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Technical Report No. 39
SOLIDS AND SURFACES:
A CHEMIST'S VIEW
0by
Roald Hoffmann
I.,
Department of Chemistry
Cornell University
Baker Laboratory
Ithaca, NY
14853-1301
July 1988
Reproduction in whole or in part is permitted
for any purpose of the United States Government
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for
EARL HUETTERTIES and MIKE SIENKO
-4,
N.
;S
'.
44
__
While in my usual
Several
We
NSP CTEDO
6
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~~ ~ ~q ~~
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I At
Spec I l.
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It was
I owe Bill
MSC furnished an
pip -. 172170..A777.-77
Vill.
iii
one reason it is easy to cross disciplines at Cornell is the
existence of the Physical Sciences Library, with its broad
coverage of chemistry and physics.
Our drawings, a
The
Earl
colors our walls, and the glass through which we look at the
outside world.
us.
Solid
1
state chemistry is important, alive and growing.
So is a surface science.
A surface
be it of metal, an
is a form of matter
bulk, discrete
It is important to find
The
9.
tools may come from physics, but the questions that are asked are
very chemical
We always knew
But it
Chemists
In
Pp.P
is not only easy, but how in many ways it includes concepts from
molecular orbital theory that are very familiar to chemists.
I suspect that physicists don't think that chemists have
much to tell them about bonding in the solid state.
disagree.
I would
clusters, and their literature and memory are particularly welldeveloped, so that one can immediately think of a hundred
structures or molecules related to the compound under study.
From much empirical experience, a little simple theory, chemists
have gained much intuitive knowledge of the what, how, and why
molecules hold together.
until
Their papers
have served solid state chemists well have not been "molecular".
At the risk of oversimplification, the most important of these
concepts have been the idea that one has ions (electrostatic
forces, Madelung energies), and that these ions have a size
(ionic radii, packing considerations).
simple notions has lea solid state chemists to use these concepts
even in cases where there is substantial covalency. What can be
wrong with an idea that works, that explains structure and
properties?
A%
the marvelous
And it is
In
some differences.
ra
.t
5-
;Ni'
visualize.
equally spaced H atoms, 1, or the isomorphic r-system of a nonbond-alternating, delocalized polyene 2, stretched out for the
moment.
7%
...
M ......
M.......
.....M .. .
..
4 ........
.....
A digression here:
.......
t
feeling for what that model chain of hydrogen atoms would do, if
we were to release it from the prison of its theoretical
-...7H ....
- 7H
band for the equally spaced polymer, then seeing that it's
subject to an instability, called a Peierls distortion.
Other
words around that characterization would be strong electronphonon coupling, pairing distortion, or a 2kF instability.
And
Incidentally,
It
sized rings on the way to that very large one are quite well
known.
..
...
S-
VT L
T T
.. IA
IT
'
--
th
hi
-_ --
-.
d g
e ner t
pairs
Th
-,:m,
,",,
4
-,
expect the
in energy.
as one rises
nodeless,
number of nodes increases polymer
level We'd
lowest
the
the same for an infinite
highest with the maximum number of nodes. In between the levels
should come in pairs, with a growing number of nodes. The
chemist's representation of the band for the polymer is given at
right in S.
%---
10
Bloch Functions. k. Band Structures
There is a better way to write out all these orbitals,
making use of the translational symmetry.
If we have a lattice
M.0
X0
4 ...
x~, xt x X
We will see in a
moment that k is much more, but for now, k is just an index for
an irreducible representation, just like a, el, e 2 in C 5 are
labels.
The process of symmetry adaptation is called in the solid
state physics trade "forming Bloch functions". 6 ,8 ,9 - 1 1
To
'
.d
C * C~**
~
.*V'...W
PC'
C. C.*J
C.
C.~*
*~~~
Ii'
.ox
.'
..
X24
k" .o/fX,
.X30C
'-
as well.
So k counts nodes
a range of k and if one goes outside of it, one doesn't get a new
wave function, but repeats an old one.
This is called
So let us
There is an energy
There is an
12
easily proved theorem that E(k) = E(-k).
Most representations of
E(k) do not give the redundant E(-k), but plot E(IkI) and label
it as E(k)).
h/p.
E W)
k/-5
there
13
You can be
sure that they can be much more complicated than this simple one,
but no matter how complicated, they can be understood.
'U
I
I~
I,-
'I
"N
"
, ,,4
-.-.
14
Band Width
One very important feature of a band is its disersion, or
bdwi,
Figure 1
unsymmetrically around their "origin", the energy of a free H
atom at -13.6eV, is a consequence of the inclusion of overlap in
the calculations.
HAB
1 SAB
The bonding E+ combination is less stabilized than the
antibonding one E_ is destabilized.
0 ....
0 ....
0.-.
.0-....0....
0 ....
20-
000
15-
10-
-P0-
Figure 1.
apart.
-JWVUU
.lllo-
--
wv
15
4
The
For a
But
.5
E W)
k..-
oe
16
10
The three-fold
for a:
infinity):
+ X
x
+
is the w orbital of
17
.5..
I
An Eclieed Stack of Pt(III Scuare Planar Complexes
This is
The
A.
Pt
Il
12
inversely related to the degree of oxidation of the material.
2a
2-
p-
,,
13
.
.,.
.5%
,IV
.5
..
'.
4. Vt .5
Y~.V'
. ...-\
~5
.,
~~.
~
'.
.N
~-
,,
181
likely to be essential, let's imagine a theoretician's generic
ligand, H-.
But a
*6"
t
S
-- m yz
-
xz
4L
Pt
L-
L-Pt-L
Figure 2.
'-L
%U-N__
W-I
-ii
.. t...*..
WA
19
II
is. yx
14
as shown in 14.
x/a).
The moment one writes these down, one sees that the z2 and xy
bands will run "up" from the zone center (the k
0 combination
is the most bonding) while the z and xz bands will run "down"
(the k -
2. :
" J .
k' .':
.'
"g
..
..
'
c'
'
"
",
4.
"4.
20
k a ir/a
&
KY
isz
fs5
To make a real
E
it , YZ
AVo
161
k-
--
w/o
,.
',
":,',,'-.'.-
.. "
"'""-'-'
.
.
21
--
these
the
If we are asked
10
from the z2 (a), xz, yz(x) and x 2 -y2 (6) frontier orbitals of each
ReCl 4 - fragment.
z
.r
-6 -_ 2-Y2 . _ _ _
___
0'
9.
0
1 0.
*
Cl
-'12
-'
XZIyZ
xy
4
*p
D
. '
F3gUre 3.
Computed band
stuctu
he orbital marked
Xz,yz
of an eclipsed
PtH4 2
doub
stack, spaced
at
degenerate
Vw
22
few more levels, but the translational symmetry helps us out with
that.
I
I:
-4.'
23
In
They fill
the a, two x and the 6 level for the explicit quadruple bond.
What about the [PtHJ-], polymer 12?
