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& & & & ) & 5 &
( #" & ) " "&
& &
> #" && " " &
''

!7 & ) & &"? & & 1CD
- & A $84H 6 CD A $8 H 6 A $8,2A (
#" & & 9
9 &) !7 "& #" ,!" 7 "&A !
( 3 ( ( !" & )
" 6 3 & "&& & &)& &
) &" & & &)& )
"&" ( "" & & & 6 3 & &
,!" "A ) & &A & & &
& 3 )! && &" )
" & " ' 0 "&& 7 10); A $$8H
- I A $$,2 6 & , 1= 32 "&
& & & ) ) 6 1 $82
6 & &" &
& ) &&& ) & 1 $$%2 & !
E ) & ! &A "&A
& 6 & " &
"# & ) & !)& 9 & ( E
!) ? & & !7A !) "# & ) A
( ( " ) ) )& &
1 2 "" " "" ( 9
) && & - ) )!
&"& & & ) !) 6
" "&" &" &)!)& && (
A " & &"" & "
9 .* &(& & && " &) "&&
!7 & & & ( & &) = "& 9 &
& &A & & & 7
&A &" 6 ) & "& & &&
&" !)& 7 ( &" 9
- ? !7 "& #" 7 ( (
&" ; " & ) "& 7A 9 !
& & 3 &" ( &)!)& 5 &
&A ) ) ) &))& & "
?A ! ) & ( 6 7 &)!) & & "A 7!7
) & ( & )(
& & 7 A ) && 7!&)!)
"A 7!7 & & 5 > !" 7
"A 3 & ) A ) & &)
9 )& 7! ) 5 7 ) &))&
) ; (A 9 & 7!&)!
)A "&" & ) & - &
7!A ! ) & & )
StateseV Atom

4
3
'
Pd3 V Cu3 Ti

dPd: 2.72
dV: 0.32
2
1
StateseV Atom
0
4
3
Pd2 V MoPt2
dPd: 2.89
dV: 0.31
2
1
StateseV Atom
0
4
3
PdV AuCu
dPd: 3.3
dV: 0.43
2
1
StateseV Atom
0
4
3
PdV3 Cr3 Si

dPd: 3.78
dV: 0.86
2
1
0
10
7.5
5
2.5
EEFermi
9 .*
6 && & "!
& 9 & 3 " A & &
3 " &A &" 6 ) &
& && &" !)& 7 (
&" 9 0

StateseV Atom
'%
Pd3 V AuCu3 , L12
3
2
1
StateseV Atom
0
4
Pd3 V Al3 Ti, D022
3
2
1
StateseV Atom
0
4
Pd3 V Cu3 Ti, D0a
3
2
1
0
10
7.5
5
2.5
EEFermi
9 .,
6 && && E 7 "&&
10 A 'A ' " )2 & &
3 " &A &"
&A ) ) '4 7 7 7A ( &
7! ) & & &
9 ., &(& 3 0 A ' ' & & 7
5
0 & A 3 &(& & " " " & 9 !
( ( " & && #" &) '
& ( &" 0 ) 9 &
& "&" 10); A $$82 6 3G& &
= 6 6 "&& & A & "#
& " & 3A ) &
E & & & " E &
&" 6 3 0 "& &
&) 3 !- A ) &" " &
& ) "
6 3 ,!" 7 " E & &?
& && 6 & & &
;&!!& & 7!& #

'
& " ( ( &) 5
& & & @ ) &" !)&A "&&
& && E ) %8 7A ; #"
%4 7 ) 3S3 && ) : 1 $. 2 6 "&
9 ! & & " " 3 & & &
( ,!& 16 A $82

5 & " & && !& && "& &A !
& & "&& & ) !"!
E & ! & ! &
) & "& ( ( E & +
& & && & & & &&
&" & " & & & &&
& & 1 ! A ) 7! & "&
2 5 ) && &" & && % & 6 & )
) &"& "&& ( &" &
) A " &" & ( &
"& & ( #

!
& !7 "&& & &" ) % % %

& % & !" & & &
"& & < ;A
& ? , , , 3 3 !
& %, O ,' O 6 ? &
&& ) ; ) & ) &
) "& ) "" # & )
1 7 ) &A &"A A D )
) 2
6 # & J " " 9 . 9 &
,' O ( ( ) E ? &A &
@& & ?
) & ) ) ' 7 " 6 !
) # "&& & )( , *' 7MA
& & ) '' '% N
& "&&
& # & )( %4 %$ N
A ! 7!7
&& && %8 %4 N
A &" 6
) # & " && & !
&&
'*

& ( 7 & " ) , O

& && " 6L' C # "
7 7!&A & & &&
( ) & & 1 ) ) = &
O 72A ( & "
)& ,' O & )
? & & 8' 7M (
"& 6& & &) & & *''= & &
) #" "&

"
6 ) &" & " "& &&
* % % ) & ( % &A & % * * 4 4 !"&
& # 3 A &"
& %, O ,' O
6 # & " " 9 . 6
& & & &
&A & && & ) # E&
" & &" & &
) '% N
& "&& 1" ) &
& &&2A ) # & & & .' 7M
7 ( A ) & & & # E&
" & 5 7
"& &
" ' N
& "&&A
,!%' 7M & # &&
)( %, %8 N
A & & & )& 7!7 "
? " 7!7 )& ) )& 1& ( !7 !
)& & & & %, N
2
( & && "
# " 7 , "& 6 & && ( "
( & & ) 1=&=A :6A >3A 92
& ( & "&&A !
) ( " &
) ( A "& & & =6 1 2
"& ) " ( & & & & ,
) &)& ( & ) & &&A
& ! ( & " 7!7 )&
4
3
Pd87.5 V12.5 fcc
StateseV Atom
StateseV Atom

dPd: 2.34
dV: 0.17
2
1
4
3
dPd: 2.69
dV: 0.24
2
1
dPd: 2.95
dV: 0.38
2
1
dPd: 3.15
dV: 0.52
2
1
0
10
2
1
4
3
Pd37.5 V62.5 bcc

dPd: 3.11
dV: 0.57
2
1
4
3
Pd25 V75 bcc

dPd: 3.37
dV: 0.65
2
1
0
Pd50 V50 fcc
StateseV Atom
StateseV Atom
0
4
dV: 0.5
0
Pd65.625 V34.375 fcc
StateseV Atom
StateseV Atom
0
4
Pd50 V50 bcc

dPd: 3.03
0
Pd75 V25 fcc
StateseV Atom
StateseV Atom
',
7.5
5
2.5
EEFermi
4
3
Pd12.5 V87.5 bcc

dPd: 3.34
dV: 0.52
2
1
0
10
7.5
5
2.5
EEFermi
9 .4
6 && & & "!
& 12 ) 1 2 & 9A & &
3 3 " &A &"!
6 ) & && !)& 7

