same.labeling.as.in.Ref..[128]..The.experimental.values.are.given.in.
parentheses..As.Table.9.1.shows,.the.calculated.spacing.of.all.peaks.is.in.good.agree-
ment.with.the.observed.data..Also.the.intensities.of.the.hot.band.and.the.fundamen-
tals.show.fair.agreement.with.experiment..The.intensity.of.the.non-Franck-Condon.
transition. 1 3
0

1 ,. however,. is. much. too. large. in. our. simulation.. We. have. observed. a.
similar.behavior.also.in.the.case.of.the.V 3 O.study.[184]..Our.studies.indicate.that.
these.disagreements.can.be.attributed.to.small.errors.in.the.force.ield.of.the.anion..
The.calculated.adiabatic.electron.afinity.is.1.39.eV..This.value.is.in.excellent.agree-
ment. with. the. experimental. reported. value. of. 1.393.±.0.006.eV. from. negative. ion.
photoelectron.spectroscopy.[128].

1

0

9.5 POLARIZABILITIES (LI, NA, CU, FE, NI)

9.5.1 S imPle m etal S yStemS (l i , n a , c u )
The.static.polarizabilities.of.atoms.and.free.clusters.have.been.extensively.studied.
both. theoretically. and. experimentally. (we. refer. the. reader. to. Refs.. [186,187]. and.