Each monomer is d 8 . If
-]
Filling a band
I
I
24
So
A typical degree of
So
'S
25
p
4.
4.
4
26
It turns
(a=lall=l2l
2 ). Some typical solutions are shown below, in 19.
The construction of these is obvious.
Consider
A look at
them reveals that they are waves running along a direction which
N.N.%
%'W
27
k,90. kysO
kx-lr/2a, kyO
k,, ky
r'/2a
r,/ky
a/O,
k,a 0, k),,
V/20..
,'0
ky'r/a
The wave
Certain
for all
, .'
28
X, r
M, X -M.
IiI
/p
21
\I
The large
peak in the DOS for the half-filled H s-uare lattice band would
make the physicist think of a lattice vibration that would create
a gap at eF.
H Square Net
4U
-to4
r1
Fiue4
atmHHsprto
-10rDO
h adsrcueadDSo
.
qaeltieo
29
operation at all k.
one-dimensional case we could talk at one and the same time about
chains of H atoms and polyenes.
The Px, Py (x, y) orbitals present a somewhat different
problem.
PI
Exx
qi,'
Ole
010
M
OKOI-0
r,
ckaeko_0
UI~1r*
o71
4-
30
of each at r, X, Y, and M.
(Y is by symmetry equivalent to X;
Zach
.1
if
M, but
structure.
This is Fig. 5.
Band
Figure 5
dispersions will increase with short contacts, and complications
due to s, p mixing will arise.
Roughly, however,
=ny square
U
4.
-X-
~-
.~
C~YC
~'
Y~
N"]-V--&
,%~
.M
ky
O.
"
U'
"
0
X
I 'I'I
kS
A.
,'
,:
""'
31
absorbed on Ni(100)17
S
% .9
32
It makes sense to
It puts
We know that
The extent of
It can also
33
One aspect
S
That piece
Half of
',
'x
~34
23 shows a four-
IC
23
Thick enough so that its inner layers approach the electronic
properties of the bulk, the outer layers those of the true
surface.
Not one
preference.
NI
00
Ni
2'I
35
adsorption, coverage = 4.
The
air
dimensional.
E vs. 1L
4\
fp.~*-
,<
4'
4...
v~
*
.~
__
00
I.
..
I-:C
'
I."
-.C-.-.c T.:..)o....
10
--,.s0
-,o
q,1
U
'1"
............
50"
4a,
of CO at two separations:
Band structures of square monolayers
and full
X.These would correspond to
(a) left, 3.52 , (b) right, 2.49
Figure
I
.,
-10
Ni
4 layer slab
Figure?.
Th., flat bands are derived from Ni 3d, the more highly
4 p.
36
(kx, ky).
r(the zone
M - (n/a, w/a).
What is being
molecule per unit cell, and that molecule has well-known 4a, 1x,
5a, 2** MO's.
This is
the energy of that orbital in the unit cell which gives rise to
the band.
because there is
The
It's no
surprise that the bands are more dispersed when the CO's are
closer together.
37
J.
They run up or
But,
There is a way.
~38
Density of States
In the solid, or on a surface, both of which are just very
large molecules, one has to deal with a very large number of
levels or states.
speaking, they are jammed into the same energy interval in which
we find the molecular or unit cell levels.
In a discrete
level among the myriad Nn orbitals of the crystal will have the
power to direct a geometry or reactivity.
There is, however, a way to retrieve a frontier orbital
language in the solid state.
There
are many ways to group levels, but one pretty obvious one is to
look at all the levels in a given energy interval.
The density
V'
V.
?-'
39
equally spaced along the k axis, and because the E(k) curve, the
band structure, has a simple cosine curve shape, there are more
t
E
E(k)E
k-
V/4
00O -
chain, Fig.
In general, the
The integral of
V,
So, the
DOS (E
z
-4-.
2-
2.
3.0
1>1'..
-1455
Pt-Ho
k
Figur.
7r/a 0
Density of States
The DOS curves are broadened so that the two-peaked shape of the xy peak in
the DOS is not resolved.
CO monolayer
0
.0
A-4
1--3-52
27r*
4)
5
,J
40-
Figure
XM
DOS-.I
$apart.
-r.
40
The
If I may be permitted
space.
There is another aspect of the return to real space that is
significant:
apDroximatelv. intuitively.
The monomer
At intermediate
27 is a
Compare 27 to Fig. 8.
41
Monomer
ol ymer
1
A
22-y
zy -
Pt-I.,Pt-0
'5
i%I|
As 28 shows,
There
42
at
We expect
,e
mainly Ti sp
S"-0 anibonding
A
antibofidilng
0o
DOS -
2S
Note that the writing down of the approximate DOS curve is
A
done k
Not that
But it is three-
dimension.
complex.
Figure 10
bands), simply because the unit cell contains two formula units,
There is not one reciprocal space variable, but several
(Ti02 )2 .
lines (r
X, X
N
N, etc.) which refer to directions in the
d.'
-400
-N
--
.,.,
.46
Figure
DO
'.36
The tWo
'.
43
If we glance
Would you like to try something a little (but not much) more
challenging?
It gives us tremendous
Goodenough, who has shown over the years, and especially in his
prescient book on "Magnetism and Chemical Bonding", just how good
the chemist's approximate construction of band structures can
be. 25ct
In 27 and 29, the qualitative DOS diagrams for PtHio and
Tio 2 , there is, however, much more than a guess at a DOS.
There
44
'aZ
45
This is how
2c1 c2S
12
is
It's
Thus center 1 is
46
In the
solid state trade these are often called "projections of the DOS"
or "local DOS".
among the atoms.
Fermi level then gives the total electron density on a given atom
or in a specific orbital.
47
Figures 11 and 12
Do we want more specific information?
to see the crystal field argument upheld.
contributions of the three orbitals that make up the t2g (xz, yz,
xy in a local coordinate system) and eg(z 2 , x2 -y 2 ) sets.
This is
If we look at the z
4% of the
0
-'
J.
. Pt- H o- , xk y2
-6
0'.
0
C
-I0
Pt d band
Pt-H oPt
Figure jI.
stack."
:. -,v ,-..
-,-. -;-..
-. ,"
.. -,_-"
,'-" ." .'-..-.
.'.." ,"-, .,
,' -'_,"..q-.
." .'.'_." .'
". ..
."
.4.
. ...-.-. '-,
-
06
Ti
in rutile
-2
in rutile
-8
-14
-2,
-23
-26-"
-29
"-352,
-
4.1
DOS--.
DOS
-5-
-2,'.
-20
-23
DOS-.
DOS---29
1Z. Contributions of Ti
-32 and 0 to the
~ ~ .A '. ~ 9. -35t
W
A
'
eq Ti
the tag and
shown at top. At.- bottom, OS'-"
.
Figure
'
.-'"
.,
Integration of DOS
- --.-
--
-6
."
(00%
---
-10-
-8
>' -10
-1
--
--
0',
.
