Quantum Mechanical Approach of Phase Transformation

7/23/2019 Quantum Mechanical Approach of Phase Transformation

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Eur. Phys. J. B 76, 379390 (2010)DOI:10.1140/epjb/e2010-00217-0

Regular Article

THEEUROPEANPHYSICAL JOURNALB

Quantum mechanical aspect of first order phase transitionof crystals

J. Kobayashia

Department of Applied Physics, Waseda University, Shinjuku-ku, Tokyo, 169-8555, Japan

Received 12 March 2010 / Received in final form 27 May 2010Published online 16 July 2010 c EDP Sciences, Societa Italiana di Fisica, Springer-Verlag 2010

Abstract. It has been generally believed that some external physical porperties, e.g. volume, enthalpy,and entropy, etc. change discontinuously at first order phase transition temperatures, since Ehrenfestsproposition. However, the deviation from this proposition was often found in many crystals. As the progressof experimental methods and the accuracy develop the number of crystals that manifest unusual transitionprocesses is increasing. Notably aberrant phenomena are as follows. An intermediate phase appears whosecrystal structure is undoubtedly different from those of the low and high temperature forms. The peakof differential thermal analysis of specific heat is splitted into two as if one transition inevitably inducesanother. The interpretation of these abnormal behaviors in the vicinity of the transition is certainly beyondreach of thermodynamic ideas. We assumed that the eigenkets of Boltzmanns H of each phase in thevicinity of the transition temperature interact to produce perturbing state. Then the intermediate phasenamed M phase emerges, and its eigenket is the superposition of eigenkets of commuting Hamiltonian ofthe two temperature phases. It is natural that the new M phase has different structure from those of thetwo phases. The above mentioned phenomena occurring in dichlorobenzophenone, NaNO2, 1-Ethyl-3-(4-methylpentanoyl)urea, and VO2 are explained by this quantum mechanical theory.

1 Introduction

Gibbs free energy G of low (1) and high (2) temperatureforms of a crystal, that is functions of temperature T andpressure P is expressed by curved planes in a regular TandPspace. The intersection of these two planes draws asingle curved line indicating common G values. In a specialcase of a constantP, the intersection line breaks into twodifferent lines crossing at certain temperature To, whereGof the two phases coincide. In this case, a transformationcan takes place from one phase to another reversibly. Theorder of such a phase transformation in solids was defined

by Ehrenfest [1]; it is the same as the derivative of theGibbs free energy which show a discontinuous change atthe transition. Volume, enthalpy, and entropy etc. are thetypical thermodynamical quantities exhibiting first ordertransition, and thermal expasivity and heat capacity arethose of the second order transition.

The general features of a first order phase transition,which is abbreviated FOPT in what follows, are knownas follows. (i) In the equilibrium state of the two phasesat To the transition occurs reversibly from the smallerentropy phase to the higher entropy one. As the changeof entropy is discontinuous, the latent heat develops. (ii)The change of the fraction of the two phases is discon-tinuous. (iii) The transitions exhibit generally hysteresis

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phenomenon. These phenomena can be perfectly under-stood by thermodynamical theories.

It is important to note that these general conditionsare not always exactly held in the real FOPTs as re-viewed comprehensively by Herbstein [2]. Discrepanciesof real phenomena against thermodynamical theories werealready noticed in days of 1950s by pioneer workers. Es-pecially Ubbelohde [3] found an intermediate phase ap-pearing in the process of FOPT between the two phases.Mnyukh[4] put forward a theory that the FOPTs are com-pleted by nucleation-to-growth mechanism. Therefore thecrystal is always inhomogeneous in the process of FOPTs.It is worth-stressing that in accordance with the progressof experimental methods and accuracy abnormal factshave been more revealed in FOPTs. Especially it needsemphasis that most of aberrant phenomena in FOPT seementirely unintelligible by thermodynamical view points.We will survey difficult problems of FOPT in the nextchapter, and try to elucidate origins of these effects onquantum mechanical ground in the later chapters.

