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THE NON-CORRELATION OF X-RAY PHOTOELECTRON AND X-RAY EMISSION
SPECTRA FOR TRANSITION METAL COMPOUNDS
P. Mcclusky, D. Urch
To cite this version:
P. Mcclusky, D. Urch. THE NON-CORRELATION OF X-RAY PHOTOELECTRON AND X-RAY
EMISSION SPECTRA FOR TRANSITION METAL COMPOUNDS. Journal de Physique Colloques,
1987, 48 (C9), pp.C9-1013-C9-1016. �10.1051/jphyscol:19879181�. �jpa-00227297�
JOURNAL DE PHYSIQUE
Colloque C9, supplement au n012, Tome 48, decembre 1987
THE NON-CORRELATION OF X-RAY PHOTOELECTRON AND X-RAY EMISSION SPECTRA FOR TRANSITION METAL COMPOUNDS
P. McCLUSKY and D. URCH
Chemistry Department, Queen Mary College, University
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on don, Mile End Road, GB-London El4NS,
Great-BritainRb-,itmB 1 . e s &.t?'k~: i n i . t i a % s et f i n a l 5 d e s t r a n s i t i a n s
el
r c . t r o n i q r - t e s q u i p r o v o q u e I 'r?!ni. ssi an d e a r a y o n r - X (ERXI son'lz s e n r s i b l e h I ' o b s e r - v a % i o n c l i r e c l : . e p a r I. a s p e c t r o s c : o p i e p h o t . ~ l e c t r o r i j . q ~ r e . D o n c i I. f ai.tt q i r e l e s& x p l i c : a t i i ? n s p o s t u i + e s p o u r 1s.; p h e n c ~ m & n e r 5 o b s e r v e s d a n s l a
s [ s e c t : r c ) s c n p i e p h o t o & l e c t r o n i q u e ( P E j marc:he a u s r - i d a n s l a d o n a i n e d e s r:ayoris-:< c-t v i c e - - v e r s a . E x a m i n a ' t i o n t f e s s p e c t r e s P E s e t ERZis d e s c:onlpor?&+.j. ci~.r f l ~ a r i q a r i & : ~ s Q t d ~ . riic:keI a d e m o n s t r b q u e l a c o r r e s p o n d e n c e ari.tlc:ilr!be n'e':st p a s to!..~.jol-tr-s t r - o c r - 4 e .
$ 2 3 t r d ~ t T h e i n i t i a l a n d f i n a l . s t a t e s o f a n e l e c t r o r 1 j . c t t - a n r j i t i o r i t h a t g i v e s r i s e . t o X - r a y e m i s s i o n c a r i b e o b s e r v e d d i r e c t l y b y
p h o t o e l e c t r - o n rjper:trnsc:opy. T h u s r a t i o n a l i ' ; s a ' t i o n a o f w p e c t r - a 1 f e a % u r e s p r o p a s e d f o r . p h n t c s e l . e e : t r o r i (F'E) s p e c t r o s c o p y z;hoc!Rd b e eqi.ta1 1. y v a l . i d f o r X - r a y e m i s s i o n l X E i s p e c t r o s c o p y , a n d v i c e v e r s a . R c o m p a r i s o n o f PE: a n d XE r e s u 1 . t ~ f o r .=,nfna m a n g a n e s e a n d n i c k e l c o r n p o i t n d s s h o w s {:hat . t h e a,-1.1:~ c:ipat.F_.d c : o r r - e l a t i o n i s rirr!t 4x1 w a y s f ocrnd.
1. Intraduction
T h e m a j . r . 1 f r a t l . . t r e s t h a t %I-6? o b s e r v e d i n b o t h X - r a y p h a t o e 1 . e c : t . r - o n (XF'Sj anid X--ray erni a a i . o r i (XES) s p e c t r - o s c z o p y c a n !.\st-tal. l v b e ra.t:sor:ai. i s a d
! r s i ng o n e e l e c : t . r o n nlode1.s a s d u e l-.o g ) h o l : a e r n i s s i o n f rorn s p e c i f i c : o r l . 3 i t . a l ~ % c3r- a?: d u e t o p e r m i t t e c f a i t ? c t r o n i c t r a n i i ~ i ' t i c 3 n s ( c l i p o l e
ssl c - t i o n rl..tl. e
--
di. a g r a m l i n e s ),
I - e s s p e ~ t i v r ? l y . C3ther p e a k s , a r e o b s e r v e c l i n bcst.ti tyl:3?+s o f s 1 : ~ e c t r - a , .iate:llitcz p e a k s , .for. w h i c h a v a r - i e t y cxf d1.f f w e n t ~ ? x p S . a n a t i . o n % h a v e b e e n a d v a n c e d . A s t h e i n i i r i a l . a n d+
i n a lsta.k.n!r; L n t h e X-r-ay e m i !s-;j.c~n prot::er;s (:an b e I. r i i j i v i ciual. l y ol?.;er-ved i n X--.r.ay 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 t h e t w o t y p e r i o f s p e c % r a a r e
i n t i m a t e l y r e l a t e d . T h u s t h e r a t i o n a l :i s a t i n r i i i i (71: s a t e l l. i.te p e a k < % o b 5 ; e r v e d i n o n e w i l . 1 h a v e i m p 1 i c : a t i o n s f o r t h e o - t h e r . A c o m p a r i ? = o r l o f s a t e l l i t e s i n t h e t w o . t y p e s of s p o c % r - a s t i o u 1 . d . t i ? s r - f o r - e p r o v i . d e a chec:tr o n t h e v a l i dl. t y o.f a pi-c?(rlr:!secl m e c t i a r i i s m f n r i-.hei r f n r r r ~ a . t i o n .