Fiwe1.z
otiuin
I.
otettlDSo
nelpe
stack.
doted The
line isan ntegration oftheZobtlcnrbto
thS ofria
stack.Tenite lin isaitegrationsit
otibution
48
poor.1 1
This is
At k
is really small.
But it
I..
-. -.
A
r
-,~~S
-ft
~~P
.~
..
.. J ..
..
..
V. .Y
.A ..
49
We saw in a
Some of
the wriggles in the DOS curves also are not real, they're a
result of insufficient k-point sampling in the computation.
Figure 14
Yet things
and
Figure 15
Figure 15
shows the 5a and 2w* contributions to the DOS.
04
In
oW% o
C.)
4J
CL
(AS
AbQ
~1W
~ PV'
~*
~=
i......................................
-
,.
.~
~ ~
0-
.,,
,~
.~
41
oo
00
4~4n
bCD
4.C3
o j4
CA
4-
cm
(U0.
4.1
co
ol
u,
a,
0
4J
0.
4.
44
C-
. a)~J
w0
gfl~
~
~
(AG) ABJGU3
f)
50
It is clear
The 2w * orbital
III
MLn
ab
We would suspect
2)
note
.|
IV
51
Figure 16
how 2s*
I haven't
'I
In 25 we drew several
Consider one of
In all
'A
2u*of CO
2vt
ofC
c(Wx)CO-NM~OO)
c(2x2)CO-NM~OO)
CO monoloyer
DOS-
DOS-
DOS-
-31of surfacesNltomn
NlIlOO) slab
--
as of surface Ni atom
c(Wx)CO-NIlOO)
54P o CID
c(2x2)CO-Nl(lOO)
Baof CO
CO monolayr
DOS-
DOS-
DOS-
DOS-
-5.
-12
-10
DOS-
S-5e
_9
W-10
-13
The
extreme left and right panels in each case show the contributions of the
appropriate orbitals Wz for 5a, xz,yz for 2rr*) of a surface metal atom (left),
and of the corresponding isolated CO monolayer MO.
then show the contributions of the same fragment MO's to the DOS of the composite chemisorption system.
52
into the ,
and z,
D-k-
It
o*of CO. 2 9
Figure 17
A third system:
II
H
'
30
three snapshots of the total DOS and its au*(H2) projection.
These are computed at separations of 3.0, 2.5 and 2.0 A from the
.........
.......
o .....................
'
"
'
44T.
.... .. . . .
O N
u
1060
.-
I4J
_1
IA
4J
-.
"0
cuE
.I
i_
In
4.i)
M".
............
Sb
V
a
"
LL.
-.
4-
EU
'
^o
-u
4J
of
UCAJ....
T
TO'
(A
53
Figure 18
nearest H of H 2 to the Ni atom directly below it.
The ag orbital
Fermi level.
Why does au* interact more than ag?
The classical
IHijI 2
Ei0Ej 0
helps one to understand this.
In addition, its
1,
(0102)
/2 (1Sl2)
The au
This has been pointed out by many people, but in the present
context importantly emphasized by Shustorovich and Baetzold. 3 1- 3 3
We have seen that we can locate the electrons in the
crystal.
But...
"OX'
z)
Pit
IS
"
0,'
....
I-
01
le
--
.o .,I
.4,= oI
CN
-.-
4'
4-
.~V
it~~S
.lI
>
-",
4-
to
-b
-+,0
4J
CL 0
.,-l
*I
CL
>
to
to
rI
:.:
o,
Ig
_ .s
.
i'sI
."+
,0
II*i n
I
t
"
I"
|1I I
....
..
..
o o ,
--
I1
I
.
-I
T
I" ..
w
II
a..
, ,o
II
(Ae)
,B~eu3
'T.
IJ4.
.5
Ir
.2
4-
-.
-S
to
0
E-"
"
-.01
r' -r
0
','"
54
If the
And the
lag and
is strongly bonding,
2 au
NV
,, ,4 ..,,,
' ,;";. .?. .. ;.
,.
:,
..;
c.
C-..-
., ,;
.--
3'a
-10.
7rg
3o-
7ruu
3o-
-o
20-
-30-
9!
4))
"DOS"--.
k,/,S
,"
-30.
Figure 19.
.j
-a
, . Fi,
gure .
The-,
..orbit . .a-,-'s
f--o
2: (l"f ). n.a.
st t.w
t.lo
.ld
55
and
3 ag
3 aU
the a* level.
It tells us that
.4
extended systems.
A bond indicator is easily constructed for the solid.
An
and DOS were given earlier, 26; they are repeated with the COOP
curve in 35.
To calculate a COOP curve, one has to specify a bond.
take the nearest neighbor 1,2 interaction.
Let's
56
....
" ..".. 'H
anta-boM11ng
bonding-
DOS-
COOP
right in 35.
If we
This points us
i""
" . ...
These are
57
It is the
1.
The
in Pt-Pt bonding.
LAI..
(AO) A6,1au 3
100
T
C
-W
oo
"
"
CL
(1 0
4.)
0
4-)
...
-4
4.)
00
.4.4
V
(AD
O.
04
58
Schenmlc decomlpostio
a-xy
Totol
36
--
++-
--
+-
--
--
0- +
If we are presented
Removing
So we
Oxidation and
59
more complicated.
The
corresponding COOP curve for the Ti-O bond (Fig. 21) is extremely
Figure 21
simple.
The
We can
4p4
6. 0 band
bow
OOS-
make some judgment as to the width of the bands from the overlap.
The s, p orbitals are diffuse, their overlap will be large, and a
wide band will result.
Fiur
21-O6n
T-
OPfo
uie
60
extensively.
At
1 5 s0 -6 2 p 0 .2 3 .
Figure 22
What would one expect of the COOP curve for bulk Ni?
As a
6b
(~p
Total
-0.
The composite
-0.
-0.
-0
'
100%
Bulk Ni
s contribution
10
00%
Bulk NI
p contribution
S.:.
:"
..........
.......
..... ..
.
.. .....
. ....
.......
.
...
...
,. .. .....
.,..
.
..
1...."
..-
-5o
'U-..,
3-
*tl
naseo
to
100% gienatp
%.
Figure
22.
bulk Ni.
"'
,
Ok%
... "
* '
; ::
61
is 38c.
The expectations
Figure 23
If we assume that a
similar band structure and COOP curve hold for all metals (in the
solid state trade this would be called the rigid band model),
then Fig. 23 gains tremendous power.
cohesive energies of all metals.
loNi-Ni
10.
-,6
-6.
"-6
DOS
-i'
.e-AnegrnS
Sondlng-.
coop
Figure
23.
The total DOS and nearest neighbor Ni-Nj COOP in bulk Ni.
p"
%'
62
Fig. 24.
"N
C-O bonding.
responsible for the Ni-C and C-0 antibonding above the Fermi
level. 2 7
It may be useful to emphasize that these curves are not only
descriptive, but also form a part of the story of tracing down
interaction.