3 !7 & 6 &" & % &A
( %8A %*A % A 4 & " )A &"
3 ) !7 & 6 % &" &
4A %A 8A * & " )
'4

9 .4 &(& 3 & && )
=" 3 "&& 19 .*2 )& & &!
"" "&" &" !)& ) "& 6
&" & E & " &A " !
)!) &" & ) &&
& & "" 3 ) & && "" #
; "&A 3 & && & &&
9 A & &"&A 3 &
& < & & && G& 1 A $8.2
& &! & 6 & 1/ 2 "
"& " & &
#" )& & " &&")
&"? ) 6 1 $8,2
- & " 3 7 & &"A
&" )& & ) & 6 !)
&& & & ( & ) & ( & 7 &
( & & "&&A & && !) "&
) - "& !) && & &
) ) ', 7 && & & ) & 6
)( 7 !) && & & 7
1)2 =" "&& !)& ( )
&A & 9 A 7
& ( & && 6& & ? & ( #
& && & 3

5 & "& " !" &
) & & ) "
6 & &&& ) ( !
A ( ) " & &!
"& && & " )& ?!
" " " & "&
6 <&? & " & & &&& ( A (
" ( & "" & )& & #"&&A &
" ! & E "& !
" E& ) ) # &
# & & &&& " & " &A
) # ) & )
"" & E & & & " & & #"&

'.
0.06
Wab eV
0.08
0.1
0.12
0.14
10
20
30
%V
40
50
60
9 ..
0 ? !
& ? & & && 1& &2A )!& $, O
? & ) & & 6 ) " &
& "&
( #& &
& ) !7 & & ! 1 2
! "&& ) #) & ! ( < &
& =" 4 3 .%

#$ $ !
6 ? & &" 0 "& & !
" & ) ? &
L 1 P 2 A ( ) & ) " !
& & (& "& & 6
# ? & ) #" && &
( ) & ) & &"? "& & (
) # " ) &A & &
& ? 1 9 ..2
&!&; !? &(& " "& &
&) ? & "" # 3 ( & ( )
& # & && ( ( )
$,O ? ? &
# & && 6L' C
& " &
&" &A " "&& ' C 6 !
& ) "" !-& ? "" #A
" ! " & )
5 & ( E #
& "&& "
& & & & 6L' C 1) % O &!

'8
a)
0.8
0.6
0.4
b)
0.2
200
400
600
TK
800
1000
1200
9 .8
12 6" !" ! " & !
)& !7 &" & &
! 7 1=2A & ! 7
1> 2A ! 7 162 6 & " !
& ) ; & " "&& 1)2 E !
" "& 1 '2 & &
& & 1 L '2 0 !" 7 &( & &
1 2 '!" 7 &( ? &! "& & 1&
2 #
2 6 " & ) ) "
& " "& & !
& && ) " "
" 5 ) & A &
"& & & " A (& & & ? & 9 !7A
&! & & !=!" 7 " 1(A
( A & &) " 7P7 # A & )(2A
( & !& & > !" 7 6!" 7
" ) ? &! A & ? ) &&
6 1& 9 .82 6& & &; & &
& & )& & "& ( A ( "&&
& & & ) ) & "&
& ! & " !" & & (
; )! > & 6 " &
!& "& && ',$ CA 8 CA .%. C 6A
> A = &" & & &"

'$
$ "
5 & & A ? & &!) &!
& ) & 6 # &
) && & ) ) & L ' /; 14 2A ( &!
& ) ! & ) & 9
? & & /; 14 2 ) &
& ( 5 & ( " & !
& 1 2 ? & & ;&A
1 2 && ) D 6 ? &
& " & L ' 1 L %2 # & ( ' 7
& & 6 ; ? & " ( "
* & &
9 & " ) &) ) &
"&& & ) & & "& ( &
1 9 .$2A " & ) & &
"A ) & & ) & E "& ) & 6
# =&= & P' 7M " && ? & &
& ( A & ) 3 " & L
L " ) 9 7
& #)& & ) & &
:6 "& 5A & 9 . &(&A & & & #
,' 7M )( =&= & ( &) )
"&&
6 ? " & ) /; 14 %2 )
; # " >&
( &" & " 3 " &
% 1 2 1 L %2
L

1. 2

0.05
0.025
EeV
0
0.025
0.05
0.075
0.1
V1
V2
0.125
10
20
30
%Pd
40
50
60
9 .$
= " &! & 7 7
)!)& !7 &" & &
'

9 ( " & & & & !
( ) 5 & " A )
)( ,'' C " *' O ) & & " )
A & ) & ? !
& ) ( !?
5 ; & " 1/; 14 %22 &
"& & & 1 3 4 %2
( A & & & & ( " & )
*' O E )( & ) &
# "&& & 1 9 .2 !
" !& "& & & ) %''' C & " "
"" # & E & "& 5
&& ( & " ! ) A !
) & " ) ) #
"" ) 6&&& 1 $$82
! "

& & & &) !
"& & ( & " ! !"
&)& & ( !
&)& ) & ( & ! A !7 "&
) & & ) & 6 &
"& 1& 9 . '2 & ( #"
13A $882A &" ! &
6 " & 7 7 !& "& && &
( & & 7P 7 & &
( *O 6 & & ( %4, O 7
,O )( #"
& "& & &
6 & & 9 . ' &( " & &) "& 6
" "& & ., O 7 & '' C
( ( 7P (!"& ) '' C )( #"
)& "&& 6 & & & &
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7! "&A ) )&
" 5 "& ,!" 7 " &
& !)& "&A ) "
&)& , "& " &
6 ) " & " )) & &"&)
( &) " " & = &
&& (! ; & &A

Theoretical PdV Phase Diagram
2000
1750
1500
1000
750
836 C
745 C
Pd3 V
500
250
910 C
786 C
Pd2 V
20. Pd3 V
657 C
Pd2 V
Pd3 VPd2 V
T C
1250
538 C
454 C
PdV L10
Pd2 VPdV3
Pd2 V
40.
%V
60.
PdV3
PdV3 80.
100.
9 . '
/#" 1 >&&&A $$'2 1"2 !
1)2 "! "& & &
( ? " & &) "&

(

) " "& & &
& ( " "&& & )( ,' O 7 - ?
4,.= *, O 7 + &
96 &A ( & "&&) & "
"&
& & &
,'M,' "& & ? ) "& & &
&A & & ) 7P ( "& #
> # & 7! "&& ( (!
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)& &" @& ,'M,' & )
> 3) 1 $4*2 & ( A &
& & & ) " "&&) & &
5 &A #& "&&) (!" 7 "&
#" #& ! " ! & &
"& & "& 6 #" "& &
& & #
# $

- " & )! &! &&
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7 ( (!" "& & = 6!" & &
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K F !7A & & & &
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6 & & ? &
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! 96 A #! !