1 4 , .+of-. e?:arnpl.s, a ].ow e r i e r - g y :;atel.li:t.e i + s oot3:~erveCI i 1 . 1 XPS t h a t i r s s3i cj t o b e d u s tc, 'st7al::c?-.-!rp ' t h e n r e 1 a:.:at:i o n o f t h a t e:.:c:j. t e d s t a k e s h o u l d b e o b s t ? r v a i ~ l c ? j.n XE?. C!I-.
,
i f e;.:c:harig~= z s p X il: t i n q i s ~:~o:sl:!..tlatc<ci i n XFS, a s f o r Ilni-+ 2;s C 1 . 3 , t h e n c o r r e s ; p o r ' ~ d i n g s p l ~ . t t i n g s a h o c . t l d b e o b s e r v e d i n XE13. ' h i s n o ' k e h r . i e ? f l y s!.tr-veyr; a f e w a;i t!.tat t o n s i.rl.1er.c s!.tcrh c:olF.t-.er.pr~r~dericre m i g h t b e c?:.:pec:.\:ed.2. Experimental Procedure
'The XP s p e c t r a w e r e m e a s u r e d u5;ing a V E E8C:A 1 1 1 i l l k 1) spectrometer.
i.ts3ing AX li n: ( ! . 1 r i ~ n n r i a c l l r c 3 m a e i s e t J ) r a d i a t i o n fc-~r- e , : c i t a t . i o n . S a m p l e c i ( p a w d e r s f r o m cornmc?rci a1 sirpl?l. i e r a ) w e r e m o u n t e d e i t h e r b y bc.?:i. rig p r c + s s e d i n t o a f i n e qa1.d c o v e r e d m e s h or b y b e i n q s t r l c i t t o ? s e l % o t : a p e . A P h i l i p s PW 1410 X--.ray f l u o r s s c : e n c e s p ~ c t r o m ~ ! t e r w a s ! . ~ s e d f c s r the? XEE . i p e c t r a . E:.:ci t a t i o n w a s b y mean:; o f a 3kW s e a l e d X - r a y t i ~ / > e !SK. Cr- c3r-
Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19879181
C9-1014 JOURNAL
DE
PHYSIQUEMo anode) o r , f o r l o n g wave % - - r a y s , a CER open-.-wi.ndow Elt=nt-.-l.O
gas--dischar-ge ttilne. @n adcii.k.iont~l collimator- C21 was f i t t e d t o tzontr-01 ' h o r - i r o n t . a l clivergeric:e' and ttiu:; g i v e enhanced re.;nl~.ltiuri.
3. R e s u l t s and D i s c u s s i o n
>-a_? K p'
--
FI:-~~s_t_-,~.~_~~~~_T~~~an.;i~tI.~lrr~ Elements-
The K p,,,: peak o f manyf i r s t row t r a n s j . t i o n meta1.s ir; c h a r - a c t ~ e r i s a d b v l:he ur-eserice o f an a d d i t i o n a l irrw--en~+rgy feaZ:urr, K p'
.
The s e p a r a t i o n between t.tie two [peaks i s s i m i l a l - . .for- niany e?lemen%s, a h r ~ u t :I.'?: .- : l 8 e V , anif .the r - e l a t r i v e i n t . e r ~ s i . t y i::: p' : I::: @ can be rot.ighl y c o r r e i a t e d w i t h t.he nt.tmher o f t..tl-lpi3fr-e!j 3cl ei.ect:r'c?nas, a,;: leas!: for- t h e I.sr;~h'ter el.eme~-~i:c,, tFe 3, 141-1 4, Ti. 5 3 . '1"hi.s corrc.:l at.i.nn has .;i.tggested 'the e:.:planation t h a t .the(.. .;.p:li-k:!:ing . a+: +:he K p peak i s due t i 3 an exctiange effec:.t., t h e c u t l p l i n g o f t h e two possj.bl.e e,pin s t a t e s c2.F 3p" w i t h t h a t o f tl-te 3 d electr-on.;.
i f t h i s irs sn t h e n ~j!.a.ch a ' f i n a l !skate' effec!l 51-~o!.tld be c l e a r - l y seen i n t h e X F spectrc.tm o f t h e 3p l e v e l . '3 comparI.son o f t h e appt-.opriate spec~tr-a f o r Rn'" iMnF=) i s shown i n F i q . I .