Nothing
W,
_J'
antibonding
---
bonding
Ni-C
......... C-0
-4.0-
S-6.027r*
..................
. .. 1.
.........
C~t
LU...................
- 8.0""
-I0.0 -d
....
:
o
block
-12.05cr
-14.0
Figure 21.
"
c(2x2)CO-Ni(100) model.
63
,1
d7,
17r Q
M
In free CO the
On
How
But
40
2-fold or
Why?
p
.
-.
4
64
CH3
CH
40
41
of this fragment.
Figure 25 clearly
*.5
VV
00
oo
04W1
==
N-
"00
.
0~
'VI
01
0o
.T
cmt
T
a.
410
T.
-4su
(AaC
4j,
65
--
There is no mystery in
prxjm
The construction
But as for
7V
or
V..
66
The Th
2SL2_Structure
To see how
However,
these compounds are there, we know their structures and they have
interesting properties.
The very
It consists of B 2 X2 2
layers
67
indication not only of covalent B-X bonding, but also some metalmetal B-B bonding.
x-x
0O
42-11
0 C,
Th 8
A
0
Si
The
098
68
Ix
On that
This contact
In Table 1
In these
68a
Table 1.
dx- x (A)
AB 2 X 2
dx-
(A)
CaCu 1 . 7 5 P 2
2.25
SrCu 1 . 7 5 P 2
2.30
CaNi 2 P 2
2.30
SrCo 2 P 2
3.42
CaCo 2 P 2
2.45
SrFe 2 P 2
3.43
CaFe 2 P 2
2.71
4i
.-
.%"
'
,-
..
. .
69
The
In
As one
--
We would like
associated with a filled octet p3-, the full P-P single bond with
a p-p4 .
-~
VW
SjE.~V
,V
S,~S~~~*S
5
~'Y
70
First
Then we formed
But in
(
MI_
MiM
mostlytly
M.i.
M(PRS) 4
4PR 3
'
'
71
Four
Four orbitals,
In addition,
there are Mn-Mn bonding contacts in the layer, and these will
lead to dispersion in those bands which are built up from
orbitals containing substantial metal character.
The combined
Most certainly.
The calculated
P is
The number
*:'
..9
-...
.-,
. '- ,, - . , .
. - . '-;."-
. - . .. ... . . . .
,. .
,..
, ,
>
,:,,
-v,"
"
,-"
"""
''
_-.
or
Mn 4p
Mn~
=Mn
s, p bands
"
Mn 4s
J m
Mn d bonds
Mn 3d
P3p
_____-
______
P p bands
P 3s., P s bands
"-.//=zz
Separate atoms
Figure
26.
Mn-P bonding
turned on
Extended interactions,
especially Mn... Mn
bonding, turned on
- layer
band structure as
derived by first turning on local Mn-P interactions and then the two-dimensional
periodicity and Mn-Mn interactions.
'
1.
%.
%.
-.
~.
..
%a.
a,
-.
.~
-.
~.,
4.
a.
4.
a~
~.
4.
V.,.
44
.a,.
.'
S
.4.
N
.4.
0
N
a-.
'.4
S.-
al-v
al-N
a'..
a.
a..
.4.
S
4.
4~a%
.4 al~
0
a,
a,
_______________________________
_____________________
a...
44
_______________________________________________________
DOS
-'.4.
a N.
Figure
27.
2-
layer.
-44
S.
4.
6
~
~jaja
a'w44~aa,~%~..
~.a
\~
*/.4.t~
'
5'.
5,4.
4.
Z,
-40 -4-
,-
Total DOS
" -.--6"
Mn Contribution to"
DOS
I-'
_8I2
-.--- ::.
o
..
-14 CV
_22-
-20
'-'16
Density of States
Figure
What is not
"
5;i
$'
72
At
OPA
..
12I
w
-18
-20
-22
-antibonding
bonding
COOP
Figure 29. Crystal orbital overlap population curves for the Mn-Mn bonds
(solid line) and Mn-P bonds (dotted line) in the Mn2P2 2
single layer.
P 3pz should
Here is
A.
Ju
Z4-
41
I
%
ID0
An
(a
Q3
4.1
Law..
4.
-4
-6
-8
-10
-0
-12
w -6
~-
----
-P
-20-22_
Density of States
Figure 31.
Phosphorus
74
But there is a
The
2-
density of states at
Below and above this metal band are P bands, and in these, quite
well localized, are P-P a and a* combinations, 47.
These bands
.'
"I77-;-%j
,LP.F r7.7vN,'17-77
-4
;0
-6
-8
100
-I0--,----
-10
- a-a-a
aa
---a
--
.a
a. -
a'
a'
22..* ...
-8
ie
on
cale
af 0
(dse
-20
- n-
he-im-ension-a
I00%.
-22
Iie
- atie
Th-hopors
Density of States
Figure
32.
Phosphorus
on a scale of 0 to 100%.
lattice.
The phosphorus-
VU)NnWVV-
.1JW
-17"
.7-7rX
IF-R
75
ir
The localization in
As a result,
At the
same time, the band filling increases as one moves to the right
p.
76
top of d
r,
V Cr
AM hg
Co
NI
It
the transition series, the area of concern to us, the Fermi level
falls as one moves to the right, the work function of the metal
increases.
Now imagine superimposed on this variable energy sea of
electrons the P-P a and a* bands for some typical, moderately
,.
Both a and a
As P-P stretches
77
d bands
Mn
Fe
Co
No
(E
Cu
this
shorter only improves
distance
P-P
the
Making
bond.
situation.
P-P distance would seem
The steady, gradual variation of the
orbital model shown here
to be as inconsistent with the molecular
If we turn on
the interaction between the P atoms and the metal layer (and we
have seen before this interaction is substantial) we will get
mixing of P and Mn orbitals.
and 0.
The experimentally observed trend has been explained.
There
78
A chemical
To second
AE
Ei
__2
-Ej"
is four-electron,
is zero-
79
af
~b
--
El
Sm
Sg
E*
d-n-
'o
50).
(D
.1
A
5Y-
"-,
Inteacton
Oas
o diect
80
11
than that of the separate isolated levels.
lb> of fragment A
Ih>
and li>.
<bli> are also much smaller than <big> then both the numerator
and the denominator of the perturbation expression single out the
81
They are the valence orbitals of the molecule, the orbitals most
easily perturbed in any molecular interaction.
In them resides
To
One way
They change in
dt
N,
82
part of the Pt(lll) band, or the Mn and P sublattices in Mn 2 P2 2 or the Chevrel phases discussed below, in all of these cases we
can describe what happens in terms of local action.
The only
Surface
53
\%.
A%
.
"
SqA
A,
'~A~j
% A, , ,%
.,
%.
*,A
~ A,
83
In interactionQ A is
In
It
In one-electron
41
This is
It will
remains filled.
N-
84
repulsion
attraction
55
--
it is
In
the two interacting levels may fall below the Fermi level, 56b.
now
no effect
attraction
56
"
85
0 and
So
Depending on the
1.