A ( &" )&& &A !D &"A
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"&& ( & !& & 1
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(!"& ? &" ( & && " &
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; & #&& #& M #&
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& & & &)
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! ( #" )& ) & &" &
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( &(& & " ) 96 &
( & & & )&& )! "&
& & 9 " & &&! " ( !
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5 A & ) & " & " " &
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9 - & 7! !) & &
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(! " &" &" ( ) & &

& && 1) )2 &( 3 !) " (
& & )! " "& ) 9 &
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& "& & ( # !
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3 &"2 & & E & & ( & 03
6 E& !)& )
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M7 & ! &)& !& 6 ?& ? & &" ( &
& & & &&
&
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0 & & & & A A & " !
&& 1 D +A $$ 2 & & &
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%'
4 k-Points in IBZ
10 k-Points in IBZ
0.72eV
1.5
DE
0.5
0
-0.5
-1
-1.5
-2
0 0.5 1 1.5 2 2.5 3 3.5 4

s
9 8
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7 " & 6 & & L 9 8%
L 9 8 6 &) && &# & 6(
& ( # & &)& & &" &&
N

6
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4
3
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dPd c : 1.6 eV
dPd a : 1.98 eV
2
1
0
4
3
2
1
Vin
3 x 3 fch
dPd c : 2.0 eV

dPd a : 2.21 eV
dV c : 0.22 eV
dV a : 0.05 eV
StateseV Atom
0
4
3
2
1
Vsub
dPd c : 1.87 eV

dPd a : 2.24 eV
dV c : 0.21 eV
dV a : 0.16 eV
0
4
3
2
1
Vin
3
2
1
7 x 7 fh1
dPd c : 1.69 eV

dPd a : 1.84 eV
dV c : 0.23 eV
dV a : 0.13 eV
0
4
3 x 3 hhV
Vin
7 x 7 hhV
dPd c : 1.69 eV

dPd a : 1.83 eV
dV c : 0.19 eV
dV a : 0.2 eV
0
10 7.5
5 2.5
EEFermi
9 $,
0 !) && && 1 &2 =!
1 &2 1 2 M7 1 2 & & 9 & 3
& &A & & & 7 " ! &)&
&" 6 &" & & ( & & " "& 1&
9 $ 2 "& 6 &" & 7 "
= & ) !) &!!&& ( &"
9 " ) 12 & ) 12
& &
6) $
&& && 9 11 2 &&M17 22 "&& !) &!!&&
1!) 7 )( !2 =! " 1 2 !7 & & 6 ? & &
&" & 7M & :) & & & & & &" A
7 & & & 7 " &" = & " && & (&
) & ) & " && & & 1 & " && &
9 $ 2
&

=

7

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1 2

% ' ! 4'
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6 ( " ( & " &&
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& ) ( 1 V L 2 " 1 2 & 1
2 6 0 > 1% )2 & & "
5 )& " ? & " & & (
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& ( A & & > " & ( &
& & &; )& & ( &"
= & "& " 1 ''2 1 ''2 & &
, ) && )( & (& &( ) /
$$8 $$8)A &"
6 ( "& 9 $4 &( = && && 1032
& " & & && & 9 $, 9 & &
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&& 48 $' 7A (
& & E & & ) & "
& " 6 > & & ) '' 7 ( &
) & &)& & & " $' 7
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&
1 2 & 6 3 = &
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&" & " E %' 7
& " & " & & & &

pure CO &
clean Pd fch
5s
1p
2
0
StateseV Atom
4
2
0
,
1p
4s
5s
4s
2p
2p
3
x
3
) R30
Vin fch & Vsub hhV
5s
1p
4s
2p
2p
7
x
7
) R19
Vin fh1 & Vsub hhV
5s
1p
2
0
4
4s
2p
2p
3
x
3
) R30 Vsub
hhV & hhPd
5s
1p
4s
0
10
2p
5
0
EEFermi
2p
9 $4
&& && = & "& 1" "A
2A = & & ) " 1 2 & 1" "A
2 M7 & &)& & 5 ( "&
& & & &)& & &"A ) "
&(& =!03 & " 7 1 2 1&
2 & L &)& 6 )& )
"&
,*

E

.' 7 )( & " ( " ( &&
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172 ) 5 ) &&
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) " 9 $4 &(& = && & & " &
&& 1 & & 7 "&& &"2 &
( & , > & ) '' 7 ( & )
& & " 6 & " & @
& = )&
5 9 $. ( " )!" < 3 &
& 7 " = & " " & 1
&2 ( " ( "&& L &)& 5
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9 & ( & ) " 3 & 3
&A & !) & &&
& & " 1 2 6 & )& (
) & " 6 "
7 )&A ( G& % ) & &)& E 7 &
9 " && && ( & ! )& &
& " " & & 1 2
( )& " & & ( ) ) %'' 7
" = & " 7 "& 6 & )& (
> & & & & " A ( & > (
!" ! )& 1 2 & & " 7
" & 6 " !)& !!&& &
' ' 7 ( & " 7 1( & " & 2
& "
9 $8 &(& &! ) "!"" 1"2

% ) 1& ) " (2 ( )
&)& & & " &"
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& && . $ N
A &
& & ; ) +&& & D
& & " 6 " " &(& "
& "
& A
" 1 2
) "& & "
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7 "&& &" 5 && & )
<& )( A ( ( & ) ( )
) " 6 & & " (
&) 7 & !
&)& & & )

9 6 1 2 7 & " & & (
) & )! ( &)& 9

0.8
0.6
,,
Pd d-bands
dclean: -2.10 eV
dhhPd: -2.32 eV
dhhV: -2.35 eV
0.4
0.2
0
0.8
StateseV Atom
0.6
V d-bands
dhhPd: -0.36 eV
dhhV: -0.34 eV
0.4
0.2
0
0.8
0.6
Pd dxz & dyz orbitals

dclean: -1.81 eV
dhhPd: -1.95 eV
dhhV: -1.97 eV
0.4
0.2
0
0.8
0.6
Pd dxy & dx-y orbitals

dclean: -2.25 eV
dhhPd: -2.47 eV
dhhV: -2.48 eV
0.4
0.2
0
10 7.5
5 2.5
EEFermi
9 $.
&& && & &

7
&)&
" = " 1 2 1 &2 1 2' M7

&)& & 1 &2 6 & V L && = &
" ( "&& 9 & & 7
& " & &" 1 9 $ )2 ( & " E
.' 7 1 6) $ 2 6 )& &( "&

,4
0.4
clean Pd(111) hch
0.2
0
0.2
coop(E) el./eV
0.4
0.4
PdV hhPd
0.2
0
0.2
0.4
0.4
PdV hhV
0.2
0
0.2
0.4
5
0
EEFermi
9 $8
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( & ) = % ) ( &)& G&
) 6" "
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= & )

&)& 7 &" 9 & 7 A
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,.
= 1&2 1 2

. .
" 7 7
172
$$ *' .. $
$'

% 1 2
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" 1=2 1 2
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6) $*
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6& & ( 7 !) & 9 $. 6
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6) $* && & " & "& )&
& " && 9 $8 (& " < "
( & &" & &A (
& & ) "&
6
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& & & )( 9 & 6 &
)( ? % ) & " E
& " && & & 6 " ) G& "
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& & " )! E&
# $

