Density Functional Calculations of Metal Clusters: Structure, Dynamics, and Reactivity - Metallic Systems: A Quantum Chemist's Perspective - page 330

H

H

H

H

C C

+C 2 H 2 +C 2 H 2 C

C

Fe q+ Fe n

C

C

Fe n

H

H

Fe n (C 2 H 2 ) q+

Fe n (C 2 H 2 ) q+

H

H

H

+C 2 H 2 C

C

H

H

C H

C C

C

H

H

H C C H

Fe n

or

Fe n C

C

C

C

C

C

H Fe n

+C 2 H 2

H

H

H

Fe n ( c -C 4 H 4 ) q+

Fe n (C 2 H 2 ) q+

Fe n ( n -C 4 H 4 ) q+

H H

H

C C

H

H H

C C

C H

C

C

Fe n or

C Fe n

C

C H

H

C C

H

H H

Fe n ( n -C 4 H 4 )(C 2 H 2 ) q+

Fe n ( c -C 4 H 4 )(C 2 H 2 ) q+

H

H

H

H

C

C C

C H

C

H C H

C

C C

H

Fe n

H

C

H

Fe n

C

C

H

Fe n ( c -C 6 H 6 ) q+

H

Fe q+ +C 6 H 6

Fe n ( n -C 6 H 6 ) q+

FIGURE 9.32 Schematic.representation.of.the.mechanism.studied.for.the.formation.of.ben-
zene.from.acetylene.on.iron.clusters,. Fe q + .( n .=.1-4.and. q .=.0-1)..(Reprinted.from.Chretien,.S..
et.al.,. J. Chem. Phys .,.119(23),.December.5,.12291,.2003..With.permission.)

employing.the.hierarchical.transition.state.inder.described.in.2.5.3.[219-222]..Here.
we.will.review.in.more.detail.the.reactions.of. FeO 2 + .and. Fe O
2

+ .with.CO..The.calcu-
lations.were.performed.with.the.gradient.corrected.PBE.functional.[223]..For.C.and.
O,.the.LDA-optimized.DZVP.basis.set.[46].in.combination.with.the.GEN-A2.aux-
iliary.function.set.[48].was.used..For.the.Fe.atom,.the.Wachters.basis.set.[224,225],.
including. f . functions,. in. combination. with. a. GEN-A2 * . auxiliary. function. set. was.
employed..In.a.irst.step,.the.various.reactants,.products,.and.intermediates.that.are.

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