86
Baetzold 31 ,3 2
--
There is a very
>
o.
.1
p
87
A Case Study:
CO on Ni(100)
The
0
C
MI--
hy
o
cT
27
xz,yz
5o-
0
5o
57
I%
16
88
dsp hybrid.1 1
explicit.
,4 9
"
,'
,
react correspondingly:
S.
CO
And the d7
orbitals,
the Fermi level into orbitals that are mainly d band, but on the
S,
89
i.
NiH5 -
CO
NiH 5 (CO) -
CO
c(2x2)CO-Ni(100)
Ni(100)
1.59
2.0
5a
--
1.62
2.0
--
0.51
0.0
2K*
--
0.74
0.0
hy
0.0
0.48
--
daa
1.93
1.43
--
4.0
3.52
--
d a
3.81
3.31
--
--
10.01
10.0
CO
--
H 5 Ni 16.0
15.99
--
5a
2
CO
Nia
1 0. 1 7 b
10.25
10.0
9.37
--
a)
b)
this number is not 10.0, because the surface layer of the slab is
negative relative to the inner layer.
'.3
4.
4.
3='
~ '%% ~y
..
. ..-.
5:5
'
.- '
''
5"
'
C%%
-
%'~.%
'%.
"
~.~~\',
V.'~%%.~
-;v%
.- ;-;;.
-';'.
'p.
"%-.%%
-'
'",-'%Lv'.,S'.-.
90
50'
S.,J
We will return to
in a while.
This
52
.,
-.
919
Barriers to ChemisorDtion
The repulsive two-orbital four-electron interaction that turns into
an attractive, bonding force when the electrons, rising in energy, are
dumped at the Fermi level is not just a curiosity.
I think that it is
The approach
Figure 33
coordinate translates into electron interaction.
But when
In reality, the
54
,."
bonding combination crosses the Fermi level, and dumps its electrons.
shorter R there is bonding.
At
,.
92
And
there may be not one, but several such, for it is not a single level,
but groups of levels which are "pushed" above the Fermi level.
There
In this section I have mentioned, for the second time, the bonding
consequences of emptying, at the Fermi level, molecular orbitals
delocalized over adsorbate and surface, and antibonding between the two.
Salahub 5 0 and Anderson 5 6 stress the same effect.
There is a close
We, and others, have worked out the details of this kind of
93
Chemisorption is a Compromis
Consider again the basic molecule-surface interaction diagram 59,
The occupied
antibonding
in
antibonding
in
surface
AiG
bonding
in A
bonding
in
surface
Surface
59
that molecule, the unfilled orbitals of A are usually antibonding.
The
situation on the metal depends on where in a band the Fermi level lies:
the bottom of the d band is metal-metal bonding, the top is metal-metal
anti'--nding.
Most of
the metals of catalytic interest are in the middle or right part of the
transition series.
5.\s
..
y%..i
a'
'
94
easiest to analyze
--
But
Bonding
weakened
strengthened
///////weakened
Surface
60
When
)or
What
..
'
.:
'
'i -
"
"*
95
3.
i')a
tthe
four-fold (3d) sites are slightly less bound, but more stable than the
one-fold site, 3a.
In
depopulated,
w,*
occupied.
a consequence, Pt-C bonds are formed, the C-C bond weakened, and
As
96
A glance at
2p
61
In the four-fold
It is clear that
In
An incisive
1:
.?i"
97
Table 3.
C2 H2
4,
Br
Surface
3.56
4.68
4.74
4.46
(eV)
Overlap Population
C-C
1.70
1.41
1.32
1.21
1.08
Ptl-Pt 2
0.14
0.12
0.08
0.09
-0.02
Pt2-Pt 3
0.14
0.14
0.13
0.07
0.06
0.13
0.54
0.01
0.15
0.52
0.19
0.06
0.33
0.27
Ptl-Pt 4
Ptl-Cb
Pt3 -C
0.14
0.13
0.30
0.00
Occuations
*o
'.
0.0
0.0
0.08
0.81
0.17
1.06
0.33
1.03
0.53
0.89
2.0
2.0
1.73
1.96
1.59
1.59
1.96
1.73
1.57
1.53
'
E(slab) + E(C2 H2 )
E(geuktry) in eV.
b The carbon atcu here is the closest to the particular Pt atan under
consideration.
oI
S.
98
.,
p%
I
-
.*
S
~ -w-wS
-!
99
In
these clusters, shown in three views in 62, sulfurs cap the eight
ba
62.
faces of an octahedron of molybdenums. The Mo 6 S 8 clusters are
then embedded in a substructure of lead cubes (this is a thought
construction of the structure!), as in 63.
doesn't remain here.
A rotation of roughly
10
PP,
63
0Pb
* MO
Ps.
0:
neighboring cube.
x s, S4,TG
the isolated cluster, Fig. 34, one finds that the five lowest
Figure 34
U-
MOS a
,I
meu
TMos
u
t.-
tig
00
CP
eg
M06S$84
Ok
101
A molecular
655
One more conclusion easily drawn from Fig. 34, one applying
what we know:
U.
--
102
That band is
We've
... X
structure, 66.65
X.N.
Cc O
Be 0
66
!C%
103
molecules below.
08
08
67
68
J]
V".r
,1
104
Folding Bands
It has
The
Or it could be s-cis,
1 "1 "1
69
vi
70
In 69a and 70a, the unit cell contains one basic electronic
unit, PtH 4 2 , a CH group.
A purely
A
E~'
Sp 5S5
5
~5.~.~ap
*'d
5. ...
%E
~s
%%
105
So if the unit
Let's
Then, subsequently,
7"1
S.
5'
-Z-n-
0:000000
.'
wo
106
-a
72
out into a band, that of the x "running up", that of 7* running
down, 73.
boundaries.
--
one node
I
k.-.
w /20
V
4,.
107
I
W/20
W/o
74'.
At this point, the realization hits us that, of course, the
orbitals of these polymers are the same.
polymer, one CH per unit cell, has been "folded back" in 74.
The
108
v/20
K'ool
rM
ldel
0
vr/a'
0',2o
75
k-
0'/
S3a
k-
/'
a' - 44
76
and so on.
There are
73
76a
76b),
109
chain, 69b.
There are twice as many bands in this region as there are in the
;'
c,
c
-\
around the z
L.i L. L. i..
77LV
L.-
l-
The
but degenerate in
eclipsed
doubled unit cell
staggered
z2
xz,yz
WL -13-
xz' yz-3
z2
Pt- H
-15-
-I5
0 k--
7r/0
k-a
7r/0
Figure 3T. The band structure of a staggered PtH4 2 - stack (left), compared
with the folded back band structure of an eclipsed stack, 2 PtH,.
in a unit
cell (right).
%S
'
''
110
U.
IN,
79
Except for this minor wrinkle, the band structures of the
folded-back eclipsed polymer and the staggered one are very, very
similar.
the staggered one in terms of the eclipsed one plus the here
minor perturbation of rotation of every second unit.