6 E 1 2 & ( & &)!
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7 !" )& " " & !& )
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7 & ) ( =
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(
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&& ( ) " (( & & " A ) (
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1 2' & /#" & & & & " &
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4
Nozzle Temperature [K]
Initial Sticking Coefficient
200
400
600
S(E(T))
0,7
Pd(111)
S(E) at T = 440 K
0,6
Seeded Beams: S(E)

T
TNozzle= 440 K
TNozzle= 285 K
TNozzle= 520 K
0,5
0,4
Pd(111) + 0.33ML V
0,3
S(E(T))
0
50
100
150
Translational Energy [meV]
9 '
6 & 1 2 1 2P7
6 & " " )) & & & "
" 6& )
E )( 1 1 22 1 2
&
& & & #" DD
" 5 & & " 1 2P7 & #)
& )& 6 " & " & DD
" & 1 1 22 & &
*
+ $
5 9 ' ( " & & ) A )
1 2 1 2M7 6 &" & 1 1 22
& ; & ( &A )& & E 6
#" 1 1 22 & ) &
DD " & " & #"
& & ( DD "
1 A $$42 & # & && 1&
)&2 ) " 1 2 (
& & 1& 3&A $882 6 #
( && & ) E )( &&
& ( & & & " &
& 1 A $$42 - & & E
& & A & " M7 &
@ ) )& 6 @ & " &
& "&&) &" E& )( 1 A $$$2
5A & )& ) E &
& " 5 & &" E & " &
& " M1 2 & &( 1 $$,2
4*
$ %

5 ( #" && && &
MP7A ( & ( ) ( A & &
& " " & & " &
& & & " & 6& &
& " & &A & " & ) && &
&" " 1 1 22 & ; & 5 &A
1%'''2 " & " ) 71 2 & &
& ) &
*
" $
6 & & & ( " !
) & #" & ) & & & & (!
&)& ;A ( )& (& " & & "!
1G/ A $8.2 & ( ) &(A & #" &
&& & ) )
& " & &
& "
5 &"? #" ) (
,'' D & &" *, ) ; "
&& &" 0!5 "? & & F "F
& & 6 & " & " ,%' C ) !
& "M& " ;) ( ) & 1)(
*$' C ( & ) & &!
2 B & " & ( 1 "" ;
2 " &
& ) & ) 1&&2 &
&
& & "" " 5 & &
& ) & "" !& )
& ! " & & 6 @#
""M& " & #) & & ) 3" "&
& " & & &!
& 1&" "2 & & " &
& &" "
5 9 '% ( &( & & #" &
1 2 & 9 ' 1 2 & ( ' >0 &)&
7 9 ) #" & " @# & ( & ; " &&
( 6 & && ( ? & ) !
" 9 & & " & " & "
!#& )& & & )!& &
& P%' 6& & ) %' 7 1DD
" 8' C2 ( "&&) " & & ) &"
" A & ( & ) %., 7 ( " &
& & & ) " ) & "
$ ! " &
4,
Pd(111)
to 77 Units
30
20 meV
275 meV
20
Incident Beam
Scattered Density [a.u.]
40
10
Surface Normal
-80
-60
-40
-20
20
40
Scattering Angle [Degrees]
9 '%
& 1,'' D2 )
1 2 & ( " ,%' C 6 & "
; & & & ! & "
&& 1" & &2 & ) & & %' 1) & 2
& " & " 1&2 & & & ) && (
" & 6 ( & " & #" & ( ) & %' 7
%., 7 &"
Pd(111) + 0.33 ML V
30
20 meV
275 meV
Incident Beam
Scattered Density [a.u.]
40
20
10
Cos(q)
Surface Normal
0
-80
-60
-40
-20
20
40
Scattering Angle [Degree]
9 '
5 #" & &( 9 '%A ) ( 1 2
P 7 & &" 5 & & & & ) &
%' 7 )A " ( & " & & " )
& 1%., 72 "" " )) && & &
& & ) & ( &
44
$

- E E &)&

& " & !
) & " & & ) 1& & ) (
&" & 2 %' 7 " )
& " ) & )( ) ( 1"& "
& ) "& &2 6& & & & ""
( ) & )
&" @
( " & "" " & A &"!
" " &"" & 9 A &A & &"
@ & ) &
#" "& " & &
& " 1 2M7 A ( & & " &
) &
) %+

9 & & ; E )( ( & !
&A ( " )! & - & 7 )!
& " 73A & & ) 3 . & ( <
( 1-2 "& 1 3 *%2 ( & !
& ( & 6 & "" #!
) ( - 1-$ 2 (& " & &
#!
6 & & ) & "&

" & & 1/32 ( # & #) & "!
&A ( )&& & E& 1 A $$.H
/ A $$8)H C &&A %'''H 0 A $$82 !
"(& && !#&A & &( " & !
"" 1) & 2 ( & & )
"(&A ( & " & @ ? & & &
&(& & )& & 5 9 '* & & &&
4!& " & M7 &" 6&
&! ) & ) /3 & &
)! 12 ) & 1 2 &"? 1?#2 "!
5 " '* '* & "& " &
" & ( && &)& A
&& ) && 1)!!)2 1& &2
6 & &? E )( /3
& & " &
"
& &" "&& ( & 6
& ( &)& 7!& && !&& (( A
& )& && 6& & ; &&&
:T & 1%'''2A &"? " & & ="!
$ ! " &

a)
h/
4.0
4.
b)
btb
btb
bb
bb
3.0
2.0
1.0
-0.280
-0.168
-0.096
0.220
c)
d)
h/
2.0
1.0
0.014
0.6
0.059
0.8
1.2
d/
1.6
0.6
0.8
1.2
1.6
d/
9 '*
& @ & "
" 1 2 & 1A2 1 2M7 1)A2 &
) & 1 2 )! 12 6
& & && 1 ! &&
!&
&A
&)& A (
7 &2
)!!) "& 12
1)2 )!) "& 12 12 = & ( '' 7
/ & & & ) "&
& 8 $ & ( E ( &
) ( )!!) )( 9
'*) & 6 "" & 1 9
'*2 & 1%8' 72 & ) & )
&& !" & 6 ) A &A &
1%%' 72 " 1$4 72 ( A
& & K F ( )(!" && (
) ) & &(& ( & ( "& (
7 A & ? "& ( & !
(& 6 & & & % N
&& (
) ) & &A ( ! "!
(& & 5 Z Z (
? & ) & & "&& 1 )!) "& 2 #"
!" && A "" &( & ( & !"
&&A ( & "&&) & ( )
5 9 ', ( & " 1 "& )!&2
!" && 9 && ) %, N