4
i i\,,,
\. F i g u r e PIn k: @ -- 1. Manganese t:: @ ',
f 1 u u r i de\. i s o l i d l i n e )
*. -. /
./. .-. XPS f i l m 3p r e g i o n j
/ .. -./.'
F' (clot---dash I. i n e )
../
P h o t o n E n e r g y / e v
Good agreement I.n ener-gy i h ~ b ' i n o t i n t e r i s i % y i between t l i e X P peaks ik:i.nefiic enet-.gies) at. / 4 l h ~ ? V arid 14:54.eV w:i:th t::: p ' and t:: p i s apparent.
1-I-te c:o~npar'i?son o.F t h e C:' p .
-
i:.' s p e c t r a f o r paramagnetic Ni"'(I'Ji i O H ) , i and dian~agnetic: Ni""' fdimethylqlyo:.:ime comp1.exi shows, F i g . 2, 1:he preser1c:e c ~ f a d i s t i n c t K p' f e a t u r e a t 825Pi -- t3254. eV. B u t e:-:aminati,c)r.~ 0.6 t h e n i c k e l I-~ydr-oxide XF q~ectr-i.tm 4 a i . l ~ ,to r e v e a l any peak a t abok.~+:. 1.2 v o l t s l e q s i < j . n e t i c energy t h a n t h e main N i '!p peal.::.
(The l:ai 1 in g t h a t i s c31rrserved for- N i :3p may be d!.!e t o shake-up, - a - f f pr-ctc:e:sii;es s i n c e l c s w energy s a t e l I. I. t e peaks
-
r e s o l v e d w i t h i n c r e a s i n g c:laril:y - a r e ?seen s.t t h e same r e 1 a t i v e p o s i t i o n , abot.ht 6.5 ev lecis l::irtet:ic energy, f o r Sp, 3rj and 2 p peaks.) It: may be n o t e d t h a t a s i i n i l a r - lack: i : ~ f c o r r e ~ p o r i i ~ c e hetween X P and Xf: s p e c t r a f o r t h e K p . peak: has been sew-I f o r i r n n compounds. Why sho!.!ld t h e e f f ccirs o fexchange cot-tpling be more c l e a r l y and c o n s j . s t e r - i t l y seen i n X E t h a n i n :fP s p e c t r a ?
!b) - .. E:.:~tianc~-,_,";-el,~~$~L~~~,,g- . . .. A c l a s s i c : e:.:ample o f e:.:change s p l j . t t i r ' ~ g i n XFS i s tti3.t nf Mn"" .35 C l I f , F i g . :5. :3s* i s t h e f i n a l s t a t e i n t h e X-ray erni.s!sion proc:esaes i.. C anti I... ?-I ( 3 s a 21'; and so i f 9s' i s , indeed, s p l i t t h e n ti-11.5 s p l i t ' t i n g shoirlci be d i r e c t 1 y o b s e r v a b l e i n t h e s e X-ray : l i n e s , u n l e s s an exe8c.kl.y s:i.mi.I.ar- s p l i t t i n g i s observed f o r t h e i n i t i a l
,7 L P I , ~ ? ancl 2 ~ 3 , : ~ s t a t e s . The XP peaks t h a t c13rre~;jpond t o t h e s e s t a t e s
?:how rsoac-? d i s.l:or-iri on buh sit:', s p l i. . k t .i ng, no new peaks -6. 5 'J away. Hut 9 p l i t t i n g i. 5 r~c!t c?h~i??r-ved f o r +he blri L. P. peal:: as can be seen i n F i g . :!;. I.ic>w can 1.k h e % t ~ n t t h e r e arl*! peal.::^ i n t h e 3s X P spectrum w h i l s t
<:he I.. C XE peal.:: i s w i k h o u t an:, l.tne:.:pected featkares'?
F i g u r e 2.
N i K p
-
I( p 'XE s p e c t r a f o r Ni ( O H ) = ( s o l i d l i n e ) a n d n i c k e l d i m e t h y l - ,
g l y o e i , m e comple:.:
( d a s h e d 1 i n e ) T h e XP s p e c t r u m f o r N i
(OH)*
i n t h e N i 3 p r e g i o n i s a l s o s h o w ni d o t - d a s h 1 i n e )
F i g u r e 9.
