ELECTRONIC STRUCTURE OF Pd ON Nb(110) INTERFACE

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Submitted on 1 Jan 1984

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ELECTRONIC STRUCTURE OF Pd ON Nb(110) INTERFACE

V. Kumar, K. Bennemann

To cite this version:

V. Kumar, K. Bennemann. ELECTRONIC STRUCTURE OF Pd ON Nb(110) INTERFACE. Journal de Physique Colloques, 1984, 45 (C5), pp.C5-449-C5-453. �10.1051/jphyscol:1984567�. �jpa-00224186�

ELECTRONIC STRUCTURE OF Pd ON ~ b ( l 1 0 ) I N T E R F A C E V. K u m a r a n d K.H. B e n n e m a n n

I n s t i t u t filr Theoretische Physik, Freie l l n i v e r s i t t l t B e r l i n , ArnirnalZee 1 4 , 0-1000 B e r l i n 33, F.R.G.

Resume - A l ' a i d e d'une methode de l i a i s o n s f o r t e s self-consistente, l e s den- s i t e s d ' e t a t s l o c a l e s Glectroniques o n t St6 calculees pour l ' a d s o r p t i o n de Pd s u r Nb(llO), avec un taux de recouvrement 0 v a r i a n t de 0, 25 a deux mono- couches. Les r e s u l t a t s sont u t i l i s e s pour comprendre l a t r a n s i t i o n s t r u c t u - r a l e commensurable-incommensurable au voisinage de 0 = 1 e t l e s changements q u i en decoulent pour l ' a b s o r p t i o n de l'hydrogene. Les r e s u l t a t s de nos c a l - c u l s sont en accord e x c e l l e n t avec l e s donnees de l a photoemission a n g u l a i r e . A b s t r a c t - L o c a l e l e c t r o n i c d e n s i t y o f s t a t e s h a v e b e e n c a l c u l a t e d u s i n g a s e l f - c o n s i s t e n t t i g h t - b i n d i n g scheme f o r Pd c o v e r a g e s ( 0 ) r a n g i n g f r o m 0 . 2 5 t o t w o m o n o l a y e r s o n ~ b ( l l 0 ) . T h e s e r e s u l t s a r e u s e d t o u n d e r s t a n d t h e c o m m e n s u r a t e - i n c o m m e n s u r a t e s t r u c t u r a l t r a n s f o r m a t i o n n e a r €I = 1 a n d t h e r e s u l t a n t c h a n g e s i n t h e h y d r o - g e n u p t a k e . R e s u l t s o f o u r c a l c u l a t i o n s a r e i n e x c e l l e n t a g r e e m e n t w i t h t h e a n g l e r e s o l v e d p h o t o e m i s s i o n d a t a .

