al,ge cation ordering in baal 2 ge 2 o 8 -feldspar: monodomain ordering kinetics

10
ORIGINAL PAPER T. Malcherek H. Kroll E.K.H. Salje Al,Ge cation ordering in BaAl 2 Ge 2 O 8 -feldspar: monodomain ordering kinetics Received: 21 April 1999 / Revised, accepted: 19 July 1999 Abstract The kinetics of monodomain order-disorder processes in monoclinic (I2/c) BaAl 2 Ge 2 O 8 -feldspar have been investigated by X-ray powder diraction, Hard Mode IR Spectroscopy, and TEM dark®eld imaging on quenched samples. Compared to the be- haviour predicted by the TDGL approximation ordering kinetics observed at low temperatures slow down sig- ni®cantly when equilibrium is approached. Such a delay is not observed in disordering experiments starting from essentially ordered cation distributions. The deviation from TDGL behaviour is interpreted in terms of partial order parameter conservation in a non-uniformly or- dered phase. Modi®cations to the uniform TDGL rate equation are tested against the available data. An acti- vation energy of 352 28 kJ/mol is obtained for Al,Ge ordering. The mixing coecient n 2 c =n 2 , which describes the degree of order parameter conservation, is obtained as a function of temperature. While this coecient vanishes in the vicinity of the transformation tempera- ture T tr , it saturates towards a level of n 2 c =n 2 0:4 for T ! 0. n 2 c =n 2 determines the kinetic stability of ordered clusters quenched from T T tr . Key words Kinetics Feldspar Fluctuations BaAl 2 Ge 2 O 8 Partial conservation Introduction The analytical description of cation ordering kinetics by means of time dependent Ginzburg-Landau (TDGL) approximations has attracted substantial interest in the mineralogical literature of recent years. This is especially true for systems in which the ordered phase does not become unstable at high temperatures, i.e. ordering is entirely driven by the chemical potential dierence between two or more lattice sites (Salje and Kroll 1991; Kroll et al. 1994; Redfern et al. 1997; Harrison and Putnis 1997). Understanding the kinetics of such non- convergent ordering processes is important for their geological application in geospeedometers and geother- mometers. On the other hand, the experimental study of phase transitions in the non-equilibrium state by means of the TDGL approach has received somewhat less attention in mineralogy so far (Carpenter et al. 1990; Carpenter 1991b; Salje et al. 1993). To some extent this is due to the lack of experimentally accessible systems in which order-disorder phase transitions occur with well known equilibrium behaviour and large ordering rates even at low temperatures T T c . In a previous paper (Malcherek et al. 1999, from now on referred to as paper I) we have reported on the equilibrium behaviour of BaAl 2 Ge 2 O 8 -feldspar (BAGF), which shows a phase transition at 1690 K due to Al,Ge cation ordering. The mean ®eld potential of this phase transition has been derived, and it was con- cluded from the mean ®eld approximation (MFA) and from the qualitative similarity to a compressible Ising model that the phase transition is of ®rst order. The MFA describes the phase transition in terms of the convergent order parameter Q od , and a coupled non- convergent order parameter Q t . In the present paper we will explore the kinetics of the phase transition, focusing on the dominant convergent order parameter Q od . The ®rst section of this paper brie¯y introduces to phenomenological theories commonly used in the anal- ysis of phase transition kinetics and to the concept of partially conserved order parameter kinetics. Then the experimental kinetic observations are presented and interpreted in the framework of the phenomenological model. We will not attempt to cover the non-equilibrium theory of phase transitions in any appropriate detail, but Phys Chem Minerals (2000) 27: 203±212 Ó Springer-Verlag 2000 T. Malcherek (&) CNR-CSCC, c/o Dipartimento di Scienze della Terra, Via Ferrata 1, 27100 Pavia, Italy e-mail: [email protected] H. Kroll Institut fuÈr Mineralogie, WestfaÈlische Wilhelms-UniversitaÈt, Corrensstr. 24, D-48149 MuÈnster, Germany E.K.H. Salje Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, UK

Upload: cambridge

Post on 01-Dec-2023

0 views

Category:

Documents


0 download

TRANSCRIPT

!"#$#%&' (&()"

!" #$%&'()(* ! +" ,)-%% ! .","+" /$%0(

!"#$% &'()*+ *,-%,)+. )+ /'!"0$%01234%"-56',7 8*+*-*8')+*,-%,)+. 9)+%()&5

"*+*,-*./ 01 &23,4 1555 6"*-,7*.8 9++*2:*./ 15 ;<4= 1555

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

08 M?,+? .*7+3,J*7:?* .*K3** BC B3.*3 2939D*:*3 +BA7*3-9:,BA8 ,7 BJ:9,A*.97 9 C<A+:,BA BC :*D2*39:<3*T [?,4* :?,7 +B*Z+,*A:-9A,7?*7 ,A :?* -,+,A,:= BC :?* :39A7CB3D9:,BA :*D2*39E:<3* !:38 ,: 79:<39:*7 :BM93.7 9 4*-*4 BC !0+!!

0 # \"] CB3! $ \T !0+!!

0 .*:*3D,A*7 :?* @,A*:,+ 7:9J,4,:= BC B3.*3*.+4<7:*37 S<*A+?*. C3BD ! # !:3T

,(5 6-)73 ^,A*:,+7 ! _*4.7293 ! _4<+:<9:,BA7 !H9&40$*0!I ! (93:,94 +BA7*3-9:,BA

:+(,*-;&()*+

>?* 9A94=:,+94 .*7+3,2:,BA BC +9:,BA B3.*3,AK @,A*:,+7 J=D*9A7 BC :,D* .*2*A.*A: $,A`J<3KE'9A.9< F>V$'G

9223BW,D9:,BA7 ?97 9::39+:*. 7<J7:9A:,94 ,A:*3*7: ,A :?*D,A*394BK,+94 4,:*39:<3* BC 3*+*A: =*937T >?,7 ,7 *72*+,944=:3<* CB3 7=7:*D7 ,A M?,+? :?* B3.*3*. 2?97* .B*7 AB:J*+BD* <A7:9J4* 9: ?,K? :*D2*39:<3*78 ,T*T B3.*3,AK ,7*A:,3*4= .3,-*A J= :?* +?*D,+94 2B:*A:,94 .,N*3*A+*J*:M**A :MB B3 DB3* 49::,+* 7,:*7 FQ94a* 9A. ^3B44 1551b^3B44 *: 94T 155]b "*.C*3A *: 94T 155cb O933,7BA 9A.(<:A,7 155cGT dA.*37:9A.,AK :?* @,A*:,+7 BC 7<+? "#"$%#"&'()'"* B3.*3,AK 23B+*77*7 ,7 ,D2B3:9A: CB3 :?*,3K*B4BK,+94 9224,+9:,BA ,A K*B72**.BD*:*37 9A. K*B:?*3EDBD*:*37T !A :?* B:?*3 ?9A.8 :?* *W2*3,D*A:94 7:<.= BC2?97* :39A7,:,BA7 ,A :?* ABAE*S<,4,J3,<D 7:9:* J= D*9A7BC :?* >V$' 9223B9+? ?97 3*+*,-*. 7BD*M?9: 4*779::*A:,BA ,A D,A*394BK= 7B C93 FU932*A:*3 *: 94T 155\bU932*A:*3 1551Jb Q94a* *: 94T 155XGT >B 7BD* *W:*A: :?,7,7 .<* :B :?* 49+@ BC *W2*3,D*A:944= 9++*77,J4* 7=7:*D7 ,AM?,+? B3.*3E.,7B3.*3 2?97* :39A7,:,BA7 B++<3 M,:? M*44@ABMA *S<,4,J3,<D J*?9-,B<3 9A. 493K* B3.*3,AK 39:*7*-*A 9: 4BM :*D2*39:<3*7 ! % !+T

#A 9 23*-,B<7 292*3 FP94+?*3*@ *: 94T 15558 C3BD ABMBA 3*C*33*. :B 97 292*3 #G M* ?9-* 3*2B3:*. BA :?**S<,4,J3,<D J*?9-,B<3 BC H9&40$*0!IEC*4.7293FH&$_G8 M?,+? 7?BM7 9 2?97* :39A7,:,BA 9: 1e5\ ^ .<*:B &48$* +9:,BA B3.*3,AKT >?* D*9A R*4. 2B:*A:,94 BC:?,7 2?97* :39A7,:,BA ?97 J**A .*3,-*.8 9A. ,: M97 +BAE+4<.*. C3BD :?* D*9A R*4. 9223BW,D9:,BA FP_&G 9A.C3BD :?* S<94,:9:,-* 7,D,493,:= :B 9 +BD23*77,J4* #7,AKDB.*4 :?9: :?* 2?97* :39A7,:,BA ,7 BC R37: B3.*3T >?*P_& .*7+3,J*7 :?* 2?97* :39A7,:,BA ,A :*3D7 BC :?*+BA-*3K*A: B3.*3 2939D*:*3 "B.8 9A. 9 +B<24*. ABAE+BA-*3K*A: B3.*3 2939D*:*3 ":T #A :?* 23*7*A: 292*3 M*M,44 *W24B3* :?* @,A*:,+7 BC :?* 2?97* :39A7,:,BA8 CB+<7,AKBA :?* .BD,A9A: +BA-*3K*A: B3.*3 2939D*:*3 "B.T

>?* R37: 7*+:,BA BC :?,7 292*3 J3,*f= ,A:3B.<+*7 :B2?*ABD*AB4BK,+94 :?*B3,*7 +BDDBA4= <7*. ,A :?* 9A94E=7,7 BC 2?97* :39A7,:,BA @,A*:,+7 9A. :B :?* +BA+*2: BC293:,944= +BA7*3-*. B3.*3 2939D*:*3 @,A*:,+7T >?*A :?**W2*3,D*A:94 @,A*:,+ BJ7*3-9:,BA7 93* 23*7*A:*. 9A.,A:*323*:*. ,A :?* C39D*MB3@ BC :?* 2?*ABD*AB4BK,+94DB.*4T [* M,44 AB: 9::*D2: :B +B-*3 :?* ABAE*S<,4,J3,<D:?*B3= BC 2?97* :39A7,:,BA7 ,A 9A= 9223B23,9:* .*:9,48 J<:

(?=7 U?*D P,A*3947 F0\\\G 0c/ 0\Xg010 ! Q23,AK*3Eh*349K 0\\\

>T P94+?*3*@ F!GU%"EUQUU8 +6B V,293:,D*A:B ., Q+,*A`* .*449 >*3398h,9 _*339:9 18 0c1\\ (9-,98 #:94=*ED9,4/ :?BD97iD,A2T*7+T+9DT9+T<@