M a n g a n e s e f 1 r t o r i d e : Mn L L (3s 4 2 p s , ~ ) XE s p e c t r u m ( s o l i d l i n e ) a n d XP ( M n 3s r e g i o n )
( d o t - d a s h 1 i n e ) a1 i g n e d u s i n g XP d a t a f o r
P h o t o n E n e r g y / e v Mn 2pJlz
-
k i n e t i cSF
575 560 e n e r g y 841 e V13% 7 395 1400 f 405
K ! n . t l c E n e r g y / e v
( c ) L cx XE a n d 2 p XP s p e c t r a <NJ?- T h e n i c k e l t a XE s p e c t r u m f r o m n i c k e l h y d r o x i d e , F i g . 4 , s h o w s c o m p l e x h i g h e n e r g y s t r u c t u r e t h a t i s a b s e n t f r o m t h a t o f t h e d i m e t h y l g l y o x i m e c o m p l e x . S e p a r a t e e x p e r i m e n t s h a v e s h o w n t h a t t h e L a : 1.. p a n d L L : 1- t-j i n t e n s i t y r a t i o s a r e t h e s a m e w h i c h i n d i c a t e s t h a t t h e L a, L p s p e c t r a a r e n o t a f f e c t e d b y s e l f - a b s o r p t i o n e f f e c 1 . t ~ . T h u s , a 1 t h o u g h t h e n e a r t . h e LI r a b s o r p t i o n e d g e , t h e h i g h - e n e r g y s t r u c t u r e i s p r o b a b l y n o t d u e t o
s e l , f - - a b s o r p t i o n .
T h e i n i t i a l s t a t e o f t h e L, a t r a n s i t i o n (Zps, "PxNa) s h o w s a cle* a n d r e l a t i v e l y i n t e n s e ' s h a k e - u p ' p e a k i n t h e XP s p e c t r u m a t a b o u t 7 v o l t s l e s s i n k i n e t i c e n e r g y t h a n t h e m a i n p e a k w h i l s t o n l y a s i n g l e p e a k is o b s e r v e d i n t h e v a l e n c e b a n d c o r r e s p o n d i n g t o 3d7. I t i s t h e r f o r e i n t e r e s t i n g t o o b s e r v e , when t h e XP a n d XE s p e c t r a a r e a l i g n e d a s i n F i g . 4 , t h a t t h e ' s h a k e - u p ' s a t e l l i t e c o r r e s p o n d s t o o n e o f t h e weak p e a k s i n t . h e h i g h e n e r g y s t r u c t u r e i n t h e L cx s p e c t r u m . D o e s t h i s p e a k r e p r e s e n t t h e r e l a x a t i o n o f a ' s h a k e - - 1 . p ' s t a t e ? By c o n t r a s t t h e
d i e m t h y l g l y n x i m e c a m p l e x s h o w s n o ' s h a k e - u p ' p e a k s i n XPS a n d n o L a h i g h e n e r g y s t r u c t u r e i s s e e n e i t h e r .
JOURNAL
DE
PHYSIQUEF i g u r e 4 .
N i L u p e a k s f o r n i c k e l h y d r o x i d e
( s o l i d l i n e ) a n d n i c k e l d i m e t h y l -
g l y o x i m e c o m p l e x ( d a s h e d l i n e ) c o m p a r e d w i t h t h e XP s p e c t r u m f o r
N i 2p5,= r e g i o n f o r n i c k e l h y d r o x i d e ( d o t - d a s h l i n e )
845
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P h o t o n ' E n a r g y / a v-wGi
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4. Concluri ons
T h e i n t e r - r e l a t i o n o f XE a n d XP s p e c t r a e n a b l e m e c h a n i s m s p r o p o s e d t o r a t i o n a l i s e t h e o c c u r a n c e o f s a t e l l i t e p e a k s i n o n e t y p e o f s p e c t r u m t o b e c r i t i c a l l y t e s t e d . N e i t h e r e l e c t r o n e x c h a n g e n o r s h a k e - u p
a p p e a r s t o g i v e e x p l a n a t i o n s t h a t c a n b e a p p l i e d c a n s i s t e n t l y t a b o t h t y p e s o f s p e c t r a , w h i c h is c u r i o u s .
Acknowledgements
T h e a u t h o r s w i s h t o t h a n k B r i t i s h G a s a n d t h e SERC who h a v e , t h r o u g h a c o - f u n d i n g s c h e m e , s u p p o r t e d a R e s e a r c h A s s i s t a n t s h i p f o r P. McC. T h e y are a l s o g r a t e f u l t o t h e R o y a l S o c i e t y , t h e C e n t r a l R e s e a r c h F u n d o f L o n d o n U n i v e r s i t y a n d t h e SERC f a r f i n a n c i a l h e l p i n t h e p u r c h a s e o f e q u i p m e n t
.
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