Advances in Physics Theories and Applications ISSN 2224-719 !Paper" ISSN 222#-$%&' !(nline" )ol.

19* 2$1& - Selected +ro, International -on+erence on .ecent Trends in Applied Sciences with /ngineering Applications

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Specific heat and Thermodynamics of Titanate Perovskite Materials
.en0 -hoithrani1 2 N. 3. 4a0r 5epart,ent o+ Physics* 6ar7at0llah 8niversity* 6hopal-4%2$2%* India 1 /-,ail9 ren0choithrani:g,ail.co, Abstract Speci+ic heat and ther,odyna,ical properties o+ the ;aTi(&<=>2 have ?een investigated +or the +irst ti,e 0sing e@tended rigid ion ,odel !/.IA". Bith the increase o+ no,inal hole doping =* the syste, 0ndergoes a phase change +ro, an ins0lating phase to a ,etallic phase at =cIA C $.$# and the low-te,perat0re anti+erro,agnetic phase disappears at =c,ag C $.$'. ;aTi(&<=>2 has ?een s0ggested to have pro,ising scienti+ic and technological applications. (0r co,p0ted speci+ic heat res0lts +ollow the sa,e trends o+ variation with corresponding e@peri,ental data. The val0es o+ speci+ic heats also increase with te,perat0re. The theoretically co,p0ted ther,odyna,ical properties o+ ;aTi(&<=>2 co,po0nd are in good agree,ent with the availa?le e@peri,ental res0lts. Keywords: Ther,odyna,ical properties* Perovs7ites* Speci+ic heat* 5e?ye te,perat0re* -ohesive energy 1 Introduction .ecently ,etal-ins0lator transitions !AIT" in &d-transition ,etal ternary o@ide syste,s have ?een intensively investigated in order to clari+y the ano,alo0s properties o+ correlated electrons1. (ne o+ the ,ost prototypical syste,s is the perovs7ite-type one* +ro, the ,ineral perovs7ite ;aTi(&. The per+ect perovs7ite str0ct0re is an e@tre,ely si,ple one with the che,ical +or,0la A6(&* where A is a ,onovalent* divalent or trivalent al7aline- or rare-earth ele,ent and 6 is a pentavalent* tetravalent or trivalent transition-,etal ele,ent s0ch as Ti or An. (ne o+ the advantages in st0dying this partic0lar class o+ titanate lies in its relatively si,ple electronic and lattice +eat0resD na,ely* in a stoichio,etric co,po0nd ;aTi(& a relevant electron is only single &d electron per each Ti site*whose networ7 +or,s a si,ple* appro@i,ately c0?ic* lattice1-&. These ,aterials are at the +oc0s o+ scienti+ic research d0e to their potential technological applications4. (r?ital degrees o+ +reedo,* in addition to spin* charge* and lattice str0ct0re* are gaining increasing interest in c0rrent solid-state physics. That is* in ,anganites the E0estion o+ or?ital order plays a 7ey role in the 0nderstanding o+ electronic properties s0ch as the colossal ,agnetoresistant e++ect. In the orthorho,?ic perovs7ite ;aAn(& !An&<9&d4" one +inds a di++erent scenario. Fere the eg ?and is occ0pied ?y one electron* the degeneracy is li+ted ?y the Gahn-Teller !GT" e++ect* and the or?itals are ordered. ;aTi(& is an anti+erro,agnetic &d1 Aott-F0??ard ins0lator with a Neel te,perat0re o+ TN = 14% 3. It has degenerate t2g or?itals. The role o+ the or?ital degrees o+ +reedo, in this syste, is still 0nclear#-'. Bith the increase o+ no,inal hole doping =* the syste, 0ndergoes a phase change +ro, an ins0lating phase to a ,etallic phase at =cIA C $.$# and the lowte,perat0re anti+erro,agnetic phase disappears at =c,ag C $.$'. It is +o0nd that o0r co,p0ted res0lts on ther,odyna,ic properties s0ch as cohesive and ther,al properties o+ ;aTi(&<=>2 0sing /.IA a+ter i,proving ,odi+ied rigid ion ,odel !A.IA" developed recently ?y .en0 -hoithrani et al9-11 and applied s0ccess+0lly on p0re and doped perovs7ite ,anganites and ,0lti+erroic ,aterials are closer to the availa?le e@peri,ental val0es. Perovs7ite-type titanate syste,* ;aTi(&<=>2 is 7nown to ?e a canonical syste, +or the +illing-controlled ins0lator,etal transition and has widely ?een st0died ?y transport* ther,odyna,ic and spectroscopic ,eas0re,ents* as well as theoretically. ;aTi(&<=>2 have ?een s0ggested to have pro,ising scienti+ic and technological applications. (0r co,p0ted speci+ic heat res0lts +ollow the sa,e trends o+ variation with corresponding e@peri,ental data ?y H. Tag0chi et al2. !ormalism of e"tended ri#id ion model $%IM The a0thor has recently developed an e@tended rigid ion ,odel !/.IA" ?y incorporating the long-range !;." -o0lo,? attraction* the short-range !S." Fa+e,eisterIJlygare !FJ" type overlap rep0lsion e++ective 0p to the second neigh?o0r ions* the van der Baals !vdB" attraction d0e to the dipoleIdipole !dId" and dipoleIE0adr0pole !dIE" interactions and Kero point energy !LP/" e++ects in the +ra,ewor7 o+ ,odi+ied rigid ion ,odel !A.IA" developed earlier ?y 0s9-11. The +ra,ewor7 o+ /.IA is derived +ro, the +ollowing interionic interaction potential9 φ/.IA C φA.IA < φLP/ !I" Bhere* φA.IA potential !?y .en0 -hoithrani et al9" is given ?y