The chemist's intuition is that the eclipsed and staggered
polymers can't be very different.
start bumping into each other, and for such steric effects there
is, in turn, much further intuition.
look different, for one polymer has one, the other two basic
electronic units in the cell.
and eclipsed polymers, shows just how alike they are in their
distribution of levels in energy.
Figure 36
There is another reason for feeling at home with the folding
process.
To go
from 71a (the linear chain, one CH per unit cell) to 71b (linear
chain, two CH's per unit cell) involves no distortion.
However,
71b
It behooves us to analyze
distances are kept constant, then the first real change is in the
1,3 interactions.
since the x overlap falls off very quickly past the bonding
region.
distortion is significant, but that has nothing to do with the isystem, it's a result of strain.
eclipsed-
staggered
-12
DOS
Fiur
cmprso
PtH4
-6e
f hDS fstaggered
2-stacks
DOS
f)adeclipsed(rgt
112
stabilized
79
destabilized
stabilized
.5,
'.'
,.,
':,:
'S
113
C'S
%"
IN
:
Ps~
114
physics have been around metals and alloys, and in these often
close-packed or nearly close-packed substances by and large
localized, chemical viewpoints have seemed irrelevant.
For
I will
take the view that the covalent approach is central and look for
bonds when others wouldn't think they're there.
Maximize bonding.
115
"I
116
They are the one below two below one set shown in 81.
We
X1
117
accomplish this.
In the case at hand the most effective normal v;i-e is
illustrated in 82.
92
..
I.NN
.-
~..*
**
,.-~
a-
~--g
*~N
NPN
N'
118
4;1
*3;
4124
-C
C
A -
"# -.
.. ..
.llc
.
-.S
5. S
..
*55.*.
* --
.
*
-.
..
'-
*'-
.
-~-~
.
-:
119
The
There is
In the
jargon of the trade one says that the partial filling leads to an
electron-phonon coupling which opens up a gap just at the Fermi
level.
The original chain has one orbital per unit cell, 85a,
The
Fermi level is halfway up the band -- the band has room for two
electrons per orbital, but for H or CH we have one electron per
orbital.
120
aI
00
k--
ra
'EF
b
0
k-...
r/2a
06
the bottom, middle (Fermi level), and top of the band, 87.
the bottom and top of the band nothing happens.
At
What is gained
Note the
I-A
121
S7
464-66%0
k .-.-
r/2'0
The action does not take place just at the Fermi level, but
in a second order way the stabilization "penetrates" into the
zone.
"before"
dasemd line
"fft"
'"
solid line
after'
pairing distortion
k-
wZ
for any Fermi level, but obviously it is maximal for the halffilled band, and it is at that GF that the band gap is opened up.
If we were to summarize what happens in block form, we'd get 89.
Note the resemblance to 80.
122
C.
would. 6 9
research. 7 0
When it is
Whangbo.8
The Peierls distortion plays a crucial role in determining
the structure of solids in general.
:4'
Let's
123
ft.
/T:?
A(.
The A layer is
Most
There are no
Take GdPS.
If we assign
rz
c~t~z
!*:
ZW~:Z7
This is exactly
124
what it does.
72
drawn after the beautiful representation of dulliger, et al.
M (0d)
A@(P)
aIS)
93
From the point of view of a band structure calculation one
might also expect bond formation, a distortion of the square net.
94 shows a qualitative DOS diagram for GdPS.
P 30
P 3:
DOS
-'V
_'.M
..
L X..
WN LIU W.
125
With the
O0
.-
Nor is
)C
126
'U,
As
5"
The DOS associated with the band structure of 97, with one
main group element of group 15 per lattice site, must have the
There are 5 electrons per atom, so if the s band
The detailed
[.
MI
DOS-
L9
*
"W.-
'
'*-
..
,.
/S*S*" 2 2
SW
. -%
-,'.
.;
, "'
515.51
;
*~~~~~~'
--
-.
.,jVTWvv.
127
This system
CA
Two of these
There are other
possibilities.
As
100
There is one aspect of the outcome of a Peierls distortion,
the creation of a gap at the Fermi level, that might be taken
from the last case as being typical, but which is not necessarily
so.
Ir
7~
128
I
create a gap.
linked together.
producing bonds, pulling some states down from the Fermi level
region.
be possible to remove all the states from the Fermi level region.
Some DOS remains there; the material may still be a conductor.
One final comment, on the ThCr 2 Si2 structure.
The reader
That,
Peierls
a.:
.
I.
.'r
,S",
a. .%=
a ~
-'.a..\.
129
Now let's
NiP distortion. 7 5
VV
a060
I60
00
0% 70Y
Qs
v
bv
Os
101
S0
* votz.O
atZs
0 vootz-05
o Satzs025
Stz075
'S
130
To be specific, let's
..........................................
*
131
contact emphasized in 102 changes from 3.33 to 2.76, but the V-V
distance perpendicular to the plane (not indicated in 102) is not
much longer, 2.94 A.
Still further distortions can take place.
In NiP, the
'._1
t
." .
.- .,."
.-
,-
,.-
..
. '....,
.-
' . 4,,,
,.',-'
.'r.
.. ,.-,w".
'.
'.-.-.
."%
',
.".
,,J',-
'.*,
"
"'.J','
J'
'5,
~k
4
A.
C
44.
o
a
-U
U,
a
U
~~)
-4
-4
-a
L.
~n
~-4
.4U
~-)
-
.4*4
U,
Lfl
.-4
.- 4
4-4
*U
-
-4
0'
4-4
I-s
-~
4.)
.~
-a
-a
f~
4-4
5.
5'4
.-4
4-4
5-
44.
L/2
5...
U,
4-4
.44
4.4
4-.
'Jo
a
I-.
4
2
U
3
4-4
.4-4
(J~
-a.4-4
U
a
a
.0
~
w .4-4
I-.
A
.'5
.~5
I
U,
.0
5'
_____
0"
.44
.0
..4
.~4
U
U
U
6
=
a
7'
c~U
-'5
I',
(pg)
5?'
AIas.a~
4
d .
d~.
..
.
....
132
understanding, just let the computer spew these bands out and
accept (or distrust) them?
We
That tells
103
10+
of course, three-dimensional.
,15
of the drawing.
133
sublattices.
Note the
There is metal-
The unit
OT
108
p-
--
bonding.
Now
..
,~..
~ ~
*~
.A
.A
134
point, 109).
z bands split more than the x,y bands) are clearly visible in the
positioning of bands 3-8 in Fig. 37b and 37a.
109
MnP
S.
S.
I.
'S
"
".
".""
-.
"
.ft
'I .'
'4
t.
.t
V..(.
1
'.-'
'.
'"r,**
~.f'
.C
.%
135
-.
The previous sections have shown that one can work back from
band structures and densities of states to local chemical actions
electron transfer and bond formation.
the qualitative construction of surface-adsorbate or sublatticesublattice orbital interaction diagrams, in the forward
direction, is difficult.