I n r e c e n t y e a r s t r a n s i t i o n m e t a l o v e r l a y e r s o n a n o t h e r m e t a l s u b s t r a t e h a v e b e e n shown / I - 3 / t o e x h i b i t u n u s u a l r e a c t i o n r a t e s a n d m a g n e t i c p r o p e r t i e s . I n o r d e r t o u n d e r s t a n d s u c h b e h a v i o u r i t h a s become i m p o r - t a n t t o s t u d y t h e i r a t o m i c a n d e l e c t r o n i c s t r u c t u r e i n d e t a i l . H e r e we a t t e m p t t o a n a l y z e one s u c h i n t e r e s t i n g e x p e r i m e n t / 3 - 6 / o n Pd o v e r - l a y e r s on N b ( l l 0 ) . As o b s e r v e d i n l o w e n e r g y e l e c t r o n d i f f r a c t i o n (LEED) / 4 / i n t h i s c a s e t h e Pd o v e r l a y e r shows a s t r u c t u r a l t r a n s f o r m a - t i o n n e a r a m o n o l a y e r c o v e r a g e ( € I ) f r o m c o m m e n s u r a t e ( C ) t o a n i n c o m - m e n s u r a t e ( I C ) s t r u c t u r e w h e r e t h e Pd l a y e r r e c o v e r s i t s u s u a l f c c ( l l 1 ) s t r u c t u r e . S u b s e q u e n t l y t h e r e i s a m a r k e d i n c r e a s e i n t h e h y d r o g e n u p - t a k e r a t e b y Nb. F u r t h e r d e p o s i t i o n o f Pd l e a d s t o f u r t h e r i n c r e a s e i n u p t a k e r a t e . T h i s makes Pd o n ~ b ( l l 0 ) t o b e a n i d e a l s y s t e m t o i n v e s t i - g a t e t h e c h a n g e s i n a t o m i c a n d e l e c t r o n i c s t r u c t u r e a s a f u n c t i o n o f c o v e r a g e a n d t o u n d e r s t a n d i t s r o l e on s u r f a c e r e a c t i o n s . A n g l e r e s o l - v e d (AR) / 5 / a n d a n g l e i n t e g r a t e d ( A I ) / 6 / p h o t o e m i s s i o n e n e r g y d i s t r i - b u t i o n (PED) m e a s u r e m e n t s h a v e a l s o b e e n d o n e on t h i s s y s t e m . T h e s e a l s o show i n t e r e s t i n g v a r i a t i o n s o f e l e c t r o n i c s t r u c t u r e w i t h c o v e r a g e . I n p a r t i c u l a r , t h e p h o t o e m i s s i o n f r o m a m o n o l a y e r o f Pd l o o k s s i m i l a r t o t h a t o f a n o b l e m e t a l . I n t h e f o l l o w i n g we p r e s e n t r e s u l t s o f s e l f - c o n s i s t e n t e l e c t r o n i c s t r u c t u r e c a l c u l a t i o n s f o r v a r i o u s c o v e r a g e s a n d i n t e r f a c e g e o m e t r i e s w h i c h when c o m p a r e d w i t h t h e p h o t o e m i s s i o n r e - s u l t s e n a b l e u s t o i d e n t i f y , i n d e p e n d e n t o f LEED, t h e s t r u c t u r e o f t h e o v e r l a y e r s a n d a l s o t o u n d e r s t a n d t h e o r i g i n o f t h e s t r u c t u r a l t r a n s - f o r m a t i o n . A d e t a i l e d r e p o r t o n t h e s e r e s u l t s i s g i v e n e l s e w h e r e / 7 / . F o r i n c o m m e n s u r a t e s t r u c t u r e s t o b e c o n s i d e r e d h e r e t h e c o n v e n t i o n a l b a n d s t r u c t u r e a p p r o a c h e s w i l l no l o n g e r b e a p p l i c a b l e . We h a v e t h e r e - f o r e a d o p t e d t h e S l a t e r - K o s t e r t i g h t - b i n d i n g a p p r o a c h w h i c h i s b e s t s u i t e d f o r t h e d - e l e c t r o n s a n d h a v e u s e d t h e r e a l s p a c e c o n t i n u e d f r a c t i o n m e t h o d t o c a l c u l a t e t h e l o c a l e l e c t r o n i c d e n s i t i e s o f s t a t e s (LDOS). Though i n p r i n c i p l e , t h e s - p e l e c t r o n s c a n a l s o b e d e a l t w i t h , we l e a v e t h e m o u t o f o u r c a l c u l a t i o n i n o r d e r t o s a v e c o m p u t e r t i m e a n d a l s o b e c a u s e a l l t h e s i g n i f i c a n t c h a n g e s i n p h o t o e m i s s i o n o c c u r i n t h e d - b a n d e m i s s i o n .

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1984567

C5-450 JOURNAL DE PHYSIQUE

For ~ ( 2 x 2 ) and ~ ( 2 x 2 ) s t r u c t u r e s of Pd, o u r c a l c u l a t i o n s show a r e s o - nance n e a r - 0 . 2 0 4 Ry which a g r e e s c l o s e l y w i t h t h e p h o t o e m i s s i o n r e - s u l t s a t low c o v e r a g e s . For a monolayer of Pd i n t h e C - s t r u c t u r e ( h e r e a f t e r t o be r e f e r r e d t o a s P d * ( l l O ) ) and i n t h e I C - s t r u c t u r e , o u r r e s u l t s a r e shown i n F i g . 1 .