OT ^3B44#A7:,:<: C<j 3 P,A*394BK,*8 [*7:C9j 4,7+?* [,4?*4D7EdA,-*37,:9j :8UB33*A77:3T 0]8 VE]I1]5 P<j A7:*38 $*3D9A=

)T^TOT Q94a*V*293:D*A: BC )93:? Q+,*A+*78 dA,-*37,:= BC U9DJ3,.K*8VBMA,AK Q:3**:8 U9DJ3,.K* UH0 X)k8 d^

3*C*3 :B 7*-*394 3*-,*M 93:,+4*7 9A. 3*C*3*A+*7 +,:*.:?*3*,A FQ94a* 15IIb '9AK*3 1550GT

<=%*,%()&'" &*+5)-%,'()*+5

#C 9 7<J7:,:<:,BA944= .,7B3.*3*. +3=7:944,A* 2?97*8 :?*+,(,+-,.'8 ,7 S<*A+?*. ,A:B :?* 7:9J,4,:= R*4. BC :?* B3E.*3*. 2?97*8 ,A:*3.,N<7,BA BC :?* B3.*3,AK +9:,BA 72*+,*7K39.<944= *7:9J4,7?*7 :?* 7:9J4* B3.*3*. 2?97*T #A :?*+97* BC :MB +9:,BA 72*+,*7 B3.*3,AK BA:B :MB 7*:7 BC7<J49::,+* 7,:*78 :?,7 ,A-B4-*7 :?* CB3D9:,BA BC :MB :=2*7BC .BD9,A7 M,:? B3.*3 2939D*:*3 BC B22B7,:* 7,KA8 ,T*T:?* B3.*3 2939D*:*3 ,7 :MBCB4. .*K*A*39:*T >?<7 :?**934= 7:9K* @,A*:,+7 93* +BA:3B44*. J= B3.*3,AK M,:?,A :?*.BD9,A7 9A. 7,D<4:9A*B<7 7<3C9+* D,A,D,`9:,BA BC:?* .BD9,A7T V<3,AK :?* 49:* 7:9K*7 BC :?,7 23B+*778 9C:*3:?* .BD9,A7 ?9-* 3*9+?*. :?*,3 ,A:*3A94 *S<,4,J3,<D.*K3** BC B3.*38 :?* 7<3C9+* D,A,D,`9:,BA 23*-9,47T >?**A7<,AK +B937*A,AK BC :?* ,"*/+-,.' 0#1,/". F&(V7G +9AK*A*3944= J* .*7+3,J*. J= 9 2BM*3 49M J*?9-,B<3&#' ( $%8 M?*3* &#' ,7 :?* 9-*39K* .BD9,A 7,`*8 $ ,7 :?*:,D* 9A. % ,7 9 +BA7:9A: *W2BA*A: FH39= 155]GT _B3+9:,BA B3.*3,AK8 :?* B3.*3 2939D*:*3 ,7 ABAE+BA7*3-*.89A. :?<7 % ) 1!0 ,7 K*A*3944= BJ7*3-*. CB3 :?* .BD9,A+B937*A,AK 23B+*77 FU932*A:*3 15519b '9AK*3 1550GT

#A:39.BD9,A B3.*3,AK ,7 .3,-*A J= D,A,D,`9:,BA BC:?* B3.*3,AK $,JJ7 C3** *A*3K=8 M?,+? ,7 9 C<A+:,BA BC:?* B3.*3 2939D*:*3 " F!(GT >?* 39:* BC :?* !( +?9AK*+9A J* 9223BW,D9:*. <7,AK :?* >V$' 9223BW,D9:,BA

#"#$

) *!#&#"

! "" +1,

& ,7 :?* C3** *A*3K= .,N*3*A+* .3,-,AK :?* 2?97* :39A7,E:,BA8 :?<7 ,: ,7 9A *S<,4,J3,<D 23B2*3:=T

#A B3.*3 :B 7*2939:* *W2*3,D*A:944= :?* /"*(,0#1,/"B3.*3,AK C3BD :?* 23B+*77*7 ,A-B4-,AK :?* .BD9,A M94478,T*T :?* ,"*/+-,.' 0#1,/" 2#3"0,(/'. F456.G8 ,: ,7 A*+*7E793= :B *7:9J4,7? :?* D9+3B7+B2,+ 7=DD*:3= BC :?* 4BM:*D2*39:<3* 2?97* J= 9AA*94,AK :?* 7=7:*D 9: :*D2*39E:<3*7 a<7: J*4BM :?* +3,:,+94 :*D2*39:<3* !+T #A :?,7:*D2*39:<3* 3*K,D* :?* &(V7 +B937*A 392,.4=8 3*7<4:,AK,A :?* CB3D9:,BA BC -*3= 493K* .BD9,A7 B-*3 3*49:,-*4=7?B3: :,D* ,A:*3-947T )77*A:,944= :?* 7=7:*D +9A J* .*E7+3,J*. 97 BA* 7,AK4* .BD9,A CB44BM,AK :?,7 23*2939:,BATk<*A+?,AK ,: :B 4BM*3 :*D2*39:<3*7 D9@*7 :?* DBABE.BD9,A B3.*3,AK @,A*:,+7 9++*77,J4* :B BJ7*3-9:,BAT &4E:*3A9:,-*4=8 :?* D9:*3,94 ,7 9AA*94*. :B 9 C<44= B3.*3*.7:9:* 9: 4BM :*D2*39:<3*7T V<3,AK 7<J7*S<*A: 392,.?*9:,AK :B ! $ !+ :?* +B33*72BA.,AK .,7B3.*3,AK @,A*:,+7+9A J* BJ7*3-*.T

>?* @,A*:,+ 23*C9+:B3 ! ,A )ST 1 +9A :9@* BA -93,B<7CB3D78 .*2*A.,AK BA :?* 23B2*3:,*7 BC :?* B3.*3,AK23B+*77T #C :?* !( ,7 <A,CB3D 9A. ABAE+BA7*3-*.8 M*?9-* ! ) "!+'! ,8 M?*3* " ) #*1 ,7 9 39:* +BA7:9A: 9A. ',7 :?* <A,-*3794 K97 +BA7:9A:T #A :?* B:?*3 *W:3*D*8 " ,7 9+BA7*3-*. B3.*3 2939D*:*38 ,T*T ,: -93,*7 BA 9 4B+94 B3D*7B7+B2,+ 4*AK:? 7+94*8 M,:? +BA7:9A: D9+3B7+B2,+9-*39K*T Q2,AB.94 .*+BD2B7,:,BA8 M,:? :?* +BA+*A:39E

:,BA (B 97 :?* +BA7*3-*. !( 23B-,.*7 9A *W9D24* CB37<+? 9 +97*T !A4= :?* 4B+94 +BA+*A:39:,BA -93,*7 97 9C<A+:,BA BC :,D*8 ,T*T (+)% $, ) (B - $+$,T >?* >V$' 92E23BW,D9:,BA ,7 :?*A 3*249+*. J= :?* U9?AEO,44,93.*S<9:,BA FUO)G FH,A.*3 1551b '9AK*3 1550G 9A. :?*23*C9+:B3 ,A )ST 1 J*+BD*7 ! ) "!+'! ,.0T " 9A. & 93*C<A+:,BA7 BC 729+* 9A. :,D*8 ,T*T "+)% $, 9A. &+"% )% $,3*72*+:,-*4=T

>?* +B937* K39,A*. C3** *A*3K=

#A B3.*3 :B .*94 M,:? !( f<+:<9:,BA7 M,:?,A :?* 7+B2* BC2?*ABD*AB4BK,+94 DB.*478 :?* C3** *A*3K= C<A+:,BA ,A)ST 1 ,7 .*RA*. J= :?* C<A+:,BA94

&' )#

)+), 10 *+."+),,0 - +'+"+),, * ,"+),$ %

+0,

+'+"+),, / 10 -"

0+), - 1] ."

]+), - ! ! ! +X,

>?* +B*Z+,*A:7 BC :?* 7*3,*7 *W29A7,BA +'+"+),, 93*:*D2*39:<3* .*2*A.*A:8 M,:? :?* 4*9.,AK :*3D - $ \J*4BM !+ 9A. - & \ 9JB-* !+ F+CT 292*3 #GT &A= ABAE`*3BR*4. :*3D ,"+), M,44 C9-B<3 9A B3.*3*. +BARK<39:,BA9A. M,44 :?<7 7<223*77 :?* 2?97* :39A7,:,BA8 :?*3*J=3*A.*3,AK :?* B3.*3 2939D*:*3 ABAE+BA-*3K*A:T

>?* K39.,*A: *A*3K= +B*Z+,*A: * ,7 23B2B3:,BA94 :B:?* 7S<93* BC :?* ,A:*39+:,BA 39AK*8 ?*A+* 7:**2 K39.,*A:77?B<4. BA4= J* *W2*+:*. CB3 7?B3: 39AK,AK ,A:*39+:,BA7J*:M**A :?* B3.*3,AK 293:,+4*7T

>?* 729:,94 -93,9:,BA "+), J*+BD*7 D9:?*D9:,+944=4*77 +<DJ*37BD* ,C ,: ,7 :3*9:*. ,A :*3D7 BC _B<3,*3+BD2BA*A:78 "*8 CB44BM,AK :?* :39A7CB3D9:,BA

"+), )&

/

"*01*) " +],

&77<D,AK :?9: :?* !( f<+:<9:,BA7 93* 72?*3,+94 9A.39A.BD4= .,7:3,J<:*.8 ,T*T / ) 0*08 9A. :?9: :?* DB.*7 "/93* .*+B<24*.8 )ST 0 +9A J* M3,::*A

"$'+/, ) 10 +2- */0,"0

/ - 1]3"

]/ * !45+ +"/, * ,"/ "

+Y,&7 ,A 292*3 #8 :?* D*9A R*4. *A:3B2= 45+ ,7 7*2939:*.

B<: 9A. :?* *A*3K= *W29A7,BA ,7 :3<A+9:*. 9: :?* CB<3:?B3.*3 :*3DT

>?* f<+:<9:,BA7 :?9: M* 7?944 .*94 M,:? 93* 74BM4=-93=,AK8 493K* 7+94* *-*A:7 +BD293*. :B :?* 2?BABAC3*S<*A+,*7 9A. :B :?* ,A:*39:BD,+ .,7:9A+*7 BC :?*+3=7:94 7:3<+:<3*T !A4= ,A :?,7 +97* +9A :?* 3*4*-9A: $,JJ7C3** *A*3K= J* *W23*77*. 97 9 C<A+:,BA BC 9 +BA:,A<B<7!( "+),T >?* 3*7<4:,AK C3** *A*3K= ,7 BC:*A .*7+3,J*. 97%#,(.' )(,/"'0 FH,A.*3 1551b '9AK*3 1550G M?,+? ,D24,*79A *N*+:,-* +<:BN -94<* CB3 +BD2BA*A:7 "/ +BA:3,J<:,AK:B "+/,T >?,7 +<:BN -94<*8 /6 ) %!68 ?97 :B J* +?B7*A7<+? :?9: 6 ,7 M*44 9JB-* :?* A*93*7: A*,K?JB<3 .,7:9A+*:?9: 7*2939:*7 B3.*3,AK 9:BD7 9A. 9: :?* 79D* :,D*7D944*3 :?9A :?* +B33*49:,BA 4*AK:? ! F'9AK*3 1550GT >?*+B33*49:,BA 4*AK:? A9:<3944= 4,D,:7 :?* 7,`* BC :?* 2B77,J4*

0\]

f<+:<9:,BA7T _4<+:<9:,BA7 M,:? 9 4*AK:? 7+94* 7<J7:9AE:,944= 493K*3 :?9A ! MB<4. CB3D :?* 7:9J4* A<+4*<7 BC 92?97*8 ,T*T 9A &(V ,A :?* 23*7*A: +BA:*W:T

&7 .*3,-*. J= P939,7 9A. Q94a* F1551G8 :?* +BD2*:,E:,BA J*:M**A .,N*3*A: .3,-,AK CB3+*7 93,7,AK C3BD .,CEC*3,AK 4B+94 -94<*7 BC "+),8 94:*37 :?* 23*C9+:B3 !83*7<4:,AK ,A :?* 39:* *S<9:,BA

#"#$

+), ) *+#'! ,*1 1* !0+!0

7,A? !.!.