How to
",
First,
Similarly, in the
solid only levels of the same k can mix with each other. 9 ,1 5
Second, the strength of any interaction is measured by the
same expression as for molecules:
4"
IHiji
AE =
1
estimated. 6 ,8, 1
level does (or does not) interact with another one", we may have
to say "this level interacts more (or less) effectively with such
1%
.7
Z~rl1z
._
_,,
136
examples.
Consider the interaction of methyl, CH 3 , with a surface, in
on-top and bridging sites, 110. 7 8
on-top
bridging
C)& &
on
C\O
CM0\ M3 /V-
~ -~ ~
P~
;.-a
~~~~~~~,
d.
,
HII
W~'/ 5~
. ..-f..~.
137
The orbitals at
While things
are assuredly more complicated in three dimensions, these onedimensional pictures are indicative of what transpires.
The methyl radical orbital (it's really a band, but the band
is narrow for low coverage) interacts with the entire z 2 and xz
bands of the metal, except at a few special symmetry-determined
points where the overlap is zero.
U,'
I/
II
-II
6i
"a".
n interacts with the entire z 2 band, but because of the
better energy match, more strongly so with the bottom of the
band, as 113 shows.
at the top and bottom of the band, and never very efficient
elsewhere (114).
l1Ob, we
There is nothing
113
138
II
O
0,,
&0
n.
0,
..
in-
'Is.X
theoretic apparatus and specifically the role of k in delimiting
interactions on surfaces goes back to the work of Grimley 4 5 and
Gadzuk 4 4 , and has been consistently stressed by Salem.4 7
For a second example, let's return to acetylene on Pt(lll),
specifically in the two-fold and four-fold geometries. 2 9
S,
In the
in
that band some metal-metal bonding levels that were at the bottom
of the band are pushed up, while some of the metal-metal
antibonding levels are pushed down.
lop
..
5.
.%
5.
...
.*,*
.**.
..-
...
139
IEF
116
',
.
140
Theory is
One
The filling of
Over
The ionization
I.
141
.. '
top of d
bond
t,
':
bottom
TI
potential
of
orbitals
also
a single
become
Cr
more
filling
Co
Fe
d electron
M.-
contracted,
therefore
the
The
less
complete;
the
former wins
out.
Thus
the
Fermi
level
What happens
general,
early
and
middle
transition
metals
break
is
broken
up,
in
detail,
is
not
known
up
How the
experimentally.
Obviously, at some point the oxygen end of the molecule must come
in
contact
with
the
metal
atoms,
even
though
the
common
'A
%N
.,*..':.-
**
.,*
.-
TVY1X
*RUVK YI
V7-V
y"v
7- -
p
142
There is a good
81
theoretical model for CO bonding and dissociation.
-.
%1%
Parenthetically,
discovery of
the
118,
and
of
some
other
inorganic
literature
and
not only to
grant applications.
two-way
street.
information
organometallic
So
chemists
read
the
surface
decorate
(or comfort
for
speculations)
largely to provide
for surface
studies,
inspired by structures
such
Can
as
18?
Returning to the problem of the metal surface influence on
the dissociation of CO, we can look at molecular chemisorption, C
end bonded, and see if there are any clues.
symptom
of
the
bonding
on
6.9.
several
different
surfaces,
the
'
143
Table 4
The population of
5a is
almost constant,
Not much is
--
surface,
one would
--
as
geometry changes
etc.
rising slowly
tilt
toward the
left
"
14354r
The
reason
for
these
bonding
trends
is
obvious.
119,.[-
i.
"
top of d
bo ttom
of d bond
side o
TI MV C
Fo Tb
that
band.
level
is
required
the
NA
eries
carbon
4monoxide
for chemisorption.
But 2pu
greater
above
extent.
disruption. 27
2w*
This
2a*
is
interacts more,
the
initial
is
occuped to
indicator
of
aV
CO
144
Table 4.
Cr(l0)
5a
1.73
1.67
1.62
1.60
1.60
21r*
1.61
0.74
0.54
0.43
0.39
Fe(I0)
Co(0001)
Ni(100)
Ni(ll)
1.59
0.40
I...,
%
JRp
V.,
145
been suggested.
CH
HSC-CH
CH 3
variety of processes.
121.
CH"-
H b
iH
H
v
I CH
--
/7"7777
/////////i
I//11
121
///I
IIII
/ll/J
L/I/ll
'
!!I
IIII
II/II
+CH
3 -CH 3
I
146
the actual C-C bond formation, once the components are in place.
Let's call this the "coupling barrier".
It is
migration +
Three
Its
The
147
The CH 3
Tp
pushed up above the Fermi level, and this is one component of the
bonding.
We started
I.
t1.
146
the actual C-C bond formation, once the components are in place.
Let's call this the "coupling barrier".
It is
migration +
Three
2-S
ie
The
148
The relative energy zero in each case is the most stable on-top
geometry.
The implication of 126 is that for Co the preferred
migration itineraries are via bridged transition states, 127a,
for Ti via capping or hollow sites, 127b, whereas for Cr both are
ARA
.V
Relative E (eV):
Co
Cr
Ti
0.0
0.0
0.0
II
1.4
0.9
0.9
0.1
0.5
competitive.
M7
54
remains a relatively uncommon surface species.
This is a
If we
The
149
07 eV
Co
0.5
Cr
Ti
-0.1
The
\F
d-band.
The actual evolution of the DOS and COOP curves allows one
to follow this process in detail.
Figure 38
the contribution of the methyl n orbital, the radical lobe, to
the total DOS along a hypothetical coupling reaction coordinate.
Note the gradual formation of a two-peaked structure.
COOP
'7irves show the lower peak is C-C bonding, the upper one C-C
antibonding.
.' . v'
- "'."'-,X".
. -. .'... --", "-"'.".
"
"' - '-
'' '
' %
f.
o(
0 t
0' ............
,-all
L)k
og
4-'
Q~
C.
LA
t/n
"
cu)
-D
0
0
*.I-
.......
4-)
f.4-)
0
.4->
4J
C
cE
(U 0
(U
~40
b
b-
(0 -
...
4-j
.......
0<
"C-
..........
4--
I04(f
QC
--
IA
0)
.-.
40
r_
0
0-'
,,
*b
("
L)
0
4-)
)4-
b-
............
0'
--
--
-) C
0
,'
Ln0
>
0)
L
=)
.
0A*
0n
'(AO
150
being formed.
The total energy of the system increases along the reaction
path, as nl-n 2 becomes more antibonding.
a*
nl-n 2 is
The
So the
p.!
151
These have
(1) This is
But
Basically
152
4.
The Schr6dinger
effective medium theory, and with time the atomic details at the
surface have come to be modeled with greater accuracy.
An example of the information the method yields is shown in
Fig. 39, the total energy and density of states profile for H 2
dissociation on Mg(0001). 8 7
5.