F i g . 1 - ( a ) LDOS f o r t h e commensu- r a t e P d * ( l l O ) i n t e r f a c e s t r u c t u r e

( 0 = 1 ) . In t h i s s t r u c t u r e t h e n e a - r e s t n e i g h b o u r d i s t a n c e between Pd- atoms i s a b o u t 4% l a r g e r t h a n i n b u l k Pd. The s p a c i n g between t h e Pd and Nb l a y e r s i s c h o s e n t o be t h e same a s f o r N b ( l l 0 ) p l a n e s . ( b ) shows t h e LDOS f o r a Pd atom h a v i n g t h r e e Nb n e i g h b o u r s and

( c ) f o r a Pd atom c h e m i s o r b e d on a b r i d g e s i t e i n t h e c a s e o f one Pd(ll1) l a y e r incommensurate w i t h N b ( l l 0 ) . I n s e t o f ( c ) shows t h e s u p e r p o s i t i o n of t h e r e c i p r o c a l l a t t i c e s c o r r e s p o n - d i n g t o P d ( l l 1 ) and N b ( l l 0 ) . T h i s i s s i m i l a r t o t h e p a t t e r n o b s e r v e d i n L E E D / 4 / . More d i s c u s s i o n of i n t e r - f a c e s t r u c t u r e i s g i v e n i n / 7 / .

24 - Pd

20 -

16 - 12 -

8 ^- 4 -

O - 3 - 2 - 1 0 1 2 3 4

E(RY)

F o r P d * ( l l O ) t h e r e a r e two p r o m i n e n t p e a k s a t e n e r g i e s - 0.227 and -0.176 Ry which a g r e e w i t h t h e r e s u l t s of AIPED. F u r t h e r t h e Nb LDOS shows a d i s t i n c t r e s o n a n c e peak a t a b o u t -0.176 Ry and i t a g r e e s w i t h t h e A R P E D d a t a . However, i t i s c o n t r a r y t o t h e i n t e r p r e t a t i o n of AIPED where t h e peak a t - 0 . 2 2 7 Ry was d e s c r i b e d t o be due t o t h e Pd- Nb r e s o n a n c e . The Pd LDOS a t t h e F e r m i - e n e r g y ( E F ) i s v e r y s m a l l and i t a g a i n a g r e e s c o m p l e t e l y w i t h t h e A R P E D r e s u l t s . For IC s t r u c t u r e , c a l c u l a t i o n s were p e r f o r m e d f o r two d i f f e r e n t s i t e s ( i ) where Pd i s c h e m i s o r b e d o n a t h r e e f o l d c o o r d i n a t e d s i t e and ( i i ) where Pd i s c h e m i s o r b e d on a b r i d g e s i t e . In b o t h t h e c a s e s t h e r e s u l t s a r e v e r y s i m i l a r ( ~ i g . 1 ) i n d i c a t i n g t h a t t h e f e a t u r e s i n t h e LDOS a r i s e m a i n l y from t h e s t r u c t u r e of t h e o v e r l a y e r . T h i s c o n c l u s i o n i s a l s o s u p p o r t e d from o u r c a l c u l a t i o n s / 7 / on u n s u p p o r t e d Pd l a y e r s . I n t e r e s t i n g l y one of t h e p e a k s l i e s a t a b o u t t h e same e n e r g y a s f o r t h e C s t r u c t u r e w h e r e a s t h e o t h e r peak ( r e s o n a n c e ) i s s h i f t e d t o l o w e r b i n d i n g e n e r g y . Note, t h a t i n AIPED, e m i s s i o n n e a r - 0 . 2 2 7 Ry c o n t i n u e s beyond 9 = 1

t h e r e a r e two v e r y c l o s e l y l y i n g p e a k s . One i s a t t h e same e n e r g y a s f o r t h e C s t r u c t u r e and t h e o t h e r i s a t a somewhat l o w e r b i n d i n g e n e r - gy a s we o b t a i n e d . T h i s l e a d s u s t o c o n c l u d e t h a t t h i s e m i s s i o n c o r - r e s p o n d s t o t h e c o e x i s t e n c e of b o t h t h e P d * ( l l O ) and t h e P d ( l l 1 ) s t r u c t u r e s . The Pd LDOS a t E F i s s t i l l s m a l l b u t i t i s somewhat more t h a n i n t h e c a s e of P d X ( l l O ) and a l s o t h e r e a r e more d - h o l e s . T h i s i s r e l a t e d t o t h e s l i g h t i n c r e a s e i n t h e H-uptake / 7 / .

For two o v e r l a y e r s of Pd we c o n s i d e r e d t h r e e s t r u c t u r e s ( i ) where b o t h t h e l a y e r s a r e P d X ( l l O ) t y p e , ( i i ) where b o t h t h e l a y e r s a r e P d ( l l 1 ) t y p e a n d ( i i i ) where t h e t o p l a y e r i s P d ( l l 1 ) and t h e u n d e r - l a y e r i s P d * ( l l O ) . O b v i o u s l y , t h i s was done t o u n d e r s t a n d t h e growth mode and t h e s t r u c t u r a l t r a n s f o r m a t i o n . Note t h a t beyond 8 = 2 . 0 b o t h t h e AIPED and A R P E D show two p e a k s a t a b o u t -0.176 and -0.052 Ry.