! "#&#"

+), +e,

M?*3* !+ ,7 :?* %#".'(&,*/#" 7'")*-T #A _B<3,*3 +BB3.,EA9:*7 )ST e 7,D24,R*7 :B

#"/

#$) *+#'! ,*1 1* !0+

!07,A !/!/

! "#&#"

+/, " +c,

>?* .*K3** BC !( +BA7*3-9:,BA *A:*37 -,9 :?* S<B:,*A:!0+!!

08 :?<7 .*RA,AK 9 293:,94 +BA7*3-9:,BA BC " 9A. 9A*N*+:,-* ,A:*32B49:,BA J*:M**A :?* :MB 3*K,D*7 BC +BAE7*3-*. 9A. ABAE+BA7*3-*. B3.*3,AKT #C :?* !( ,7 +BAE7*3-*.8 ,T*T !0+!!

0 ) 18 :?* UO) ,7 3*+B-*3*.T "*-*37*4=8,C !0+!!

0 ) \8 :?* K39.,*A: B2*39:B3 -9A,7?*7 9A. :?*23*C9+:B3 ! ) "!'! ,7 ,.*A:,+94 :B :?9: BC :?* >V$'9223BW,D9:,BAT

>MB 4*AK:? 7+94*7 *A:*3 )ST e 9A. ,:7 _B<3,*3 729+**S<,-94*A:8 )ST c8 -,9 :?* 39:,B !0+!!

0/ :?* %#".'(&,*/#"7'")*-8 !+8 9A. :?* %#(('7,*/#" 7'")*-8 !T #A B3.*3 :B ,4E4<7:39:* :?,7 +BA+*2:8 BA* D,K?: :?,A@ BC :?* 29392?97*BC :?* #7,AK 9A:,C*33BD9KA*: 97 9A *W9D24* BC 9 .,7B3E.*3*. 7=7:*D8 &"' ) \8 M,:? 9 +BA7*3-*. !(/ AB D9::*3?BM D<+? 9 f<+:<9:,BA &"+7, .*-,9:*7 C3BD :?* D*9A8BA 9-*39K* ,: ,7 +BD2*A79:*. J= f<+:<9:,BA7*&"+7 - !+,T &7 :?* +B33*49:,BA 4*AK:? +B33*72BA.7 :B:?* .,7:9A+* J*:M**A :?* :MB f<+:<9:,BA78 B3 :?* M,.:?BC :?*,3 +BDDBA ,A:*3C9+*8 ,: CB44BM7 :?9: !0+!!

0 # 1T&++B3.,AK :B )ST c8 B3.*3,AK 4*9.,AK :B &"' & \ 3*S<,3*7,ARA,:* :,D* ,A :?* D9+3B7+B2,+ 4,D,:8 M?*3* / ) \ 9A.7,A+!/,!+!/, $ 1 7B :?9: ! $ \1T &7 :?* B3.*3*. 2?97*J*+BD*7 7:9J4* 9: ! $ !+ 9A. :?*3*CB3* K3BM7 :BM93.7,ARA,:* 7,`*8 !+ C9447 :B ,A:*39:BD,+ .,7:9A+*7T >?<787:3,+:4= 72*9@,AK !+ J*+BD*7 ,33*4*-9A: ,A :?* 2?*ABD*EAB4BK,+94 DB.*4 BC 9 7=7:*D M,:? ABAE+BA7*3-*. !( 9A.,: +B<4. J* 3*249+*. J= 9 +BA7:9A: *W23*77,BAT OBM*-*38! .,-*3K*7 9: 9 +BA:,A<B<7 2?97* :39A7,:,BA8 :?<7 3*AE.*3,AK !0+!!

0 ) \ ,A ,:7 -,+,A,:=T _3BD :?,7 7,D24* 2B,A: BC-,*M8 M* MB<4. *W2*+: :?* !( @,A*:,+7 :B CB44BM +BAE-*A:,BA94 >V$' J*?9-,B<38 97 *DJB.,*. J= )ST 1 BA4=9: :*D2*39:<3*7 +4B7* :B !+8 M?*3*97 9: 4BM*3 :*D2*39E:<3*7 B3.*3,AK ,7 .*49=*. 9++B3.,AK :B )ST cT >?* 493K*7:.*49= B++<37 ,A :?* D9+3B7+B2,+ 4,D,:8 / ) \8 M?*3*! ) +1* !0+!!

0,!+'! #,T [?,4* )ST e 23*.,+:7 74BM*3 B3E.*3,AK @,A*:,+7 :?9A )ST 18 :?* B3.*3,AK 39:* CB3 / ) \ ,723B2B3:,BA94 :B :?* 79D* @,A*:,+ .3,-,AK CB3+* ,A JB:?*S<9:,BA7T

>?* J949A+* J*:M**A !( fBM 9A. ABAE+BA7*3-*.B3.*3,AK ?97 :B J3*9@ .BMA *-*A:<944= ,A 9A= 7<J7:,:<E

:,BA94 B3.*3E.,7B3.*3 23B+*778 J*+9<7* :?* f<+:<9:,BA9-*39K* ,7 +BA7:39,A*. -,9 :?* 3*49:,BA&1&"+),20' ( "+1* ",T O*A+*8 ,C :?* C<44= B3.*3*. 7:9:*8" ) 18 ,7 9223B9+?*. <A.*3 ABAE*S<,4,J3,<D +BA.,:,BA78:?* 2B77,J4* 7?B3: 39AK* B3.*3 ,7 4,D,:*.T >?*3*CB3* :?*J949A+* J*:M**A :?* ,A+3*97* BC "+), 9A. !( fBM C3BD4*77*3 B3.*3*. :BM93.7 DB3* B3.*3*. 4B+94 93*978 M?,+?,7 ,A?*3*A: ,A )ST e8 ,7 J3B@*AT >?* 729:,94 K3BM:? BC :?*B3.*3*. +4<7:*37 .BD,A9:*7 <A.*3 :?*7* +BA.,:,BA7F_,KT 1GT

>MB 9223BW,D9:,BA7 ?9-* J**A 23B2B7*. ,A B3.*3 :B23*.,+: :?* :,D* *-B4<:,BA BC :?* D9+3B7+B2,+ !( <A.*37<+? +,3+<D7:9A+*7 FP94+?*3*@ *: 94T 155cGT HB:? 93*J97*. BA :?* 977<D2:,BA :?9: :?* B3.*3 2939D*:*3 +9AJ* 724,: ,A:B 9 ABAE+BA7*3-*. 9A. 9 +BA7*3-*. +BD2BEA*A:T >?*,3 +BA:3,J<:,BA :B :?* D9+3B7+B2,+ 9-*39K* ,7M*,K?:*. J= +1* 8, 9A. 8 3*72*+:,-*4=8 M?*3* 8 ) !0+!!

0T>?* ABAE+BA7*3-*. +BD2BA*A: +9A J* ,A:*323*:*. 97

9 <A,CB3D 4*-*4 "18 :?9: 3,7*7 9: 9 39:* K,-*A J= )ST 1T>?* 7*+BA. +BD2BA*A:8 "08 ,7 :?* 9-*39K* BC 9 .,7:3,EJ<:,BA BC +4<7:*37 M,:? 4B+94 B3.*3 2939D*:*3 "*S 7<3E3B<A.*. J= 9 .,7B3.*3*. B3 293:,944= B3.*3*. D9:3,WT)-*A:<944= :?* B3.*3*. +4<7:*37 K3BM :BM93.7 9 <A,ECB3D4= B3.*3*. 7:3<+:<3* 9A. :?<7 ,D2,AK* BA *9+?B:?*3T >?* 49::*3 +BD2BA*A: ,7 :?*3*CB3* -*3= 7,D,493 :B:?* :39A7CB3D*. -B4<D* 23B2B3:,BA ,A 9 A<+4*9:,BA 9A.K3BM:? 23B+*77T >?,7 ,7 +BDDBA4= .*7+3,J*. <7,AK :?*^B4DBKB3B-E;B?A7BAEP*?4E&-39D, F^;P&G *S<9:,BAB3 +BD24*:,BA CB3D<49 Fh9A Q,+4*A 155eb '9AK*3 1550G9A.8 J= M9= BC +BDJ,A9:,BA M,:? :?* 7B4<:,BA BC )ST 189A *D2,3,+94 *S<9:,BA CB3 :?* :,D* .*2*A.*A+* BC " ,A:?* 23*7*A+* BC !( f<+:<9:,BA7 +9A J* M3,::*A .BMA 97

&"'$ ) +1* 8,"1+$, - 8":)\ - 8+"*S * ":)\,

3 1* *W2 *#'+1* 8,$

#0

! "5' () *" +I,

O*3* "1+$, ,7 :?* 7B4<:,BA BC )ST 1 M,:? +?939+:*3,7:,+:,D* #T d7,AK 8 ) #*1

0 !+#*11 - #*1

0 , ) #*10 !#*1 FP939,7

9A. Q94a* 1551G8 :?* +?939+:*3,7:,+ :,D*7+94* #0 <A.*3M?,+? " ll.,N<7*7mm :BM93.7 :?* B3.*3*. +4<7:*37 ,7.*RA*.T #' ,7 :?* &#731' 8(,%*/#" BC B3.*3*. +4<7:*37

89:" ; Q+?*D9:,+ .,9K39D BC 9 ABAE<A,CB3D!( M,:? 79:<39:*. +4<7:*3F7'8*G 9A. <A79:<39:*. +4<7:*3 F(/)-*GT 9+'" ,((#:. ,A.,+9:* :?*23B29K9:,BA 9A. ,A+3*97* BC ;F)G M,:? :,D*T </77'0 ,((#:. ,A.,+9:*fBM BC " :BM93.7 B3.*3*. 3*K,BA7 9A. 3*7<4:,AK 4B+94 3*:93.9:,BA BCB3.*3,AKT >?* 0#**'0 7/"' D93@7 :?* D9+3B7+B2,+ 9-*39K* 9A. :?*.97?*. 4,A* ,7 " ) 1

! H*+9<7* ,A :?* 29392?97* #'!#( ) "8 D9+3B7+B2,+ B3.*3,AK ,7 BC+B<37* 947B 23*-*A:*. J= :?,7 49+@ BC .3,-,AK CB3+*T

0\Y

,A,:,944= 23*7*A:T >?* A<+4*9:,BA 39:* ,7 :?<7 977<D*. :BJ* `*3BT

#C :?* :*D2*39:<3* .*2*A.*A+* BC :?* :MB :,D* +BAE7:9A:7 "1 ) #*1

1 ,A )ST I CB44BM7 9A &33?*A,<7 J*?9-,B<3

"1+! , ) #*11 ) 21 *W21*+9-,1!+'! ,2 +5,

M,:? C3*S<*A+= C9+:B3 4 9A. 9+:,-9:,BA *A*3K= 9-8 :?*9JB-* .*RA,:,BA BC !0+!!