$

48
0
0.00
Pd/V
-0.02
E (meV)
-50
-0.04
-100
-0.06
90(flat)
E / eV
2.4
-150
2.5
3.0 3.5
h ()
4.0
Pd
2.6
h / 2.8
45
3.0 0 (upright)
9 ',
& " !" "&&
1 2 1 &2A 1 2M7 1&2 7 1 2 12 & &
@ 1 &2 " 1) &2 & 1)2 &(& & &
!" && M7 & & & 1 2
1!2
" & 6& ) & ) "" #
/3 ) &" "& "& ( !
& 5 ( !& " &
" & 1) & L 2
" " & 1 L 2 6& " &
&& & A ? &
"& & " && &( & ( )
%, N
& ) )& & :( @ &
"" & &A ( "( " & !
&& &" 5 9 ',) & )( & ( &
K & F & && - /3 &
& ( ) )( & ( & & "&&)A
M7 &( "&& " " & & 5
!& " 9 ',A " 0 !& &
"&& ) & & &) 5 & ? ( &"
& 7 1 2A ( 1 & 2 & & )
)& 1 A %'''2 9 & & & )&A A & &
& &A ( & & ) &( & "
" && 1 1 ''2A 1 ''2 1/ A $$8)2 :1 '2 1C &&A
%'''22 ) " & & )
%' 7A ( &" & &A &;
& Z ? & " Z & @ &
" & " & ( &

$ ! " &
4$
) & &A " & & &?
) &( & "&& ) ( A ( &
" " ( &)& A
) "" & "&& ) 6 ( & "&& "!
( (& && - (
( ! & &
& ( & ( A ( )& "
"&& " ( ) & ( " &
; & (
) &

/3 M7 & & " "
; & A & ) E #&& & !
A ( " & " A ( 1& 2
( @ & "" & ( &? &
6& " )( ( &A ( ) & ) (
" "(& &( 9 ',A & ( "&& " (
& " & & " ) )& &
& & & " " &&
##
*

+ "###$

&
(
6 & & " " " & 9 1 2
& ) & " & " 1 2
& ( &"!& !)& &
" && " & &
& #" & & "&A & &
) 9 ) ) & " 6&
& )& = 5 & ) & !
) &A ) & !)& ( & ) &
6 & " & E&
) & ) " && && !) !
)& 6 & A &" " & &
; " 5 & &" ( & @
& & A & 9 1 2 & & &
E & & & )&

5 =" & 8! ' ( &&& & ! & E
" " & " &
:( ( # & & )
)& &A 9 3A &( ) &
" !& & & &A (
" & " &&& ? & 1 A $$'H
/& A $$.H > A $$,H A $$.2 & &
" & ( < ) )& <A =L =L= -
.
.%

" & & " =L= ) ) & A (
" & && ( & "
=L )
6 " & " & & &
9 1 2 & & ( & & )& & ? &
&" ( & #" & & 5 #&
" & ; ( ) ); 3 1 $$42 &
&!" # & " ) & )&A (
& ) # 6 "& "
& & " " & & & ; & &
" ) 6 & &"& "&&) & ) ) &
&
6 " " & ) &"& 9 1 2 & & & & )
& #" ) $$* $$%A &"
6 & & & ( & ) & #!
& #" 0(! E 10//2 #" & (
" ) 1 $$')2A S! "&& ! &" &"
) 1 $$%2A (! & 10/532 ) = &
1 $$.2 && ? & ( &
& 6 &; &&& 9 !
" ) & " 6 "
9 & ) ) && ) &
& 6 1 2 & & &"& " (
!; "&& && ) #& !#& 9
& ) &)& A &" &
& !A & 9 & "& &&
; & " & &
&& ) ? &!" "& & )& &"
&! 6 #& 96 &"!" & &&& &
) 1 $.%2 &"?
&& & 3 %A #
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& & & )& " & 3 , - &
& @ "&&) 9 " & &
& )& 5 3 4 ( &&& E&
& & " & "& && (
#" & 9A 3 . & & " &
5 # " ( ( " & " & &" " !!
& & 9 6& ( " & ( (
")& 1); 3A %''%2A &&& & " !
& " 1 2 &
' ( ! "
.

+ !& &A & #&A & " &A
& ) ( &"!&
6 &!" C!3 ;& ( & & "!
(!)& 7 ) 3 173A 3 .2 &
& #& & "" #
) ( - 1 $$%2A & -$ A (& &
& +&& & & & " &" 6
"!( E & ) & ) "& ) *'' 7
& 1&& (& & )(2 !" & (&
& & & &" 1 % % 2 !"& " 1 2
& 6& & & ( &"
E ) !"&
&& " < ( "& 1 3 *%2
% 4 N
9 &"A " &&
& &&
6 &) & &&& * & &)&
&" ) *!4 & 9 &)& & & &!
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9 & & & 3 )( 5 #
"& & & & " & ;&!:(
& # !9 & 1 3 ,%2 = &
( && &)!&"
0 " && && ( & & )
3 ,, A ) ;& & 3 ,* 9
& & ) ; 1& ) =
) D!#& 2 & & &
" & & ? &" !
&" ) & 6 <&?
& ;G& " & ) ) & & #
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& " & ) ; &
) ( ) & < & )& A
& " & ) 0E 1 $$$2
&
*
9 ) & ( ) ., O && 0
1= 2 & )( & " ) ,'' C
" & "& & &) " &
4'O + 8,O
.*

%
& A 9 1 2 & & )
& #& #" 9 &A 0// && )
1 $$')2 &( & & ( & & 6
" $4 *A 88 .A 8, , O
"" & & &A &" 6& & &
( & & ) & & : & #)
& " ? 9 #" : 1 2 &
? & & & " ) : & 1$$ O2 ( &
& ' , O : 1+ A $8,2
6 0// & &"" ) ! "&& &"!
&" && ) 1 $$%2 & ( & 0/53 & & ) = &
1 $$.2 " $''!$,' C :, , &&
&( & $88 $$. O & ( &
) 6& " & ( )( !& "&
& ) 6 & & & ? ) &
& & 1= & A $$.2 &
( & ) & & " & "&
) = && 1 $$.2 ) 1 $$$2A " '4 '.
7M &" # && 9 ) 5 &
# & & ) = & 1 $$42 9
) !