One e x p e c t s t h a t t h e s e w i l l have most c o n t r i b u t i o n s f r o m t h e t o p - l a y e r b u t a l s o some c o n t r i b u t i o n from t h e u n d e r - l a y e r s . A l s o s i n c e i n A R P E D t h e r e was o n l y one peak up t o a m o n o l a y e r c o v e r a g e , one would e x p e c t t h a t t h e e m i s s i o n beyond 0 = 2 . 0 a r i s e s from o r b i t a l s o f t h e same s y m m e t r i e s which a l s o c o n t r i b u t e t o t h e e m i s s i o n a t -0.176 Ry a t low c o v e r a g e s . R e s u l t s of o u r c a l c u l a t i o n s a r e p r e s e n t e d i n F i g . 2 .

F i g . 2 -LDOS f o r two Pd l a y e r s on N b ( l l 0 ) i n

d i f f e r e n t g e o m e t r i e s . ' p a r t of t h e LDOS n o t

shown d o e s n o t show s i g n i f i c a n t c h a n g e s . The p a r t i a l d e n s i t i e s of s t a t e s a r e shown o n l y f o r Pd. y z and zy- o r b i t a l s a r e d e g e n e - r a t e w h e r e a s xy h a s v e r y s i m i l a r f e a t u r e s and i s t h e r e f o r e n o t shown. Axes were c h o s e n a l o n g t h e cube e d g e s and t h e s u r f a c e was c r e a t e d by c l e a v i n g t h e c u b e . The i n s e t shows t h e LDOS f o r a c l e a n P d f l l l ) s u r f a c e .

Had t h e r e been two P d * ( l l O ) l a y e r s , we would e x p e c t s t r o n g e m i s s i o n n e a r - 0 . 0 8 Ry and some e m i s s i o n n e a r -0.23 Ry. We t h u s d i s c a r d t h i s p o s s i b i l i t y . For two P d ( l l 1 ) l a y e r s , t h e LDOS l o o k s v e r y s i m i l a r a s o b s e r v e d . Note a l s o t h a t b o t h t h e p e a k s have a l m o s t e q u a l c o n t r i b u - t i o n from a l l t h e o r b i t a l s . In t h e c a s e o f one P d ( l l 1 ) and one Pd*(llO) l a y e r , t h e LDOS of t h e P d ( l l 1 ) l a y e r i s q u i t e s i m i l a r t o t h e c a s e o f

C5-452 JOURNAL DE PHYSIQUE

t w o Pd l a y e r s , b u t t h e LDOS o f t h e u n d e r l y i n g P d * ( l l O ) l a y e r d i f f e r s s i g n i f i c a n t l y . I t i s d i f f i c u l t t o d i s t i n g u i s h b e t w e e n t h e s e t w o i n t e r - f a c e g e o m e t r i e s w h i l e c o m p a r i n g w i t h t h e p h o t o e m i s s i o n r e s u l t s . How- e v e r , t h e c a l c u l a t i o n f o r o n e m o n o l a y e r g i v e s c l e a r e v i d e n c e o f s t r u c - t u r a l t r a n s f o r m a t i o n . The q u e s t i o n now a r i s e s how t h e s t r u c t u r a l t r a n s f o r m a t i o n s t a r t s . We s t u d i e d t h e c h a n g e s i n LDOS o f t h e u n d e r l y - i n g Nb l a y e r a s a f u n c t i o n o f c o v e r a g e . I n a l l c a s e s t h e r e i s a s i g - n i f i c a n t d e c r e a s e o f Nb s t a t e s n e a r t h e EF ( F i g . 3 ) w h i c h d o e s n o t c h a n g e much when t h e s e c o n d l a y e r i s d e p o s i t e d . H o w e v e r , t h e

F i g . 3 - D i f f e r e n c e o f t h e Nb LDOS a f t e r a n d b e f o r e i n t e r f a c e f o r - m a t i o n . O n l y t h e t o p Nb l a y e r i s t r e a t e d t o b e d i f f e r e n t i n t h e s e l f - c o n s i s t e n t p r o c e - d u r e t o c a l c u l a t e t h e i n t e r f a c e LDOS.