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Advances in Physics Theories and Applications ISSN 2224-719 !Paper" ISSN 222#-$%&' !(nline" )ol.19* 2$1& - Selected +ro, International -on+erence on .ecent Trends in Applied Sciences with /ngineering Applications

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φA.IA = − e2

 n b1 β kk M e@pO! rk + rk M − rkk M " > ρ 1N +   Z k Z k M r +  nM ∑  b2 [β kk e@p{(2 r k − r kk ) > ρ 2} + β k Mk M e@p{(2 r k M − r k Mk M ) > ρ 2}] 2 kk M 2    −% −' − ∑ c kk M r kk M − ∑ d kk M r kk M !1"
−1 kk M kk M kk M

!2" and φLP/ C !9>'" N 36θ5 The sy,?ols involved eE0ations !1" and !2" are the sa,e as those de+ined in o0r earlier papers11. Fere* 7 !7P" denote the positive !negative" ions and the s0, is ta7en over all the ions !77P". In /E. !1"* the +irst ter, represents the long-range -o0lo,? attraction* the second and third ter,s are the shortrange Fa+e,eister-Jlygare12 type rep0lsion operating 0pto the second neigh?o0r ions. The +o0rth and +i+th ter,s in it are the vdB attraction energies d0e to the dipole-dipole !d-d" and dipole-E0adr0pole !d-E" interactions with ckk’ and dkk’ as the corresponding vdB coe++icients. The val0es o+ these coe++icients are esti,ated ?y 0sing the +ollowing e@pressions9 c77Q C !&e2R7 R7Q > 2," S!R7>N7"1>2 < !R7Q>N7Q"1>2T-1 !&" d77Q C !27e2R7 R7Q > '," S!R7>N7"1>2 < !R7Q>N7Q"1>2T2 S!R7>N7"1>2<2$>&!R7R7Q>N7N7Q"!R7Q>N7Q"T-1 !4" derived +ro, the Slater-3ir7wood )ariational !S3)" ,ethod1&. Fere* , and e are the ,ass and charge o+ electrons* respectively. αk!αk’" are the polariKa?ilities o+ 7!7Q" ions D N7 !N7Q" are the e++ective n0,?er o+ electrons responsi?le +or the polariKation o+ 7!7Q" ions. The val0es o+ ckk’ and d77’ are eval0ated 0sing the /Es. !&" and !4" and +ollowing the proced0re prescri?ed ?y 0s911 . /.IA has ?een developed and applied ?y the a0thor* pro?a?ly +or the +irst ti,e* to descri?e the transport properties o+ the perovs7ite ,aterials. The speci+ic heat* ,odel para,eters and the transport properties s0ch as cohesive and ther,al properties o+ ;aTi(&<=>2 co,po0nd 0sing their e@pressions given in o0r earlier papers9-11. The co,p0ted res0lts th0s o?tained are presented and disc0ssed ?elow. & %esult and discussion The inp0t data +or di++erent co,positions !=" are o?tained +ro, the )egards law14 0sing the e@peri,ental data1-&* #-' reported +or the parent ,e,?ers and ther,odyna,ic relations on the lines o+ re+s.9-11. 8sing these inp0t data and the vdB coe++icients !ckk’ and dkk’" calc0lated +ro, the S3) ,ethod1&* the ,odel para,eters !ρ1* ?1 and ρ2* ?2" have ?een eval0ated +or di++erent co,positions != C $.$1* $.$4* $.$%* $.$'* and $.1%" and te,perat0res !T2 U #$ 32" +or ;aTi(&<=>2 and listed the, in Ta?le 1. The ,odel para,eters !ρ and ?" have shown decreasing trend with increasing co,position* indicating the decrease in the strength o+ these perovs7ite-type titanate syste,s. 8sing the ,odel para,eters !ρ and ?"* the val0es o+ cohesive energy !