0 ,D24,*7 :?9: !0+!!0 ) 1 9:

> n \ ^8 97 "0+! ) \, ) "+! ) \,T >?,7 ,7 AB: 9 -*3=3*94,7:,+ 977<D2:,BA 9A. 8+! ,8 ,C .*RA*. ,A :?,7 M9=8 ,74,@*4= :B 7+94* M,:? 9 +BA7:9A: 23B2B3:,BA94,:= C9+:B3M,:? 3*72*+: :B !0+!!

0+! ,TQ:93:,AK C3BD :?* 79D* J97,+ 977<D2:,BA8

&"' ) +1* 8,"ABA*+BA7" - 8"+BA7"8 9A 9223BW,D9:,BA7+?*D* :?9: *W24,+,:4= +BA7,.*37 :?* ,A,:,94 .,7:3,J<:,BA8"/+$ ) \,8 ?97 J**A .*3,-*. FP94+?*3*@ *: 94T 155cGTQ*2939:,BA BC :?* 7:3<+:<3* C9+:B38 ,T*T :?* _B<3,*3:39A7CB3D9:,BA BC :?* *S<94 :,D* 29,3 +B33*49:,BA C<A+E:,BA8 ,A:B 9 <A,CB3D 293: 4+/ ) \% $, ) "0+$, 9A. 9 ABAE<A,CB3D 293:#

/ 4)\4+/% $,)/ ) &1"+), * "20' +1\,

944BM7 :?* *-94<9:,BA BC :?* 49::*38 <7,AK

&1"+), * "20' 5 +"*S * "+$,,+"+$, * "0+$,, " +11,

>?* f<+:<9:,BA 9-*39K*8 )ST 118 ,7 23B2*34= .*RA*.CB3 2?97* 7*2939:,BA 23BJ4*D78 M?*3* "+$, ,7 :?* J<4@+BD2B7,:,BA 9A. :?*3*CB3* 9 +BA7:9A: 23B2*3:= F'9AK*31550GT O*3* ?BM*-*38 :?* B3.*3 2939D*:*3 ,7 ABAE+BAE7*3-*.8 ,T*T "+$ $ 6, ) "*ST H97*. BA :?* 9JB-*9223BW,D9:,BA CB3 :?* D9+3B7+B2,+ 9-*39K* &"'8 M* +9A*W23*77 :?* 4BM*3 4,D,: "0+$, 97

"0+$, )"+$, * +1* 8,"*S

8# 8 & \ " +10,

#A )S7T 11 9A. 10 ,: ,7 977<D*. :?9: :?* ABAE+BAE7*3-*. B3.*3,AK 23B+*77 ?97 943*9.= .3,-*A :?* <22*34,D,: BC :?* !( .,7:3,J<:,BA ,A:B 4B+94 79:<39:,BAT >?<7:?* 9JB-* *S<9:,BA7 BA4= ?B4. CB3 :?* 49:* 7:9K*7 BC B3E.*3,AKT >?* 3*K,D* M?*3* :?* 9223BW,D9:,BA ,7 -94,. ,7"+$, & +1* 8,"*ST V<3,AK *934,*3 7:9K*7 )ST c +9A J*<7*. M,:?B<: DB.,R+9:,BAT

#C :?* 4?7 BC )ST 1\ ,7 7<J7:,:<:*. J= :?* 9-*39K* BC.,7+3*:* 7:3<+:<3* C9+:B3 +BD2BA*A:7 "0

/ 9A. ,C C<3:?*3BA:?* H39KK ,A:*A7,:= "0+$, ,7 9..*. ,A B3.*3 :B ,A+4<.* :?*<A,CB3D 293:8 :?* f<+:<9:,BA 9-*39K* 3*9.7

&"0/'/ ) "+$,"*S - "0+$,+"+$, * "*S, " +1X,

_,A944=8 :?* :,D* .*3,-9:,-* BC )ST 1X 3*7<4:7 ,A

#"#$

! ") 8

"+$, * +1* 8,"*S"/

#"/

#$

+ ,

/" +1],

>?* 497: :*3D BA :?* 3?7 BC )ST 1] ,7 :?* /E729+*9-*39K* F<2 :B :?* ,A-*37* +B937* K39,A,AK 4*AK:?GB-*3 :?* 23B.<+: BC .,7+3*:* 39:* +BD2BA*A:7 K,-*AJ= )ST c 9A. :?*,3 3*72*+:,-* DBD*A:93= 7B4<:,BA78"/+$,T >?* *S<9:,BA BJ-,B<74= ?97 9 7,AK<493,:= CB3"+$, ) +1* 8,"*S8 4*9.,AK :B 9A ,ARA,:* B3.*3,AK 39:*9: :?,7 2B,A: 9A. :?<7 :B 9 a<D2 ,A "+$,T >?,7 93:,R+,94.,7+BA:,A<,:= 3*7<4:7 C3BD :?* 49:* 7:9K* 9223BW,D9:,BA9A. ,: +9A J* 9-B,.*. J= 944BM,AK :?* ,A:*K39:,BA BC)ST c :B 23B+**. M*44 J*=BA. :?,7 2B,A:8 J*CB3* )ST 1],7 ,A-B@*.T

>?6%,)8%+('"

& .*:9,4*. .*7+3,2:,BA BC H9&40$*0!IEC*4.7293 9A. BC :?* 9A94=:E,+94 D*:?B.7 *D24B=*. ,A ,:7 7:<.= ?97 J**A K,-*A ,A 292*3 #T

>MB 7*3,*7 BC 9AA*94,AK *W2*3,D*A:7 93* 3*2B3:*. ?*3*T >?* R37:BA* 7:93:*. C3BD D9:*3,94 9AA*94*. 9: 1eIX ^ CB3 1 .9=T H9:+?*7 BC:?,7 D9:*3,94 M*3* ?*9:*. CB3 -93,B<7 :,D*7 9: 1YcX ^8 10cX ^8110X ^ 9A. 1\0X ^8 97 .*:9,4*. ,A >9J4* 1T >?* 7*+BA. 7*3,*7 BC*W2*3,D*A:7 7:93:*. C3BD D9:*3,94 9AA*94*. 9: 11cX ^ CB3 e\ .9=78:?<7 J*,AK 94DB7: C<44= B3.*3*. F+CT 292*3 #GT H9:+?*7 BC :?,7D9:*3,94 M*3* 9AA*94*. 9: 1Y0X ^8 1YcX ^ 9A. 1e]X ^ ,A B3.*3 :BCB44BM :?* .,7B3.*3,AK @,A*:,+7 F>9J4* 1GT &44 79D24* 72*+,D*A M*3*7*94*. ,A:B (:6"?Y +927<4*78 M?,+? M*3* S<*A+?*. ,A:B M9:*3 9C:*3?*9:,AKT

>)P .93@R*4. BJ7*3-9:,BA ,A :?* 4,K?: BC 7<2*37:3<+:<3* 3*Ef*+:,BA7 ,- / ) 0%- 18 6 ) 0%- 1 7?BM*. BA4= M*9@4= +<3-*.7*+:,BA7 BC &(H7 <A.*3 4BM D9KA,R+9:,BA8 ,A.,+9:,AK 9 493K* 9-E*39K* 7,`* BC :?* &(V7 F&#' 7 1 $DGT #A7,.* :?* .BD9,A7 DB::4*.+BA:397: ,A.,+9:*. :?* 23*7*A+* BC !( f<+:<9:,BA78 M?,+? 93* -,7,J4*,A :?* M*9@4= B3.*3*. 7:93:,AK D9:*3,94 BC 9AA*94,AK 7*3,*7 #Eh##8 97M*44 97 ,A @,A*:,+944= DB3* B3.*3*. 79D24*7 9: ! 8 10cX ^F_,KT 09GT !A 9223B9+?,AK :?* *S<,4,J3,<D 7:9:* 9: ! ) 10cX ^ :?*DB::4*. +BA:397: .,7922*937 9A. 79D24*7 *-*A:<944= 922*93?BDBK*A*B<7T OBM*-*38 &(H7 7**A ,A :?* >)P ,D9K*7 3*D9,A3<KK*. 9A. .,7:B3:*. <2 :B :?* 4BAK*7: 9AA*94,AK :,D*7 F_,KT 0JGT

!$2%( ; &AA*94,AK :*D2*39:<3*7 9A. 9AA*94,AK :,D*7 BC H&$_ 79D24*7T V,N*3*A: 7:93:,AK D9:*3,947 93* ,.*A:,R*. J= :?*,3 9223BW,D9:*,A,:,94 B3.*3 2939D*:*3 -94<*7

%BT "B.+$ ) \, ! F^G * F. n .9=78 ? n ?B<378 D n D,A<:*7G

# \TY0 1YcX \TcY D 1T0Y D 0 D X D ] D I D 1e D 1 ? 0Y ?## \Te\ 1YcX \TY D 1 D 1TY D 0TY D YTY D 11 D 00 D X ? ] .### \TY0 10cX e D 1e D X1 D 1 ? 0 ? ] ? I ? 1e ? X0 ?#h \Te\ 10cX 11 D ]Y D 1TY ? X ? e ? 10 ? 1 . 0 . ] . 1e . e] .h \TY0 110X 1 ? ] ? I ? 1c ? 1 . ] . 1I . ]\ . I\ . 1e\ .h# \TY0 1\0X X . 1\ . ]\ . I\ . 1e\ . X01 .h## \Te\ 1\0X 0 . 1e . X0 . e] . 10I . 0YI .h### \T5e 1e]X \TY D \TcY D 1 D 1TY D 0 D X D ] D Y D e D I D 1\ D 0\ D 1 ? 10 ?#L \T5e 1YcX \TY D 1 D 1TY D X D Y D c D 1\ D 1Y D X\ D 1 ? 0 ? 10 ?L \T5I 1Y0X \TY D 1 D X D Y D I D 1\ D 1Y D 0\ D X\ D 1 ? 0 ?