&A ( & ) $'' C && "
,, O

,
- & ( " & & ) @ &&& 5
&&& " " 9 )A !
& '' ., O " & &" 1
9 2 5 9 & A & 9 &
" ) ( & 6 & ( &
& "&&A ) % - & &
&)& 9 & ) & ) & 6 @
& ) #" ) ( %
& 6 & & ) " & & ) ); 3
1 $$42 # && & &
5 & & & A ( ( & & ?&
) & A ( "& 9 & &
( ) ) 9 1 2

$ -$
6 ? 9 &; &
A & " )& & 6
' ( ! "

2.82 2.76
Fe
Pt1
Fe
Pt1
Fe
Fe
Pt1
Fe
Fe
Pt2
Fe
side
view Pt
2
Fe
Pt2
Fe
Fe
Fe
Pt2
Fe
Fe
Dh
Fe
Fe
Pt2
Fe
Pt2
2.79
Fe
Pt2
Pt2
.,
Pt2
Fe
Fe
Pt2
Pt2
Fe
Fe
Fe
Pt2
Pt2
Pt2
Pt2
Fe
Fe
Fe
Fe
Dz
d12
d23
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
d34
9
> 9 1 2 & 6 &"
1; & 2 & ) & 6
) 9 )! & %.$ N
/#" &
! &&A J A J 6) )(
9 & 9 & & ) ) 5(&
1 $$42 & &"!" & & ! & !"
" ( 190-2 6 ) % & ;
( L %8 9 ) 6 !
&& & ) 6 ) &(& ( &
? & 1> A %'' 2 5 & "&A ) !
& 1) & & ) &2 " &" 1
& "& Q 2 & & & & ? &&!
"& 9 & " &" "& 1 Q%2 9
&A ( A & & ?
9 ?& "# ( E # &)& & & & &&&
> 1%'' 2 6 & ) &(&
! & !" ) & &)& !"
"&&
5 ( & & & ? !
" E & &)
"& Q ( ; 4* & & &) -
Q% "&&
& & ) ) & !E '' 7A &
& & 6 & & L '
9
9>
N
[\ [O\
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%% % !%$
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# A 9A 9 1 2 & & 6 (& 1:>2A !
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) & & ( & /#" & 1 $$')2

J
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%
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&
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& %, A ) & & ( & &

! .
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9 &" ? A ( & ' %8 O &
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9 1& 9 2 5 & & &"
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&" J
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6 & & & & & )
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& && @ & 12
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9 !) ) ' & 6 && ""
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#" - & & ) " !
< " ( #" (& &
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b)
a)
c)
d)
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0 && && 1032 & & 1 2
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1 2 12 12 6 &!!&& !)& A
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& 5 ) 1 " 2 & & &)& & !
) ' % & & & 6
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#" A " ( & )
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9 & ) A #" & ''% 7 (
&" " & 6 #" " A
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9 % &(& & && 1032 & & 5
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8'

) !!&& 1!=>2 & %' 7 )( !A ) & &
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9 & 1 2 L .8 &&M17 2 5 03 &)& !
9 ( & " &" " &
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& A ) & ' 4 7 ) (
9 )& &"
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( & & & #& - "
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& )& 6 % )& &( #" & A
; 9 & & & ) )& #)
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9 < ) 6& )& " ( &
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& " " &
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J L '% 7 =&; & )& % &"& ( KF
9 & &"!" &
0.8
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8
Pt1
dxz(-2.19 eV)
0.8
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8
dyz(-2.26 eV)
0.8
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8
d3r-z(-2.31 eV)
Fe
Pt1
Fe
Pt2
dxz(-2.08 eV)
StateseV Atom
StateseV Atom
' ( ! "
dyz(-2.14 eV)
5
0
EEFermi
0.8 Pt2
0.6 dxz(-1.82 eV)
0.4
0.2
0
0.2
0.4
0.6
0.8 dxz(-1.79 eV)
0.8 dyz(-1.82 eV)
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8 d (-1.79 eV)
yz
0.8 d3r-z(-1.91 eV)
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8 d (-1.89 eV)
3r-z
d3r-z(-2.19 eV)
10
10
5
0
EEFermi
9
&& && 132 12 % 1 2
& ! )& 9 1 2 6 ) & "&
!) !!&& &" ) &" " 7
/ ! 6 ( )( ( "& &(& "&
&" & & ( &" ( &
%

- ( & " & & &"&
& & " " ! & & & )&A =
A ) #& & " 1 2 & & 1& &
)(2 #& #" & 9 & =
1 A $$*2 & ( & 1 A $$%2
& " (& & !& "&&
#

8%
t2
h1
b3
f2
b1
f1
t1
h2
b2
9 *
& & " "&& 9 1 2 & &
& & & 1& 2 9 & 1
&2 &" 1 9 2
1% %2 & ; !& & " &&A
& 9 * 6 ( " 1 A%2A ( " ( 1 A%2A (
( 1 A%2 "&&A
&" )
% & & 9 & "
& " "&& % & 9 & 1 " %2A (
(& # % & "& ) 9 !
( ; ) "&&A ) % & (
) A )% ) ( & ) &
&A &"
6 && "&&) & & & %% &
) & 9& * 6 1 (&2
& & V L " ! & 1>02 & )
&

&'
6 & " = 1 2 & ) #& & #"

1& 3 A $8%2 = & )& " ?
( ) " (( & 9 ( & "
&& " ) V L '%* ) ;
&& ( ) " & )& 0// #" & V L ',
( 1* %2%= & "& ( ; ) =
& " ) && 6 ! ) ) & )
) 0// 1 A $842 ) 8, %'8 N
"
N
) && &" ( =Z ) , ) && 6
& & && && 1& 9) A
%'' A & 2
&& = & " & &
' ( ! "

1
"&

[7\
"
,8,
) .%

.*.

.$
9 1 2
"&

[7\

%8*
%
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3A %''%2A 12 && ;? & "#
& )A "
6 & " & " & ( & " & !
6) %% ( ? & " 1 2 ( & "
&& ( & ); 3 1%''%2A ( & E
&" 1 & 1 32 & - "&2 (& & !

;

? >
< 1=

< 1= >

? >
< 1=

< 1= >
6) %%
& " & " " & ) " & & & " &
E & & 1& # <&? &2 & )!& & &
& & " & ( " &A # &

%'%

' ( ! "

(a)
(b)
(c)
(d)
(e)
%'
(f)
9 %
& " & " & & & &
** 12A * 1)2A " ! & 12A " 12A !& 12 ! * 12 6 & )
(& & A &"& & && &
& " & A & & & ' 7 " " & "
1 M *$ 7M2 " 1 2 &
** & " & ) &) & " =L
)!) ( A & " ) )!)& &A & L ' CA
& &) ? 6 & ? &
(& " & " 1 2A E )( **
* &
6 ( "! & ( )& !
& " &A & " & ?& & "
= & 1=" 2 9 &
) & % &A ) && @ ) &A )
& ) &A ( & & & # & !
& ) 9 & " & ** * ( &;
" %!= & 6 & " E )(
%'*

? & =L= =L )!)& & & '.$' 7
" 1 2 & '4* 7 & 9 A !
& )& & ) & " A ' *' 7 &)
" ! &A ( & & " " & "
1! *2 & "
7 & " 1"!2 (& " ; !
& & " ""
& & & % N
A &)& )& : && & "
& @ & " ? & 6 &
6) %% ( " & 1 3 %%2A ( !
& & ) 4'Z.' 7A & " &
" & &)
9 " & " =L= )!) & (
( "& = 6 A ( A @
& " =L )A ) & " E )!
( ( ? & ( '%, 7 6 !& & &
&)& " & " )& "& )(
# " 5&A " !& ? !
A =L= )!) ( % & A
& & & ) ? A **
/ ( & @ 9 ) " &
& 1 9 %%2A G& #
6 & 9Z )& && & " &
& # ( & 9
* & '% 7 &) **A =L= )!
) & ) 9 & " ! & !& ) )
& &) ? &A &) ? A
" 1 2 & 6 & & " A (
=L )!)A ( & #"&
!& )
& & " )& " )&
"&&) " & & 6) %%
& & ) ) .' 7 4 7MN
V L *
3 & & & ) ? & "!
" ( A " & "
& 1) " 2A " E& )
6 " & ) & & ) " ( "
; 1 &2 "& ; & & &
" " ; "& "" # &
" & & & & " &&
& " " !& & " & ( )( '' CA
& && @ & " &
' ( ! "