d e p l e t i o n o f o t h e r s t a t e s w h i c h w e r e p u l l e d t o w a r d s h i g h e r b i n d i n g e n e r g i e s i s s i g n i f i c a n t l y r e d u c e d . T h u s , we b e l i e v e t h a t t h e b i n d i n g e n e r g y o f u n d e r l y i n g Pd l a y e r w i t h Nb d e c r e a s e s when a s e c o n d l a y e r

i s d e p o s i t e d . B e y o n d 6

=

i n t e r a c t i o n b e t w e e n Pd a t o m s f a v o r s t h e i r own e q u i l i b r i u m d i s t a n c e a n d h e n c e a s t r u c t u r a l t r a n s f o r m a t i o n . T h i s p r o c e s s may a l s o b e a s s i s t e d b y t h e e n e r g y r e l e a s e d i n t h e p r o c e s s o f c h e m i s o r p t i o n o f Pd a t o m s a f t e r t h e f i r s t l a y e r i s c o m p l e t e d .

The c h a r g e t r a n s f e r a c r o s s t h e i n t e r f a c e i s q u i t e s m a l l a n d i t s e f f e c t on t h e w o r k f u n c t i o n h a s b e e n d i s c u s s e d a t l e n g t h e l s e w h e r e / 7 / .

l a r g e i n c r e a s e i n t h e H - u p t a k e . H o w e v e r , t o r e g a i n t h e d e t a i l e d f e a - t u r e s o f t h e LDOS, o n e w o u l d n e e d t h r e e o r more l a y e r s a s i t was a l s o c o n c l u d e d f r o m e x p e r i m e n t s . The Pd-Nb r e s o n a n c e s h i f t s t o l o w e r b i n - d i n g e n e r g i e s w i t h t h e c o v e r a g e i n a g r e e m e n t w i t h A R P E D . However, f o r t w o l a y e r s i t i s d i f f i c u l t t o d i s t i n g u i s h i t a s t h e s t a t e s a r e d i s - t r i b u t e d a l m o s t u n i f o r m l y . A l s o t h e c e n t e r o f g r a v i t y o f t h e Pd band s h i f t s t o l o w e r b i n d i n g e n e r g i e s w i t h i n c r e a s i n g 9. Such s h i f t s w i l l a l s o be r e f l e c t e d i n c o r e - l e v e l s a n d c a n be m e a s u r e d by X - r a y p h o t o - e l e c t r o n s p e c t r o s c o p y .

I n b r i e f o u r c a l c u l a t i o n s a r e i n e x c e l l e n t a g r e e m e n t w i t h t h e ARPED a n d AIPED r e s u l t s o f Pd on N b ( l l 0 ) i n t e r f a c e a n d p r o v i d e f o r t h e f i r s t t i m e t h e e l e c t r o n i c s t r u c t u r e c h a n g e s f o r a w i d e r a n g e o f c o v e r a g e s a n d i n c o m m e n s u r a t e i n t e r f a c e s t r u c t u r e s a n d h e l p t o u n d e r - s t a n d t h e s t r u c t u r a l t r a n s f o r m a t i o n s f r o m a m i c r o s c o p i c p o i n t o f v i e w . We h a v e a l s o shown t h a t t h e p h o t o e m i s s i o n m e a s u r e m e n t s c a n p r o v e h e l p f u l t o i d e n t i f y s t r u c t u r a l t r a n s f o r m a t i o n s i n o v e r l a y e r s .

/ I / SACHTLER J.W.A., BIBERIAN J . P . , a n d SOMORJAI G . A . , S u r f a c e S c i . 1 1 0 ( 1 9 8 1 ) 4 3 .

/ 2 / ~ G M A N N G . , P h y s . Rev. L e t t . 41 ( 1 9 7 8 ) 2 6 4 ; P h y s i c s t o d a y 3 2 ( 8 ) ( 1 9 7 9 ) 2 5 .

/ 3 / P I C K M . A . , DAVENPORT J.W., STRONGIN M . a n d DIENES G.T., P h y s . Rev. L e t t . 43 ( 1 9 7 9 ) 2 8 6 .

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/ 6 / W E N G S . a n d E L B A T A N O U N Y M . , P h y s . Rev. L e t t . 44 ( 1 9 8 0 ) 6 1 2 . / 7 / K U M A R V . a n d B E N N E M A N N , K . H . , P h y s . Rev. B 2 3 ( 1 9 8 3 ) i n p r e s s .