0\e

'"! D*97<3*D*A:

!3.*3 2939D*:*37 "B. M*3* 3B<:,A*4= *W:39+:*. C3BD 2BM.*3 L"V29::*3A7T >?*7* M*3* 3*+B3.*. ,A :39A7D,77,BA K*BD*:3= <7,AK 9D<4:,M,3* 93*9 .*:*+:B3 FQ94a* 155YG M,:? DBAB+?3BD9:,+ U<E^(139.,9:,BAT

"B. M97 .*3,-*. C3BD :?* ,A:*A7,:= BC 7:3BAK 7<2*37:3<+:<3*3*f*+:,BA7 FJE:=2*b ,- / ) 0%- 18 6 ) 0%- 1G 3*49:,-* :B :?B7* BCA*93J= C<A.9D*A:94 3*f*+:,BA7 F9E:=2*b ,- / ) 0%8 6 ) 0%GT#A:*A7,:= -94<*7 : M*3* BJ:9,A*. J= R::,AK K9<77,9A 2*9@ C<A+:,BA7:B :?* ,A:*K39:*. 2*9@ 23BR4*7T >?* S<B:,*A:

:.!- ):+101, - :+\1X, - :+\X1, - :+$011, - :+$10X,

:+\00, - :+$0\0, - :+0\\, - :+1X\," +1Y,

M97 +94+<49:*.8 M?,+? +9A J* 3*49:*. :B :?* B3.*3 2939D*:*3 -,9 :?**S<9:,BA F+CT 292*3 #G

:.!- ) \"c1+X,"0B. " +1e,

Q"! D*97<3*D*A:

#" 9J7B32:,BA 72*+:39 M*3* 3*+B3.*. 9: 3BBD :*D2*39:<3* <7,AK 9H3<@*3 #_Q 11X- 72*+:3BD*:*3T Q9D24* 2*44*:7 M*3* 23*293*. <7,AK7:9A.93. ^H3 :*+?A,S<*T )9+? 2*44*: M*,K?:*. 0\\ DK 9A. +BAE:9,A*. \TY DK BC 79D24* D9:*3,94T >?* 79D24*7 M*3* K3B<A. J=?9A. ,A 9A 9K9:* DB3:93 <A.*3 9+*:BA*T &44 72*+:39 M*3* ,A:*K39:*.B-*3 Y10 79D24* 7+9A7 ,A :?* C3*S<*A+= 39AK* 0Y\ +D*1gc\\ +D*1T& ABD,A94 ,A7:3<D*A:94 3*7B4<:,BA BC ] +D*1 M97 <7*.8 M?,+? ,77<Z+,*A: K,-*A :?* 493K*3 2?BABA 4,A* M,.:? 9: 3BBD :*D2*39:<3*T>?* 72*+:394 3*7B4<:,BA ,7 1 +D*1T

&J7B32:,BA 4,A* J3B9.*A,AK 93,7,AK C3BD +9:,BA .,7B3.*3 ?97J**A 9A94=`*. S<9A:,:9:,-*4= ,A :?* :MB 72*+:394 3*K,BA7 0c\ +D*1g]X\ +D*1 9A. e\\ +D*1gee\ +D*1T &.?*3,AK :B :?* :*3D,AB4BK=<7*. ,A 292*3 #8 :?* :MB 72*+:394 3*K,BA7 93* 3*C*33*. :B J= :?*,39-*39K* M9-*A<DJ*37 XY\ +D*1 9A. eX\ +D*1T

#A B3.*3 :B 9-B,. :?* 9DJ,K<,:,*7 BC R::,AK *D2,3,+94 4,A*23BR4*7 :B :?* BJ7*3-*. 72*+:39 :?* 9<:B+B33*49:,BA D*:?B. M97*D24B=*. :B *W:39+: 9 3*49:,-* D*97<3* BC 9-*39K* 4,A* J3B9.E*A,AKT >?* 23B+*.<3* <7*. ?*3* ,7 ,.*A:,+94 :B :?9: .*7+3,J*. ,A292*3 #T

>?* 9J7B32:,BA J9A. ,A :?* 72*+:394 3*K,BA 93B<A. eX\ +D*1 ,7M*44 7*2939:*. C3BD A*,K?JB<3,AK 2*9@7T >?,7 944BM7 *D2,3,+9423BR4* R::,AK <7,AK :MB 'B3*A:`,9A 23BR4* C<A+:,BA7T #A _,KT X :?*3*7<4:,AK _[OP BC :?* 2*9@7 ,7 24B::*. 9K9,A7: :?* 9-*39K* & BC 94472*+:394 .9:9 BJ:9,A*. CB3 9AA*94,AK 7*3,*7 ### 9A. #hT >?* *W2*+:*.4,A*93 +B33*49:,BA J*:M**A JB:? 23B2*3:,*7 ,7 +BAR3D*. M,:?,A *WE2*3,D*A:94 *33B3 F+9 1 +D*1GT

@%5;"(5 '+- -)5&;55)*+

>?* BJ7*3-9:,BA7 +BA+*3A,AK :?* *S<,4,J3,<D J*?9-,B<3BC H9&40$*0!IEC*4.7293 ?9-* J**A .*:9,4*. ,A 292*3 #T>B K,-* 9A B-*3-,*M BC :?* :*D2*39:<3* .*2*A.*A+* BC:?* !(7 ?*3*8 :?* *S<,4,J3,<D J*?9-,B<3 BC "B.8 ": 9A.BC :?* Q"!E2939D*:*3 ;B. FeX\G ,7 7?BMA ,A _,KT ]T

dA,CB3D 9223BW,D9:,BA

_B3 9 <A,CB3D4= B3.*3*. 79D24*8 7B4<:,BA7 BC :?* 92E23B23,9:* >V$' *S<9:,BA 93* BJ:9,A*. J= 7B4-,AK

##"B.

#$) -"B.

!-

."XB.

!* ] 93:9A?+"B., % +1c,

M?,+? CB44BM7 C3BD )ST 1 9A. :?* 2B:*A:,94 K,-*A ,A292*3 #T >?* 2939D*:*37 93* - ) eeY1 ^ 9A.. ) X1Y1 ^T & "<AK*E^<::9 94KB3,:?D F(3*77 *: 94T1550G M97 <7*. :B 7B4-* :?* *S<9:,BA A<D*3,+944=T >?*+94+<49:*. !( .9:9 M*3* 3*RA*. 9K9,A7: :?* BJ7*3-9E

89:" < (?BABA 4,A*M,.:? BJ:9,A*. C3BD 2*9@ R::,AK 97 C<A+:,BA BC9<:B+B33*49:,BA ?94CM,.:? &T 'B3*A:`,9A 23BR4* C<A+:,BA7 M*3* <7*. :BR: :?* 72*+:39T & 4,A*93 J97*4,A* ?97 J**A 7<J:39+:*.

89:" =$ >)P V_ D,+3BK392? BC H&$_ 9AA*94*. 9: ! ) 10cX ^ CB3$ ) I ? M,:? M*9@4= +<3-*. &(H 7*+:,BAT 2 dA,CB3D4= B3.*3*. 79D24*BC H&$_ 9C:*3 9AA*94,AK CB3 $ ) ]) 9: :?* 79D* :*D2*39:<3*

0.8

0.6

0.4

0.2

0

Q

18001600140012001000T (K)

Qod

q (630)odQt

89:" > "B.8 ": 9A. ;B.FeX\G 97 C<A+:,BA BC :*D2*39:<3* ,A*S<,4,J3,<DT >?* +<3-*7 7?BM :?* +94+<49:*. J*?9-,B<3 BC "B. 9A.": ,A :?* D*9AER*4. 9223BW,D9:,BAT Q** 292*3 # CB3 .*:9,47

0\c

:,BA78 M,:? :?* 2939D*:*37 -% . ?*4. RW*.T >?* B3.*3,AK@,A*:,+7 M*3* K*A*3944= 7B4-*. <7,AK :?* 7D944*3 BC :?*:MB *W2*3,D*A:94 7:93:,AK -94<*7 +"B.%$)\ ) \"Y0,T Q,KEA,R+9A: .,N*3*A+*7 ,A :?* @,A*:,+ J*?9-,B<3 .*2*A.,AKBA :?* +?B7*A -94<* BC "B.%$)\ J*+BD* BA4= 92293*A: 9::?* 4BM*7: 9AA*94,AK :*D2*39:<3*8 M?*3* 3*RA*D*A:7M*3* :?<7 2*3CB3D*. 9K9,A7: :MB 7*2939:* 7B4<:,BA7 BC"B.+$, F*TKT _,KT YGT

9(0'(/") =/"'*/%.

#A :?* <A,CB3D DB.*4 :?* +94+<49:*. +<3-*7 C<44= 9K3**M,:? :?* !( .9:9 BA4= 9: :?* ?,K?*7: 9AA*94,AK :*D2*3E9:<3* F! ) 1YcX ^G8 M?,4* 9K3**D*A: ,7 BJ7*3-*. BA4=.<3,AK :?* *934= 7:9K*7 9: 4BM*3 :*D2*39:<3*7 F7** :?*.97?*. +<3-*7 ,A _,KT YJGT

>?* ?,K? :*D2*39:<3* B3.*3,AK @,A*:,+7 93* 293:,+<E4934= M*44 9223BW,D9:*. <7,AK )ST 1c BA 9 7?B3: 39AK*B3.*3 4*AK:? 7+94*8 ,T*T ,C :?* 93K<D*A: "B. ,7 7<J7:,:<:*.M,:? ;B.FXY\G B3 ;B.FeX\G 3*72*+:,-*4= F_,KT eGT #A B3.*3:B 9++B<A: CB3 :?* .,N*3*A: *S<,4,J3,<D J*?9-,B<3 BA:?*7* 4*AK:? 7+94*7 9A *D2,3,+94 R*4. :*3D ,; # 00\ ;6DB4 ,7 977<D*. :B +B<24* :B :?* 4B+94 B3.*3 2939D*:*3T!A 9 7?B3: 39AK* 4*AK:? 7+94* ,; *N*+:,-*4= 7<223*77*7:?* 2?97* :39A7,:,BA J= 7:9J,4,`9:,BA BC :?* B3.*3*.+4<7:*37T #A )ST 1c :?* :*3D ,;!+'! , ,7 9..*. :B :?* 3?7T

&7 .*RA*. J= )ST 1c :?* :,D* +BA7:9A: "+! , ) #*1

.*-,9:*7 C3BD :?* 9A:,+,29:*. &33?*A,<7 J*?9-,B<38)ST 5T >?* ABAE4,A*93,:= BC 9 >>>E24B: 9: "B.+$, # \"eF_,KT cG ,A.,+9:*7 :?9: 9..,:,BA94 C9+:B37 ,Af<*A+* :?*:*D2*39:<3* .*2*A.*A+* BC :?* :,D* +BA7:9A:T

V<3,AK 49:*3 7:9K*7 9: :*D2*39:<3*7 J*4BM 1YcX ^B3.*3,AK @,A*:,+7 D<+? 74BM*3 :?9A :?B7* 23*.,+:*. J=)ST 1c 93* BJ7*3-*.T #A C9+: :?* 49:*3 7:9K*7 BC :?* B3E.*3,AK 23B+*77 MB<4. J* DB3* 9++<39:*4= .*7+3,J*. <7,AK9 2BM*3 49M 9223BW,D9:,BA " ( $%T

>?,7 92293*A: +?9AK* ,A :?* @,A*:,+ 23B+*77 ,7 29394E4*4*. J= :?* :,D* .*2*A.*A+* BC :?* !( f<+:<9:,BA9-*39K*T _,K<3* I 24B:7 :?* .*+9= BC &1&"+),20' 97 BJ:9,A*.-,9 :?* .,N*3*A+* ;0B.+XY\, * "0

B. 97 C<A+:,BA BC :,D* CB3:?* 9AA*94,AK 7*3,*7 #EhT #A :?* -,+,A,:= BC :?* :39A7ECB3D9:,BA :*D2*39:<3* :?* f<+:<9:,BA 9-*39K* .*+9=79223BW,D9:*4= 97 $*18 M?*3*97 9: 4BM*3 9AA*94,AK :*DE2*39:<3*7 :?* :,D* .*+9= J*+BD*7 7,KA,R+9A:4= 74BM*3T

>/.#(0'(/") =/"'*/%.