%',
$
= & ) & " & "& & ) &
? & " ? 9 & &
9 %* 6) % 6 &! && " & &
&) &! 1) *' 72A ) & & A 6) %
9 %*A &" ) & &? E
)( &! &! & = Z=%Z= A ( &&& (
& 6 " & && 1& - "&2 &
& ( 3 "&"& 1); 3A %''%2
" & " & )& ( &
! & 9 !& & "
" & 19 %*2 ( & = Z=Z=
) 4 ( &" & "& 9 A = Z=Z=%
& & ) 8 & & "& #
" = Z=%Z= & & ) . ( &"
& "& # ( & A =L )!
) & & " &!"& "
& ( & )G& # ) &
"
6 =L ) & ( ,.O ( &" &!"&A
Z= Z=% & ) % ""& & )
& " & " " ! &
5 6) % ( )& & & 6 # (
& "! & & ( 6 Z )
!& & "A ) %*4 N
A & & ) & Z )&
120
1.36
6
50
1.4
1.50
116
128
127
1.52
1.51
1.47
1.23
1.
112
1.52
112
1.50
1.44
110
1.53
110
1.53
1.30
1.25
121
126
123
124
9 %*
5 ) & & && &!" 1"2A
" !& & ) " 9 1) 2A &
& " ? 9 1) 2 & ! &
&! & ( 1 " & ) ) &2
&& N
6 @ 9 & & @
& )

%'4

!

"#
"#
"#
"#

6) %
5 !& ) )!& " & )
"! ? 9 !& &&
N
9 " & )!& & "&
"#& 1+ && A $8,2 6 ) &
) & %' O ( # & ( 9 6 E & & A
A " ! & & "
6 " ( ) & & &
" & "& =" ( & " & (
A ( )& & )
( &)& ) ) 'OA & && " 1 2 &
- ( =L= ) ) & ( &
? A ) & ; & =" &
)! & =L )!) " & "A &
& 'O & * "! &
" ! & ? & 5 " ! & & "
"! & ? & )!
& & 4O 3 ( ( && "
& 1); 3A %''%2 !I 13& !) A
%'' 2A )!)& ( & ) !?
& 4O 3 & & &
- && )
=L )!) A ( & & "
& " "! &
%
,
6 ;&! ( & & ) & "!
9 & & ) 3& 4% %%% 5 &
) & ) # !& &&& ) = &
1 $$.2A & ) & & ( &
& A ( & & " & 5" " &
' ( ! "
%'.
) & & &
" A ( & # - " & &
" & ( #" & & &)
# ,'!,' O A ( )!
& 6 # (& 9 A
& & & &" & & ? ) & 5
) & !& "
? 9 & &&" & )! &
& 'O 96 6& <&?& &
; && &
3 & & 9 & & &
9
1= &A $$42 !S & 1SLAAA=2 1&& A

$$42 5 A & " ,, O
(& ( A ) & && E & )&
& " ? 3 C 1%''%2 & E
&" "& " ? ! !&&A > C
1%'''2 &" & ) & &! !S !" & 6
<& &&
5 : & &
& && *, O 8' O " & "
= 6 & " E = & ) : & ' 7
& )! & " ? & & ) & #!
" & 1 $$'2 " "!
" ?& & & 1>/532 6 & #!
& : 1 2 & & 1 & A $$')2
A 1%'' 2 & & )! &
= 1 '2 & & 6 ) & " &
& A ( & " = = & =!& 6
= ? & & 4, O &
,. O . O " & " A%Z
% C ( &
6 && & &( 9 %, 6 & &
)! & ) 1%' O 92 (& !
& 9 ( ) &)& 6
" 1" & 2 & $, O 1 ; !
&& & & & ) &
& 9 & 2 5 ( #" A
& " & &&& & " &
- & " & & A & !
& ) &? & & " "!
& - )& 9 %, & "!
E &( )( %'' *'' 7 (M(
& & A & %'' C & &!
& '' O & ) 8' O - 8' O
#

%'8
100
DEad = 0.0 eV
DEad = 0.2 eV
Pt surf [at. %]
95
DEad = 0.4 eV
90
85
8eV
=0.44
DE ad
400
600
DEad = 0.6 eV
t)
nal fla
V (pr
.650e
0
DE ad=
80
200
right)
al up
(pren
800
1000
T [K]
DEad = 0.8 eV
1200
1400
9 %,
& "! & &"
;&! & 9 ( &)& &
9 1 2 && E & E & "
& 9 & 6 & & & & " E &
@ " " (M( & &

& (& 6 & "! !
& ) *,' 7 & ) 4,' 7 D
& ) " 6& & ( ) ( & ) & "!
& !" ? & 9 #"
& "! & !" ? & !
" = 1 '2 1 A %'' 2 &&
&A ( & E& & "
& " & & & 1 ) !
" 1'' C2 & )2A & & )! "&
&

6 (A " & & & !
"# && & & & & ) &! !& &
? & " "& & ) & 5 ? & !
&& 9 && ); 3 1 $$42 &&&
)! & & && & & "!
A & ) &!" ! #
& 5 & " &"! & 96 &
9 1 2 & & ?& ) & & )& (
" & 5 " & " A ( ( & && &&
' ( ! "
States/eV Atom
%'$
Isolated Fe atoms
d (sub-surf ) = -2.97eV
d (surf ) = -2.78eV
-1
-2
d (sub surf ) = -0.01eV

d (surf ) = 0.14eV
-8
-6 -4
-2 0
E-EFermi
9 %4
0 & && &)& & "!
9 !& & 1 &2 & & ? 9 1
9 %%A & &2 !) && && 7 )( !
@ & & & !
M&)& "#
- ) ( & K&F &)& & 9
& 9 ? 9 & & 19 %42 !) &!
!&& 1=>2 7 )( ! 6 & & !)
=> 9 & "! & ( &" &
9 %1)2 & & E &" & & (
& & 1 $ &!) & &
% &)& 2A " < !&" "
& && & ( & ) & 6 < !&" ) 9
& & & ( !)& )&
& !) & !A & & & &
&)& &A & & )M&)& &
( (&
K F )& &)&
( " )& & ) & & )&
& E A ) && !
& ? &)& )& ( ? )&
) ) !A "
6 ( " "& 1A)2 9 %. &" && &&
& & ( # " A "
&" & & & 6 &
&& " & 19 %.2 !
#