φ" +or ;aTi(&<=>2 have ?een co,p0ted to test the validity o+ o0r ,odel. It is +o0nd +ro, Ta?le 1 that the ,agnit0de o+ the cohesive energy decreases +ro, φ C -142.71 e) !+or = C $.$1" to -141.'7 e) !+or = C $.1%". Also* the co,p0ted val0es o+ cohesive energy at all given co,positions are in good agree,ent with the availa?le ,eas0red data +or the parent ,e,?er ;aAn(&1# o+ the ,anganite +a,ily. The negative val0es o+ the cohesive energy indicate the sta?ility o+ the co,po0nd. The val0es o+ .estrahalen +reE0encies +ro, = C $.$1 to $.1% shows con+or,ity with the e@peri,ental val0e !V$ C 1$.7%4 TFK" availa?le only at &$$ 31% +or ;aTi(&. It is also noticed +ro, Ta?le 1 that the higher val0es o+ 5e?ye te,perat0res indicate the presence o+ higher phonon +reE0encies in these ,aterials. The calc0lated val0es o+ 5e?ye te,perat0res o+ ;aTi(&<=>2 != C $.$1* $.$4* $.$%* $.$'* and $.1%" are +o0nd to lie in the range #$1.7%1-#$$.&%2 3* which is closer to the reported val0e o+ θ5 !C #1%.% 3"1% +or ;aTi(& and also co,para?le to the range !&$$-##$ 3"9-11 o+ten +o0nd in perovs7ite ,aterials. The co,p0ted val0es o+ 4rWneisen para,eter !γ" is decreasing slightly on varying co,position = C $.$1 to $.1% and its val0e lies in ?etween 2 and & as reported ?y 5ia et al17. The speci+ic heat c0rve o+ Perovs7ite-type titanate syste,* ;aTi(&<=>2 != C $.$1* $.$4* $.$%* $.$'* and $.1%" o?tained 0sing /.IA is in good agree,ent with the e@peri,ental c0rve2 !see Jig. 1". It is interesting to note +ro, Jig.1 that ?oth the calc0lated and e@peri,ental speci+ic heats increase linearly with te,perat0re indicating the display o+ phononic contri?0tions !∼T&" in ;aTi(&<=>2. J0rther* the val0es o+ speci+ic heat increase rapidly with the increase o+ = +ro, $.$1 to $.$' whereas decreases +ro, $.$' to $.1%. This critical ?ehavior is d0e to the anti+erro,agnetic insta?ility that has ?een investigated +or the +illing controlled ins0lator-,etal transition syste,* ;aTi(&<=>2* ?y transport and speci+ic heat ,eas0re,ents2. It is noticed that electronic speci+ic heat coe++icient ta7es a ,a@i,0, val0e !X17 ,G>,ol.32" at = C $.$' and is red0ced in the anti+erro,agnetically ordered phase o?served ?y Tag0chi et al2.

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Advances in Physics Theories and Applications ISSN 2224-719 !Paper" ISSN 222#-$%&' !(nline" )ol.19* 2$1& - Selected +ro, International -on+erence on .ecent Trends in Applied Sciences with /ngineering Applications

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Ta?le1- Aodel Para,eters and Ther,odyna,ic Para,eters o+ ;aTi(&<=>2 Aodel Para,eters Ther,odyna,ic Para,eters = Ti-( Y1 !Z" $.#7$1 $.##9' $.#&79 $.#14% $.#2%2 Ti-( ?1!1$-12 erg" $.997' $.9'%1 $.9%14 $.92&7 $.942# ;a-( Y2 !Z" $.7&7% $.719' $.712# $.7$19 $.7$72 ;a-( ?2!1$-12 erg" $.%47$ $.%&17 $.%2$# $.%19' $.%2$1 φ !e)" -142.71 -142.$9 -141.9% -141.79 -141.'7 !141.'1"1# V$ !TFK" 1$.4#9 1$.4&' 1$.4&& 1$.427 1$.4&$ !1$.7%4"1% [5 !3" #$1.7%1 #$$.7#2 #$$.#14 #$$.21$ #$$.&%2 !#1%.%"1% \