V<* :B :?* C97: .,7B3.*3,AK @,A*:,+7 :?*7* +B<4. BA4= J*D*97<3*. +4B7* :B :?* *S<,4,J3,<D 7:9:* F_,KT 5GT [,:?,A:?,7 4,D,: :?* *S<,4,J39:,BA :,D*7 93* M*44 9223BW,D9:*.J= :?* >V$' 39:* 49MT &: ! ) 1e]X ^8 ,T*T \T5c0 !!!:38"B. 922*937 :B C944 :39A7,*A:4= J*4BM ,:7 *S<,4,J3,<D-94<*8 97 .*RA*. J= :?* P_&T !(7 BJ7*3-*. <7,AKOP#Q -93= :B 9 D<+? 7D944*3 *W:*A: M,:?,A :?* 79D*:,D* ,A:*3-94T V<* :B :?* +BA7,.*39J4* 7?B3: 39AK* B3.*3

0.82

0.80

0.78

0.76

0.74

0.72

0.70

0.68

0.66

Time (min)

q (630)t=0

q (350)od

q od

q (630)od

q (350)t=0

10 10 10 10 10 10 10-2 -1 0 1 2 3 4

89:" ? UBD293,7BA BC :?* <A,CB3D >V$' 23*.,+:,BA 9A. BJ7*3-*.Q"! .9:9 9: 1YcX ^8 ,T*T \T5X1!!!:3T >?* 7B4<:,BA BC )ST 1c ,7 .39MAM,:? ;B.FXY\G 97 93K<D*A: 9A. 9C:*3 9..,:,BA BC 9 R*4. :*3D;B.+XY\, ,; F7** :*W:GT 4((#:. ,A.,+9:* :?* ,A,:,94 -94<*7 BC ;B.

89:" @$ QB4<:,BA7 BC )ST 1] CB3 :?* 9AA*94,AK 7*3,*7 #Eh##T !(/,")7'.+#/"*/") 0#:":,(0. .*AB:* 79D24*7 M,:? &"B.%$)\' ) \"e 9:! ) 1\0X ^8 3+(/)-* *(/,")7'. :?B7* M,:? &"B.%$)\' ) \"Y0T &44 B:?*32B,A:7 M*3* R::*. <7,AK &"B.%$)\' ) \"Y0T 2 >?* 79D* 24B: CB3 )ST IT>?* 0,.-'0 7/"'. 7?BM :?* J*?9-,B<3 *W2*+:*. CB3 9 <A,CB3D4= B3.*3*.79D24* 9: 1YcX ^ 9A. 9: 10cX ^

0\I

9: :?,7 :*D2*39:<3* F+CT 292*3 # 9A. _,KT ]G8 ;B. ,7 493K*3:?9A "B.T ;B.FeX\G8 ,A 293:,+<4938 .B*7 AB: *W?,J,: :?*:39A7,*A: .3B2 J*4BM *S<,4,J3,<DT >?,7 .,7+3*29A+= +9AJ* 9::3,J<:*. :B :?* ?,K? 9AA*94,AK :*D2*39:<3*8 M*44M,:?,A :?* f<+:<9:,BA 3*K,D* BC :?* 2?97* :39A7,:,BAT

>?* ABAE<A,CB3D 9223BW,D9:,BA/ 9224,+9:,BABC :?* *W:*A.*. >V$' *S<9:,BA

#A B3.*3 :B 9223BW,D9:* :?* BJ7*3-9:,BA7 <7,AK :?* DB3*7B2?,7:,+9:*. )ST 1]8 :?* ,A,:,94 +BA.,:,BA7 ?9-* :B J*+92:<3*. ,A :*3D7 BC +BD2BA*A:7 "/8 :?*3*J= :9@,AK :?*ABAE<A,CB3D,:= BC :?* B3.*3 2939D*:*3 ,A:B 9++B<A:T

_,K<3* 1\ 7?BM7 :?* +,3+<4934= 9-*39K*. _B<3,*39D24,:<.*7 BJ:9,A*. C3BD 9 >)P V_ D,+3BK392? BC :?*7:93:,AK D9:*3,94 S<*A+?*. C3BD ,:7 9AA*94,AK :*D2*39E:<3* 9: 1eIX ^T &293: C3BD :?* 39AK* +4B7* :B / ) \:?*7* _B<3,*3 9D24,:<.*7 93* M*44 9223BW,D9:*. J= 9'B3*A:`,9A 2*9@ C<A+:,BAT >?* .,7922*939A+* BC "/ CB3/ $ \ ,7 +9<7*. J= :?* RA,:* 7,`* BC :?* <A.*34=,AK,D9K*T d7,AK :?* *W2*3,D*A:944= @ABMA f<+:<9:,BA 9-E*39K* 9A 9223B23,9:* AB3D94,`9:,BA BC :?,7 'B3*A:`,9AC<A+:,BA#

/ 4)\"0

/ ) &1"+7, * "20' # ;0B. * "0B. # \"1e +1I,

+9A J* BJ:9,A*.T H97*. BA :?,7 AB3D94,`9:,BA8 .,7+3*:*7:93:,AK -94<*7 "/ +$ ) \, CB3 \ $ / $ /6 93* +94+<49:*.T>?* f<+:<9:,BA 9-*39K* <7*. ,A )ST 1I .*3,-*7 C3BD :?*BJ7*3-*. .,N*3*A+* BC 7?B3: 9A. 4BAK 39AK* B3.*3 D*9E7<3*D*A:7 <7,AK OP#Q 9A. L"V 3*72*+:,-*4= F+CT :?*,A,:,94 -94<* ,A _,KT IGT

>?* ,A,:,94 .,7:3,J<:,BA "/ +$ ) \, ,7 23B29K9:*.:?3B<K? :,D* 9++B3.,AK :B :?* 9223B23,9:* 39:* *S<9:,BAT_B3 "+$<, 8 +1* !0+!!

0,"*S :?,7 ,7 )ST cT [,:? :?* .3,-E,AK CB3+* .*3,-*. C3BD )ST Y M* +9A M3,:*

##"/

#$) 1* !0+

!07,A+!/,!/

! "3 -"/+$,

!* */0"/+$,

'!

)

- ."X/+$,!

* ]93:9A?+"/+$,,*

"

+15,

89:" A V*-,9:,BA C3BD &33?*A,<7 :*D2*39:<3* .*2*A.*A+* BC :?* 39:*+BA7:9A: CB3 9 <A,CB3D .3,-,AK CB3+*T >?* 4BK93,:?D BC :39A7CB3D9:,BA:,D* 9: "B. # \"e ,7 24B::*. 9K9,A7: 3*+,23B+94 :*D2*39:<3*T >?* 4,A* ,7+BA7:39,A*. :B 2977 :?3B<K? :?* R37: :MB .9:92B,A:78 +B33*72BA.,AK :B9 D,A,D94 9+:,-9:,BA *A*3K= BC 9- ) 0ee @;6DB4

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0

t=0

Time (s)10 10 10 10 10 10 101 2 3 4 5 6 7

q(3

50) -

Qod

2od

2

89:" B _4<+:<9:,BA 9-*39K* 97 .*:*3D,A*. J= ;0B.+XY\, * "0B. 97 9

C<A+:,BA BC :,D*T >?* +<3-*7 93* K<,.*7 :B :?* *=*T >?* -94<* BJ7*3-*.9: $ ) \ ,7 \T1e

89:" C V,7B3.*3,AK @,A*:,+7 9A. +B33*72BA.,AK 7B4<:,BA7 BC )ST 1T?1,77 #+'" .@12#7. 3*23*7*A: ;B.FeX\G8 .1,77 A77'0 .@12#7. ;B.FXY\G 9:\T5\1 9A. \T5c0!!!:3T B,()'( .@12#7. :/*- '((#(2,(. 7?BM "B.

0\5

>?* K39.,*A: *A*3K= ,7 9223BW,D9:*. <7,AK 9 -94<* BC* ) 1\\ @; AD06DB4T &A ,A+3*97,AK * .,D,A,7?*7 :?*B3.*3 2939D*:*3 k 9: +BA7:9A: :,D* .<3,AK 49:* 7:9K*7 BCB3.*3,AK 9A. * :?*3*CB3* +B33*49:*7 M,:? "+$<,8 ,T*T M,:?:?* 2B7,:,BA BC :?* JB<A.93= J*:M**A >V$' 9A. +4<7:*3K3BM:? 3*K,D*T * 9A. !0+!!

0 +9A :?<7 AB: J* .*:*3D,A*.,A.*2*A.*A:4= C3BD :?,7 *W2*3,D*A: 94BA*T OBM*-*38 :?*+?B7*A -94<* BC * ,7 BC 3*94,7:,+ B3.*3 BC D9KA,:<.*8 K,-*A:?* *W2*+:*. ,A:*39+:,BA 39AK* J*:M**A A*93*7: A*,K?EJB<3 +9:,BA .,7:9A+* F#X &o G 9A. <A,: +*44 .,D*A7,BA7F#10 &o GT

_B3 -94<*7 "+$<, & +1* !0+!!0,"*S :?* 3?7 BC )ST 15

,7 D<4:,24,*. M,:? ,:7 7B4<:,BA8 "/+$,8 9A. 7<J7:,:<:*.,A:B )ST 1]T >?* /E729+* 9-*39K* ,7 +94+<49:*. CB3 1\\*S<944= 729+*. +BD2BA*A:7 "/8 M,:? :?* +B937* K39,AE,AK +<:BN 9: /6 ) %!1"0 AD ) 0"e0 AD*1T >?* 49::*3-94<* ,7 J97*. BA 9A *S<,-94*A: ll,7B:3B2,+mm <A,: +*44.,D*A7,BA CB3 H9&40$*0!IEC*4.7293T >?* 3*7<4:7 BJE:9,A*. CB3 :?* -93,B<7 9AA*94,AK :*D2*39:<3*7 93*7?BMA ,A _,KT YT

&A &33?*A,<7 24B: BC :?* 3*RA*. 39:* +BA7:9A:7 ABM=,*4.7 4,A*93 J*?9-,B<3 B-*3 :?* *A:,3* :*D2*39:<3* 39AK*F_,KT 11GT

&A 9+:,-9:,BA *A*3K= BC )- ) XY0" 0I @;6DB4 9A. 9C3*S<*A+= C9+:B3 BC 2 ) Y"e ! 1\5 O` 93* BJ:9,A*.T>?*7* ?9-* J**A .*3,-*. M,:? 74,K?:4= 7D944*3 M*,K?:K,-*A :B :?* :MB 4BM :*D2*39:<3* .9:9 7*:7 F110X ^ 9A.1\0X ^G ,A B3.*3 :B 9++B<A: CB3 :?* C9+: :?9: *S<,4,J3,<D+B<4. AB: J* *7:9J4,7?*. 9: :?*7* 4BM :*D2*39:<3*7T

d7,AK :?*7* -94<*78 :?* 2B77,J,4,:= BC 3*B3.*3,AK .<3E,AK S<*A+?,AK +9A J* 977*77*.T [* *7:,D9:* 9 4,A*93S<*A+?,AK 39:* BC 0\\ ^67 ,A :?* +3<+,94 :*D2*39:<3*3*K,D* J*:M**A 1X\\ ^ 9A. !:3T [,:? "B. # \"Y M?*AS<*A+?,AK C3BD ! # !:38 ,A:*K39:,BA BC :?* 23B.<+: BC,A-*37* S<*A+?,AK 39:* 9A. B3.*3,AK 39:* B-*3 :?* :*DE2*39:<3* ,A:*3-94 ,A S<*7:,BA =,*4.7 9A 9223BW,D9:*3*B3.*3,AK BC &"B. ) \"\\0T >?,7 ,7 J*4BM :?* D*97<3*ED*A: *33B3 *A+B<A:*3*. ,A :?* 2BM.*3 LE39= .,N39+:,BA*W2*3,D*A:7T

_,K<3* 10 7?BM7 :?* .*3,-*. -94<*7 BC :?* D,W,AK+B*Z+,*A: !0+!!