H2 on Mg (0001)
A
ordnt
Recio
U-U
0
,p%
Recto
Coodiat
0'
-.~0
ofSae
Desty
Figure
Soecluae
39.
32.~~~~~
~ ~
M =chmiore
mlc
fo emiopi
c
density~~~
of
sae
two
moeua
~
~~
hrceitc"f
To:shmtcptnileeg
uv.P
e;B=
~~
atcranc
The line
dashedis the ou*
fe
Botm/eeomn
rceiti
ons
ons
iffrn
dens~~~imvn
eeec
pyiopinmnmm
hm iso daos
n discaton
hmsrt
g00S
2o
fteoeeeto
,adM
itne
tolwre
rniinsae
orsodt
rmtesrae
rg
as
hed
sci
in
proceeds
--
4-rl
Ali
iL
\A'6
4..
153
88
But
the two pictures is by recognizing that mine is not selfconsistent, does not account for proper screening of H 2 as it
approaches the surface.
au
drops
M1 - M 2
B.
bond is stretched.
87
The barriers to chemisorption in the work of Norskov et a1
,4'N
It becomes
154
One is Alfred P
for the first new ideas on what determines solid state structures
since the pioneering contributions of Pauling. 5 , 6
His work is
93
consistently ingenious and innovative.
all
-,
~.d~
m%'4~.%~~
"
-~.
J.
155
i.e. if there is
Recall in organic
21
The
4'
156
a
156
-~---jSite
I
Site I
0*
~4 '~
a
~-Site
129
The diagram has been drawn in such a way that the more
electronegative element is X.
yet made -- the orbital blocks are just that, blocks, indicating
the rough position of the levels.
(here X) element.
or BeGeV.
much farther apart from each other than the site I atoms (recall
here the short metal-metal contacts in the ThCr2Si 2 structure).
157
and 132.
131
i3Z
Which layer will be most stable and which will have the
higher Fermi level depends on the electron filling.
For a case
poorer donor.
The stability conclusion bears a little elaboration.
It is
When
Filling
I
Il
.5
DI
158
positions.
That means the layer in which the Ge enter the more dispersive
sites
upper layer.
A reasonable question to ask is the following.
If one layer
159
92
.I
/s
,,
s\
.s
IS4-
,.... -. /
/-
..
__/
.....
"
-S
160
6
counts for a closed-shell low-spin structure should be then d
Forming the
the d 6 marcasites
161
I
It seems
What in fact
But
135.29
29i
IN%
AS
162
1621
ra
and Ira*
"
that band.
(a
(Pt,Pta
and 0
attractive interactions.
163
In fact,
Normally we would
2
these are bonding combinations of ir* with the top of the z
band, as indicated in 137 -- come below the Fermi level and are
occupied.
populate x
and , operate to
164
interactionQ,
139
from Pt bulk levels, from Pt surface atoms not involved with the
acetylene, even from the Pt atoms binding the acetylene, but from
orbitals of these atoms not used in that binding.
While the
Together with
o,.,
and
reconstruction.
1I
165
!!
I
In general, as I already outlined in a previous section,
non-dissociative chemisorption is a delicate balance of the very
same interactions, which weaken bonds in the adsorbed molecule
and in the surface.
"Not much".
to learn much more solid state physics than I've tried to teach
here if they are to understand these observables, and they must
--
SI
II
166
to form a link between chemistry and physics by introducing
simple band structure perspectives into chemical thinking about
surfaces.
These deal
Where
delocalization.
I have concentrated on the most chemical notion of all
--
V.
W.%d F"
',~,
~.,
~%
~
167
References
1.
Ertl, G. Eds.,
"The Nature of
52.
168
1963,
references therein.
4.
The
1979,
A366, 23.
5.
6.
7.
'.
.
X.
169
9.
Harrison, W. A.:
"Electronic
11.
1985, 4, 125.
Whangbo, M. H.
13.
14.
170
15.
17.
18.
19.
20.
literature of reconstruction:
171
21.
London, 1971.
(b) Mingos, D.M.P. Nature (London) Phys. Sci.,
1972, 236,
99.
22.
The local
(b) Yu, J. J.; Freeman, A. J.; Xu, J.-H. Phys. Rev. Lett.,
1987, 58,
172
2566.
26.
27.
28.
578.
We disagree on its
Langmuir,
30.
1985, 1, 621.
31.
-.-.
..
.~u~
173
32.
33.
A. B. Anderson finds
See e.g. Anderson,
papers.
34.
1983,
105, 3528.
(b) Wijeyesekera, S. D.; Hoffmann, R. Orcanometal., 1984,
3, 949.
(c) Kertesz, M.; Hoffmann, R. J. Amer. Chem Soc.,
1984.
106. 3453.
(d) An analogous index in the HUckel model, a bond order
density, was introduced earlier by van Doorn, W.;
Koutecky, J. Int. J. Quantum Chem.,
1977,
12, Suppl. 2,
13.
35.
36.
S
.
174
37.
references therein.
38.
39.
1986, 108,
3078.
40.
41.
original references).
-)~-~.
for
175
J. Phys.
42.
Chem. Soc.,
sampling of these.
43.
44.
Gadzuk, J. W.,
45.
1971, 8, 31; in
'S
.|
306.
176
46.
47.
1986, 21,
to be
published.
49.
50.
1953, 2939.
1982, 11, 283;
I
177
53.
X. Surf. Sci.,
See also
1985, 150,
L115.
54.
1987,
56.
57.
Hoffmann, R. in "IUPAC.
-"X
~~~~
v&.5.-;%~~~
5.~
V,
.~%
'S
N'.
-V
-,r
4,.
V.
-Wy
- . W
7W
I.
178
60.
1984, 136,
1986, 165,
221.
61.
I
Press, New York, 1981, Chap. 10.
62.
63.
64.
1982, 5, 21.
1983,
1150.
:.
1977,
65.
66.
Excellent
A discussion of the
179
The
69.
1959,
A251, 172.
70.
71.
references therein.
72.
73.
74.
1981, 75,
5774.
1983, 105,
1079.
(c) Burdett, J.K.; McLarnan, T.J. J. Chem. Phys.,
1981, 75,
5764.
%.
180
.,
1984,
11~, 229.
1986, 108,
1986,
116~, 113.
76.
1968, 49,
114.
78.
06,
Soc,
453
184,
79.
80.
1979, 28, 1.
1984, 53,
1986,
L675.
On Pt 3 Ti a similar assignment
surfaces:
188, L693.
181
81.
1986, 169,
82.
or a recent review, see Anderson, R.B. "The FischerTropsch Synthesis", Academic Press, New York, 1984.
83.
1983,
1983, 7, 535.
182
86.
87.
1981, 4-,
A1133.
257;
1984,
137, 65.
We should
90.
91.
Nouv. J. Chim.,
1986,
1983,
-21x
183
93.
94.
52.
1985, 24,
4108.
5,,
'%
.1V
.5,