$.$1 $.$4 $.$% $.$' $.1%

2.'9 2.'# 2.'1 2.7' 2.'$ !2-&"17

Jig. 1 The variations o+ speci+ic heat with te,perat0re +or ;aTi(&<=>2* where the solid lines and lines with circles are the present ,odel calc0lation and e@peri,ental data2* respectively. ' (onclusions The syste,atic trend o+ variations o+ ther,odyna,ic properties and the closer agree,ent with the availa?le e@peri,ental data on speci+ic heats reveal the s0ita?ility and appropriateness o+ /.IA +or the ;aTi(&<=>2 ,aterials. So,e o+ the res0lts are* pro?a?ly* ?eing reported +or the +irst ti,e and hence o0r co,,ent on their relia?ility are restricted 0ntil the report o+ e@peri,ental data on the,. Presently* these val0es are o+ acade,ic interest and they can serve as g0ide to the e@peri,ental wor7ers in +0t0re. It ,ay ?e concl0ded that /.IA is e++ectively 0se+0l ,odel +or the 0ni+ied and co,prehensive st0dy o+ the perovs7ite ,aterials* ?eca0se the ?ea0ty o+ o0r potential lies in satis+actory e@planation o+ the variety o+ physical properties !s0ch as cohesive* ther,al* elastic* ther,odyna,ic" with sa,e s0ccess9-11 +or the ,0lti+erroics* ,anganites and other perovs7ite ,aterials. Acknowled#ement .en0 -hoithrani wo0ld li7e to ac7nowledge with than7s the Science and /ngineering .esearch 6oard* 5epart,ent o+ Science and Technology !5ST"* 4overn,ent o+ India* New 5elhi +or providing the +inancial assistance and the Jast Trac7 Ho0ng Scientist Award. %eferences 1. 4eorges A* 3otliar 4* 3ra0th B 2 .oKen?erg A G* Rev Mod Phys, %' !199%" 1&. 2. Tag0chi H* (70da T 2 To70ra H* Phys Rev B, #9 !1999" 12. &. Fe,?erger G* 3r0g von Nidda F-A* Jritsch )* 5eisenho+er G 2 ;o?ina S* arXiv:cond !at* $&$&$7$v& Scond-,at.str-elT* 7 A0g* !2$$&". 4. .odrig0eK / /* Pro++en Th* ;lo?et 2 .yne G G* Phys .ev 6* 71 !2$$#" 1$44&$. 1$7

Advances in Physics Theories and Applications ISSN 2224-719 !Paper" ISSN 222#-$%&' !(nline" )ol.19* 2$1& - Selected +ro, International -on+erence on .ecent Trends in Applied Sciences with /ngineering Applications

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#. %. 7.

5agotto /* Fotto T 2 Aoreo A* Phys .ep* &44 !2$$1" 1. 3ho,s7ii 5 I* Int G Aod Phys 6* 1# !2$$1" 2%%#. Saitoh /* (7a,oto S* Ta7ahashi 3 T* To?e 3* Ha,a,oto 3* 3i,0ra T* Ishihara S* Aae7awa S 2 To70ra H* Nat0re !;ondon"* 41$ !2$$1" 1'$. '. Paras7evopo0los A* Aayr J* Fartinger -* Pi,enov A* Fe,?erger G*;0n7enhei,er P* ;oidl A* A07hin A A* Ivanov ) H0 2 6al?ashov A A* G Aagn Aagn Aater* 211 !2$$$" 11'. 9. .en0 -hoithrani* 4a0r N 3 2 Singh . 3* G Alloys 2 -o,p* 4'$ !2$$9" 427. 1$. .en0 -hoithrani* 4a0r N 3 2 Singh . 3* G Aagn Aagn Aater*&21 !2$$9" 4$'#. 11. .en0 -hoithrani* N. 3. 4a0r* AIP -on+. Proc.* 1447 !2$12" 11#9. 12. Fa+e,iester 5 B 2 Jlygare B F* G -he, Phys* 4& !19%#" 79#. 1&. Slater G - 2 3ir7wood 3 4* Phys .ev ;ett* &7 !19&1" %'2. 14. )egard ;* L Phys* # !1921" 17. 1#. 5e So0Ka .oger A* Sai+0l Isla, A* Ivers- Ti++e /* G Aater -he,* 9 !1999" 1%21D 3ovalova N 1%. N* 4avartin G ;* Shl0ger A ; 2 Stoneha, A A* Physica 6* 7&4 !2$$2" &12. 17. ;i0 -h0n-Aei* Ni-Na4e* -heng Han* 40ang-J0Gi* Physica 6* 4$% !2$11" 192%. 1'. 5ai P* Giandi Lhang* Aoo7 F A* ;ion S F* 5ow?en P A 2 Pl0,,er / B* Phys Rev B, #4 !199%" . &%94.

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