0 97 9 C<A+:,BA BC :*D2*39:<3*T >?*7*CB44BM C3BD :?* 79:<39:,BA 4,D,:8 "+$<,8 BJ:9,A*. 9: *9+?:*D2*39:<3*T >?*,3 9J7B4<:* -94<*8 ?BM*-*38 .*2*A.7 BA:?* 977<D*. -94<* BC :?* K39.,*A: *A*3K= *T &47B 7?BMA,7 :?* C<A+:,BA !0+!!

0 ) <#*10 !#*18 7+94*. :B R: :?*7*

.9:92B,A:7 J= 9.a<7:,AK :?* 2939D*:*3 <T >?* :,D* +BAE7:9A:7 <7*. :B .*RA* :?* C<A+:,BA ?9-* J**A BJ:9,A*.,A.*2*A.*A:4=8 J= R::,AK :?* *D2,3,+94 DB.*4 )ST I :B:?* @,A*:,+ !( .9:9T >?* 9+:,-9:,BA *A*3K= BJ:9,A*. CB3:?* &48$* B3.*3,AK 39:* #*18 :?9: *A:*37 )ST I -,9 :?*,A:*K39:*. -94<* "1+$,8 ,7 74,K?:4= 7D944*3 ,A :?,7 +97*89- ) X0c"I @;6DB4 M,:? 2 ) \"I ! 1\5 O`T #*1

0 ,7 .*RA*.J= 9-0 ) cI"0 @;6DB4 9A. 20 ) \"\]5 O`T >?* ^;P&*W2BA*A: ,7 3*RA*. :B 5 ) \"YI 9A. :?* A<+4*9:,BA.*A7,:= ,7 #' ) \"]c0T [,:? :?*7* 2939D*:*37 ?*4. RW*.:?* 7+94* C9+:B3 3*RA*7 :B < ) \"XI8 :?<7 .*:*3D,A,AK :?*-94<* BC !0+!!

0 *W:392B49:*. :B \ ^T

-20

-18

-16

-14

-12

-10

-8

-6

-4

ln k

0.00100.00090.00080.00070.00061/T [K ]-1

89:" ;; (4B: BC 4A+", -*37<7 3*+,23B+94 :*D2*39:<3*T C(#..'0 %/(%7'.3*23*7*A: 39:* +BA7:9A:7 BJ:9,A*. C3BD .,7B3.*3,AK *W2*3,D*A:7T >?*4,A* ,7 9 M*,K?:*. 4*97: 7S<93*7 R: :B :?* .9:9

89:" ;D$ >)P V_ D,+3BK392? BC ,A,:,94 !( f<+:<9:,BA7 ,A :?*7:93:,AK D9:*3,94 S<*A+?*. C3BD \T55e!!!:3 F7,`* # 10\ AD 310\ ADGT 2 U,3+<4934= 9-*39K*. _B<3,*3 9D24,:<.*7 "/ BJ:9,A*. C3BD$T >?* 0,.-'0 %3(&' ,7 9 'B3*A:`,9A C<A+:,BA R::*. :B :?* .9:9 CB3/ & \"X AD*1

01\

A*+&";5)*+5

>?* ,A:39.BD9,A B3.*3,AK @,A*:,+7 BJ7*3-*. ,A H&$_93* ,Af<*A+*. J= :?* ABAE<A,CB3D,:= BC :?* 7:93:,AKD9:*3,94 9AA*94*. ,A7,.* :?* f<+:<9:,BA 3*K,D* BC :?*2?97* :39A7,:,BAT >?* f<+:<9:,BA7 S<,+@4= 7<J7,.* ,C :?*C*4.7293 ,7 9AA*94*. 9: :*D2*39:<3*7 +4B7* :B :?* :39A7,E:,BA :*D2*39:<3* 9A. :?* B3.*3 2939D*:*3 @,A*:,+7 ,7:?*3*CB3* 9223BW,D9:*. <7,AK 9 >V$' *S<9:,BA M,:?ABAE+BA7*3-*. B3.*3 2939D*:*3T &AA*94,AK *W2*3,D*A:79: 4BM*3 :*D2*39:<3*7 *W?,J,: 9 74BM,AK .BMA BC :?*B3.*3,AK @,A*:,+7 M?,+? +9A J* ,A+B32B39:*. ,A:B :?*>V$' 39:* *S<9:,BA <7,AK 9 M*,K?:*. 9-*39K* BC :MB+BA:3,J<:,BA7 :B :?* D9+3B7+B2,+ 9-*39K* BC "T >?* R37:+BA:3,J<:,BA +9A J* ,A:*323*:*. 97 9 <A,CB3D !( ll4*-*4mm8M?,4* :?* 7*+BA. 93,7*7 C3BD :?* 9-*39K* BC 9 .,7:3,J<:,BABC B3.*3*. +4<7:*37T #C :?* K39.,*A: *A*3K= * ,7 977,KA*. 93*97BA9J4* -94<*8 :?* D,W,AK +B*Z+,*A: !0+!!

0 +9A J*BJ:9,A*. 97 9 C<A+:,BA BC :*D2*39:<3*T >?B<K? ,:7 9JE7B4<:* -94<* .*2*A.7 BA :?* 293:,+<493 -94<* BC *8 :?*:*D2*39:<3* .*2*A.*A+* BC :?,7 23B2*3:= 7?B<4. J*39:?*3 <A,-*3794T #A +97*7 M?*3* * 7 0208 ,T*T CB3 -*3=493K* ,A:*39+:,BA 39AK*78 :?* .*K3** BC +BA7*3-9:,BA J*E+BD*7 A*K4,K,J4* *-*A 9: 4BM :*D2*39:<3*7 9A. f<+:<9E:,BA7 93* @,A*:,+944= <A7:9J4*T OBM*-*38 ,A :?*7* +97*7493K* f<+:<9:,BA7 93* ,D23BJ9J4* <A.*3 *S<,4,J3,<D+BA.,:,BA7 97 M*448 97 :?* P_& 23B-,.*7 9A *W9+: .*E7+3,2:,BA CB3 :?* *S<,4,J3,<D J*?9-,B<3 BC 7<+? D9:*3,947*-*A ,A :?* -,+,A,:= BC !+T

&7 ,A.,+9:*. J= :?* .,7B3.*3,AK *W2*3,D*A:7 :?*>V$' 9223BW,D9:,BA ?B4.7 M?*A :?* B3.*3 2939D*:*3 ,79 <A,CB3D 23B2*3:=T OBM*-*38 :?* *W2*3,D*A:7 7<KK*7::?9: ,A :?,7 +97* .*-,9:,BA7 B++<3 +4B7* :B :?* *S<,4,J3,<D7:9:* CB3 ! $ !:3T & :39A7,*A: 4BM*3,AK BC "B. J*4BM ,:7*W2*+:*. *S<,4,J3,<D -94<* +9AAB: J* .*7+3,J*. J= 2<3*4=.*:*3D,A,7:,+ 39:* *S<9:,BA7T V*-,9:,BA7 C3BD .*:*3D,AE,7:,+ J*?9-,B<3 +B<4. J* 9::3,J<:*. :B :?* BA7*: BC :?*3E

D94 f<+:<9:,BA78 97 B22B7*. :B :?* .,7922*939A+* BCS<*A+?*. f<+:<9:,BA7 BJ7*3-*. .<3,AK B3.*3,AKT >?,7 ,7+B33BJB39:*. J= :?* BJ7*3-9:,BA :?9: :?* !(8 M?*A CB4E4BM*. BA 9 4B+94 4*AK:? 7+94*8 3*D9,A7 +BA7:9A: A*93 ,:7*W2*+:*. *S<,4,J3,<D -94<*T >?,7 D,K?: ,A.,+9:* :?9: :?*+?9AK*7 7**A BA 9 4BAK 39AK* 7+94* 93* 3*49:*. :B :,D*.*2*A.*A+* BC :?* 9-*39K* +4<7:*3 7,`* CB3D*. 9: :*DE2*39:<3*7 +4B7* :B !+T dA9DJ,K,B<7 D*97<3*D*A: BC :?*7*2?*ABD*A9 MB<4. 3*S<,3* ,AE7,:< *W2*3,D*A:7 :?B<K?T

1&*E-6%(7:(F(E43 _,A9A+,94 7<22B3: J= V*<:7+?* _B37+?<AK7EK*D*,A7+?9C: F^3 ceI610G8 V*<:7+?*3 &@9.*D,7+?*3 &<7E:9<7+?.,*A7: FV&&VG 9A. :?3B<K? >P" A*:MB3@ K39A: )"HE_P"LEU>5cE\1\I 93* K39:*C<44= 9+@ABM4*.K*.T UBDD*A:7 D9.*J= :MB 9ABA=DB<7 3*-,*M*37 ?*42*. :B ,D23B-* :?* D9A<7+3,2:T

@%4%,%+&%5

H,A.*3 ^ F1551G Q2,AB.94 .*+BD2B7,:,BAT P9:*3,947 Q+,*A+* 9A.>*+?AB4BK= hB4T YT hUO8 [*,A?*,D 22 ]\eg]c1

H39= &; F155]G >?*B3= BC 2?97*EB3.*3,AK @,A*:,+7T &.- (?=7]XFXG/XYcg]Y5

U932*A:*3 P& F15519G P*+?9A,7D7 9A. @,A*:,+7 BC &4EQ, B3.*3,AK,A 9AB3:?,:*/ #T #A+BDD*A7<39:* 7:3<+:<3* 9A. .BD9,A +B937E*A,AKT &D P,A*394 ce/111\g1115

U932*A:*3 P& F1551JG P*+?9A,7D7 9A. @,A*:,+7 BC &4EQ, B3.*3,AK,A 9AB3:?,:*/ ##T )A*3K*:,+7 9A. 9 $,A`J<3KE'9A.9< 39:* 49MT&D P,A*394 ce/110\g11XX

U932*A:*3 P&8 VBD*A*K?*::, PU8 >9``B4, h F155\G &224,+9:,BABC '9A.9< :?*B3= :B +9:,BA B3.*3,AK ,A *D2?9+,:* ##/ ^,A*:,+J*?9-,B<3T )<3 ; P,A*394 0/15g0I