%'
1.5
(a)
(b)
0
-0.5
-1.0
-1.5
States/eV Atom
(c)
0.8
Fe atom interacting
with O
d (clean surf) = -2.78eV
d (h3 (flat)) = -2.80eV
d (top) = -2.89eV
States/eV Atom
0.5
-1

d (h3 (flat)) = -2.23eV
d (top) = -2.18eV
-8
-6
-4
d (clean surf) = 0.14eV

d (h3 (flat)) = 0.09eV
d (top) = 0.14eV
-2
-2 0
E-EFermi
O atom - h3 mode
-8
(d)
0.6
0.4
0.4
0.2
0
-0.2
O atom
top mode
-0.2
-0.6
-0.6
2.5 5.0
-2 0
E-EFermi
-0.4
-7.5 -5.0 -2.5 0

E-EFermi
-4
0.2
-0.4
-0.8
-6
0.8
0.6
States/eV Atom
States/eV Atom
1.0
Pt atom interacting with O

d (h3 (flat)) = -2.36eV
d (top) = -2.15eV
-0.8
-7.5 -5.0 -2.5 0

E-EFermi
2.5 5.0
9 %.
03 & ( G& #
@ 1A &2 " 1"A & &2 & "!? &
12 9A 1)2 9 ? 9 1 03 &" &
& ) &2H 03 #
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12 & "!A 12 " & "!

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6 # ( & 19 %.)2 & & A
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& A & " & "
& ) )& - & " ! ) &)& &
)A " & ( ) & &
( & )A & & & ' & " & " 6&
& &" )A &;
A ) %% & ? A
&& & %
& 12 12 9 %. &( && &&
# !& ) 12 "!& ) " 12A "
9 1 &2 ? 9 1& &2 "
( &)? & ( & ! ) "& )
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? 9 12 ? 9 1)2 5
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"& 6 @(
=L= )!) & & ) 6 & &&&
) & < !&& &? &!

)

%%
Oxygen
(a)
Platinum
Oxygen
(b)
Iron
9 %8
5&& E !& " ! &&!
( &" & & !&
& "! 9 12 ? 9 1)2 = &&
& " & ) &A &"
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- .

7) &" "( & & & " & &
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)

%*
prenal (gas)
disCC
h3 (norm)
h3 (mod)
top (norm)
top (mod)
3500
3104
3000
C-H
2801
3051
C-H
3059
C-H
2883
2763
3045
C-H
2921
3110
C-H
2908
3102
C-H
2925
1646
C=C
C=O
1611
1609
C=C
C=O
1543
2500
cm-1
2000
1500
1704
C=O
C=C
1614
1678
C=O
1198
C=C
1000
1528
C=O
1200
C=C
1281
C=O
C=C
1202
500
9 %$
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& )& @ ? 1 2 ( ) )!)&
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162 "& & & 6 & &
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"
6 @ & & & (&
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( "& = 2 " A & &"
" & &A ) & &
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3A ( ;&& A & " ) &( &"!

- & & ( =L )!)
& ( " " & 1 &
& &2 & & ] 9 " 1 2 &
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6) % 2A ( & &" ? & &"
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& " & 5 & ( " & &&
1 2 & & )
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( ( & &&&
#(

.& .

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& " & "!
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=" & && ) & (& & ) #!
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> G& 0( 1> A $4,2A " "( ) "
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%8

& 1962 & 1) '1( 2A ( ( !
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1 2 & & 5 & ( !
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& 1& A $$.A & 3 % 2 6& && !
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6 & && & & &
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= = 6 (
( & & !&& " 7555 & & && E
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6 && & " & & (&
!
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# " & ( &! !& &

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( &"!" & & & "!( )&
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- 1-$ 2 & "" # 1 ( -A $$%2A
& & "" #A (& & &
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6 & & && ; &
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& " & "( 6 & ) 1:/2 &
3 , (& "" & " & &
"(& && ( ? & )(
? & (& & ? " &" & "
&& )( & "& &" (& & ""
) :/
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( & & 16362 3 4 " &
& "

) &A & & &A &)
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& & & & " &
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=!& " " & & &
V L
5 9 ( " & & & & 3)!
? 12 &(& &" 1 2 & 9 1 2 & & )

'(
(a)
(b)
Fe
(c)
Pt1
Pt2
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Robin Hirschl II PDV Thesis

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& '       %    

 "&  &

 (  )   "  

. . 6"  "   

* +   "   ( ,- 

 !  "   ( )+ % 

. / 0 "   ( ,- 1 +

  ( 2 ,- % 

 3     %   ( 2 ,% 5 

!"  5 )  &     A 

+ C &&A    A 

  

7 &  &)&;  &   "&& %*,4.  % % A

' ' 4,$

Palladium-Vanadium alloys - Phase stability (T=0K)

Pd3V (D0a, Cu3Ti)

atomically ordered alloys

$4.2   &   "&&)   & (!" 

)  &&   2A ( &  L  % L **%  &!"  

    "&   7!"   &"  &  &

6  )& &(     "&&  "&

5 & 7!  A  ) "  7 & #"  ) 

   

   

Pd3 V Cu3 Ti

PdV3 Cr3 Si

Pd3 V AuCu3 , L12

Pd3 V Al3 Ti, D022

Pd3 V Cu3 Ti, D0a

  

&    !7 "&&  &   &"  )  % % % 

   &   ( 7  & "  ) ,  O

Pd87.5 V12.5 fcc

Pd37.5 V62.5 bcc

Pd25 V75 bcc

Pd50 V50 fcc

Pd50 V50 bcc

Pd12.5 V87.5 bcc

   

#$ $   !  

      

 $   "  

! "  

Theoretical PdV Phase Diagram

   (      

!  96 A      #!  !

(! "  &" &" ( )    & &  

  

! %  

   

) &  &"  " )&  !) E& )  "

1    P    2

   

0 0.5 1 1.5 2 2.5 3 3.5 4

2.28 2.20 2.20

2.28 2.33 2.27

   

!"" "" #

& 1/32

& ' %

"& &

( ) "

.. 6" "

* + " ( ,-

! " ( )+ %

. / 0 " ( ,- 1 +

(2 ,- %

3 % (2 ,% 5

!" 5 ) & A

+ C &&A A

7 & &)&; & "&& %*,4. % % A

' '4,$

$4.2 & "&&) & (!"

) && 2A ( & L % L % &!"

"& 7!" &" & &

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5 & 7! A ) " 7 & #" )

& !7 "&& & &" ) % % %

& ( 7 & " ) , O

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3 $* 6 ?& &&& 3 $, ? & &

# &'

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"& #$% &%

,' O !& "&&

[7\ [\ [\

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#

clean Pd fch Q=1/3

dPd c : 2.0 eV

dPd c : 1.87 eV

dPd c : 1.69 eV

dPd c : 1.69 eV

&

E

" = " 1 2 1 &2 1 2' M7

K & && ]F ) + D C D 1 $842

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