O933,7BA ";8 (<:A,7 & F155cG >?* +B<24,AK J*:M**A D9KA*:,+ 9A.+9:,BA B3.*3,AK/ 9 D9+3B7+B2,+ 9223B9+?T )<3 ; P,A*3945FeG/111Yg11X\

^3B44 O8 Q+?4*A` O8 (?,44,27 P[ F155]G >?*3DB.=A9D,+ DB.*4E4,AK BC ABAE+BA-*3K*A: B3.*3,AK ,A B3:?B2=3BW*A*7/ 9 +BD293E,7BA BC +4977,+94 9A. '9A.9= 9223B9+?*7T (?=7 U?*D P,A*394701/YYYgYe\

'9AK*3 ;Q F1550G &A ,A:3B.<+:,BA :B :?* @,A*:,+7 BC R37:EB3.*32?97* :39A7,:,BA7T #A/ $B.3*p +?* U F*.G QB4,.7 C93 C3BD *S<,E4,J3,<DT U9DJ3,.K* dA,-*37,:= (3*778 U9DJ3,.K*

P94+?*3*@ >8 Q94a* )^O8 ^3B44 O F155cG & 2?*ABD*AB4BK,+949223B9+? :B B3.*3,AK @,A*:,+7 CB3 293:,944= +BA7*3-*. B3.*32939D*:*37T ; (?=7 UBA.*A7 P9::*3 5/I\cYgI\I]

P94+?*3*@ >8 U932*A:*3 P&8 ^3B44 O8 Q94a* )^O F1555G U9:,BAB3.*3,AK ,A H9&40$*0!IEC*4.7293/ ,D24,+9:,BA7 CB3 :?* #$1 9 U$12?97* :39A7,:,BA ,A 9AB3:?,:*T (?=7 U?*D P,A*3947 0eF]G/XY]gXee

P939,7 Q8 Q94a* )^O F1551G V*3,-9:,BA BC 39:* 49M CB3 ABAE<A,CB3D7=7:*D7 9A. +BA:,A<B<7 B3.*3 2939D*:*37T ; (?=7 UBA.*A7P9::*3 X/XeecgXec\

(3*77 [O8 >*<+?B47@= Q&8 h*::*34,AK [>8 _49AA*3= H( F1550G%<D*3,+94 3*+,2*7 ,A _B3:39AT U9DJ3,.K* dA,-*37,:= (3*778U9DJ3,.K*

"*.C*3A Q&>8 O*A.*37BA UPH8 ^A,K?: ^Q8 [BB. H; F155cGO,K?E:*D2*39:<3* B3.*3 .,7B3.*3 ,A F_*\"YPA\"YG0Q,!] 9A.FPK\"YPA\"YG0Q,!] B4,-,A*7/ 9A ,AE7,:< A*<:3BA .,N39+:,BA 7:<.=)<3 ; P,A*394 5F0G/0IcgX\\

Q94a* ) F155YG & AB-*4 cE+,3+4* .,N39+:BD*:*3 CB3 :?* 392,. 9A94=7,7BC *W:*A.*. .*C*+:7 ,A :?,A R4D78 7,AK4* +3=7:947 9A. +*39D,+7T(?97* >39A7,:,BA7 YY/XcgYe

Q94a* )^O F15IIG ^,A*:,+ 39:* 49M7 97 .*3,-*. C3BD B3.*3 2939DE*:*3 :?*B3= #/ :?*B3*:,+94 +BA+*2:7T (?=7 U?*D P,A*3947 1Y/XXegX]I

Q94a* )^O8 ^3B44 O F1551G ^,A*:,+ 39:* 49M7 97 .*3,-*. C3BD B3.*32939D*:*3 :?*B3= ###/ &48Q, B3.*3,AK ,A 79A,.,A*T (?=7 U?*DP,A*3947 1c/YeXgYeI

0.35

0.30

0.25

0.20

0.15

0.10

0.05

15001400130012001100Temperature [K]

(ζ/ζ)

c2

89:" ;= !0+!!0 97 C<A+:,BA BC :*D2*39:<3* CB3 * ) 1\\ @; AD0T >?*

0,.-'0 %3(&' 7?BM7 :?* *W2*+:*. J*?9-,B<3 ,C !0+!!0 ,7 *W23*77*. ,A

:*3D7 BC 39:* +BA7:9A:78 ,T*T !0+!!0 ( #*1

0 !+#*10 - #*1

1 ,

011

Q94a* )^O8 [3<+@ H8 $39*D*EH93J*3 &8 U932*A:*3 P& F155XG)W2*3,D*A:94 :*7: BC 39:* *S<9:,BA7/ :,D* *-B4<:,BA BC &48Q,B3.*3,AK ,A 9AB3:?,:* U9&40Q,0!IT ; (?=7 UBA.*A7 P9::*3Y/05e1g05eI

h9A Q,+4*A UV F155eG "9A.BD A<+4*9:,BA 9A. K3BM:? @,A*:,+7T(?=7 "*- H Y]F1cG/11I]Yg11I]I

!66%+-)?

(39+:,+94 972*+:7 BC :?* +94+<49:,BA7

>?* ,A:*K39:,BA BC >V$' *S<9:,BA7 7<+? 97 )ST c ,A+BAA*+:,BA M,:? 2?97* :39A7,:,BA @,A*:,+7 K*A*3944= 3*ES<,3*7 :?* <7* BC A<D*3,+94 D*:?B.78 K,-*A :?* ?,K?B3.*3 BC :?* !(E:*3D7 ,A :?* @,A*:,+ .3,-,AK CB3+*T #C "+$,.*2*A.7 BA 9 39AK* BC /E-94<*78 97 ,A )ST 1]8 9 493K*A<DJ*3 BC 7<+? *S<9:,BA7 ?97 :B J* 7B4-*.7,D<4:9A*B<74=T >?* CB<3:? B3.*3 "<AK*E^<::9 F"^]GP*:?B. 23B-,.*7 9 C97: 9A.8 K,-*A :?* *W2*3,D*A:943*7B4<:,BA BC "8 7<Z+,*A:4= 9++<39:* M9= :B 7B4-* 7<+? 97*: BC B3.,A93= .,N*3*A:,94 *S<9:,BA7 F!V)7GT

& 7<,:9J4* "^]E94KB3,:?D ,7 K,-*A J= (3*77 *: 94TF1550GT #: 9.-9A+*7 :?* 7B4<:,BA BC 9A !V) C3BD 9@ABMA 7:93:,AK 2B,A: $ :B $ - !$ J= <7,AK :?* @ABMA.*3,-9:,-* )"!)$ 9: :?* J*K,AA,AK 9A. :3,94 .,N*3*A:,947D,.M9= :?3B<K? 9A. 9: :?* *A. BC :?* :,D*7:*2 $ - !$T)"!)$8 ,T*T :?* 39:* *S<9:,BA8 ?97 :B J* 23B-,.*. 97 9C<A+:,BA +944*. J= :?* 94KB3,:?DT

#A )ST I a<7: 9 7,AK4* !V) ,7 7B4-*.T >?* 3*7<4:8 "1+$,8,7 +BDJ,A*. M,:? :?* ABAE<A,CB3D F9A94=:,+94G 293:T "+9A :?*A J* 3*RA*. 9K9,A7: *W2*3,D*A:94 -94<*78 :?*3*J=B2:,D,`,AK :?* 2939D*:*37 :?9: *A:*3 )ST IT

& DB3* +BD24*W 23B+*.<3* ,7 A**.*. :B 7B4-* :?**W:*A.*. 39:* *S<9:,BA )ST 1]8 *72*+,944= ,C :?* 3*7<4:793* :B J* 3*RA*. 9K9,A7: *W2*3,D*A:94 .9:9/

1T QB4<:,BA BC :?* 39:* *S<9:,BA7T#A.,-,.<94 7:93:,AK -94<*7 CB3 "+$ ) \% /, D<7: J*

@ABMAT >?* 39AK* J*:M**A / ) \ 9A. / ) %!6 ,7 .,E-,.*. ,A:B 9 7<Z+,*A:4= 493K* A<DJ*3 BC *S<,.,7:9A:7:*27T h94<*7 BC :?* :,D* +BA7:9A: 93* +94+<49:*. 97C<A+:,BA BC / 9A. 7:B3*. ,A 9 K4BJ94 9339=T & 7<,:9J4*9339= BC :,D*E7:*27 !$ +9A J* .*:*3D,A*. ,A 9.-9A+*B3 J= 9.92:,-* 7:*27,`* +BA:3B4 F7** (3*77 *: 94T 1550GT>?* 9++<39+= BC :?* "^E94KB3,:?D7 +9A J* +?*+@*.<7,AK 9 .3,-,AK CB3+* CB3 9 +4977,+94 7*+BA. B3.*3 2?97*:39A7,:,BA8 ,A M?,+? +97* 9A 9A94=:,+94 7B4<:,BA BC)ST c +9A J* BJ:9,A*. F7** )ST 1Y ,A P94+?*3*@ *: 94T155cGT

>?* +94+<49:,BA BC :?* B3.*3 2939D*:*3 "+$, ,A :?*:MB 7:9K* DB.*4 ,7 .,-,.*. ,A :MB 293:7/

F9G V<3,AK :?* *934= 7:9K*7 :?* <A,CB3D +BD2BA*A:"F/ ) \8:G .*:*3D,A*7 :?* !(T >?* B:?*3 +BD2BEA*A:7 93* BA4= 23B29K9:*. :?3B<K? :,D*T

FJG #C "+$, & "+$<,8 )ST 1] ,7 ,A-B@*.T >?,7 ,7 .BA* 9:7<Z+,*A: .,7:9A+* :B :?* :?3*7?B4. F1g0q 9JB-*"+$<,G8 ,A B3.*3 :B 9-B,. :?* ,A?*3*A: .,7+BA:,A<,:= 9::?,7 2B,A:T >?* 7M,:+? C3BD BA* 39:* *S<9:,BA :B :?*B:?*3 ,7 +B.*. ,A 9A /8 +BA.,:,BA 97 293: BC :?*C<A+:,BA :?9: 23B-,.*7 )"!)$T &44 :?* 3,K?: ?9A. 7,.*93K<D*A:7 BC )ST 1] 93* +94+<49:*. .<3,AK 9 "^]7:*2 9A. 9223B23,9:* 9-*39K,AK B-*3 944 +94+<49:*.+BD2BA*A:7 / K,-*7 "+$,T

0T "*RA*D*A: 9K9,A7: BJ7*3-*. "T#C $ +B33*72BA.7 :B *W2*3,D*A:94 -94<*78 "+$% =, ) "+$,

,7 7:B3*.T >?<7 )0 ) "=+"+$% =,>.< * "+$% =,(-6(,0 ,7 BJE

:9,A*.T P,A,D,`9:,BA BC )08 M,:? 3*2*9:*. +9447 :B :?*"^]E3B<:,A*78 944BM7 :?* 3*RA*D*A: BC :?* 2939D*:*37,A-B4-*. ,A +94+<49:,AK )"!)$8 7<+? 97 39:* +BA7:9A: 9A.D,W,AK +B*Z+,*A:T

010