2 Problems of first order phase transitionin crystals

Accurate knowledges of FOPT in crystals cannot be ob-tained without having overcome various experimental dif-ficulties. Especially care must be paid to keep constant
http://www.epj.org/http://dx.doi.org/10.1140/epjb/e2010-00217-0http://dx.doi.org/10.1140/epjb/e2010-00217-0http://www.epj.org/


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380 The European Physical Journal B

Fig. 1. Smeared free energy in the vicinity of transition pointof low and high temperature phases (after Herbsten[2]).

temperatures accurately for long time, and to avoid localcoagulation of constituent components in the body. How-ever, it has been confirmed that the following phenomenaare often observed even under sufficiently careful treat-ments.

(i) Generation of an intermediate phase which is appre-ciably different from 1 and 2 phases in the processof FOPT. Ubbelohde [3] drew attention on the pre-monitory phenomena preceding FOPT and found a

specific intermediate phase to form between 1 and2 phases, on which he named hybrid crystal orsmeared transition. The hybrid crystal is consistedof sub-units associated with cells of 1 and 2 phasesfulfilling the characteristics of a single crystal on aver-age. As the temperature moves away from the trans-formation point, the distinguishable sub-units disap-pear. In essence the hybrid crystal seems independentfrom 1 and 2 phases but resembled to be a mixingmedium of them. Ubbelohde struggled to interpretthe formation of hybrid crystal on the thermodynam-ical stand, and reached a concept that G1 and G2lines become smeared near To as shown in Figure1.Rao and Rao [5] suggested that the aforementionedfree energy planes of both phases might swell whenTo is approached. At any rate, this effect cannot begiven rational solutions from macroscopic ideas.

(ii) Nucleation and growth mechanism. Mnyukh [4] in-vestigated the process of observations that the trans-formation proceeds mostly as inhomogeneous media.Mnyukhs idea certainly explains the characteristicproperty of FOPTs, viz. transformation hysteresis ac-companied by superheating and supercooling. On theother hand, Gooding and Morris[6] assured theoret-ically that in the case of FOPT, the fluctuation ofdensity of the transforming phase does not increasewhen the transition temperature is approached.It is natural to consider that the nucleation of a newphase in the body of the host phase requires ad hoc

Fig. 2. Temperature dependence of specific heat of [Fe(2-pic)3]Cl2-C2H5OH (after Herbstein [2]).

strain energysand internal surface energyw. Let thecommon free energy of 1 and 2 phases in process ofFOPT is defined as

G| = G (P , T , s12, w12) for superheating,and

G = G (P , T , s21, w21) for supercooling.(1)

It is readily understood that owing to the presence ofadditive energy s and w, transitions take place dif-ferent temperatures from original To. Thus it appearsthat Mnyukhs theory assists to understand one char-acteristic nature of FOPTs, but is unable to sustainthe criticism on the aforementioned inhomogeneity ofcrystal media.

(iii) Aberration of physical properties on FOPT. Aberrantphysical properties are found in certain crystals thatare unintelligible by the thermodynamical idea. (a)Physical properties of the intermediate phases areunambiguously not the mixture of those of the con-

stituent 1 and 2 phases. (b) A peak of specific heataround To is splitted into two with different extentsof separation. One example of Fe(2-pic)3Cl2-EtOH isshown in Figure2. Then a serious conclusion is likelyto be led that a FOPT is apt to induce another one.(c) It appears appreciably that the crystal structureof the interleaved phase is different from those of anyone of 1 and 2 phases.

The reasonable explanations of these unusual phenom-ena have not yet been given. It seems to us that thereis scarcely possibility to resolve these phenomena on thethermodynamical basis. It appears worth-while to con-sider them on quantum mechanical view point, sincethe phase transitions of crystal are essentially related tochange of microscopic atomic motions.


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J. Kobayashi: Quantum mechanical aspect of first order phase transition of crystals 381

3 Quantum mechanical analysis of first orderphase transition

3.1 Basic theory

A dynamical state (q) of the systems in a quantum me-chanical ensemble containing the similar non-interactingsystems is generally represented by a linear combinationof the eigenkets of any other observable, where q is co-ordinate observable. The density operator of an ensem-ble reads,

=i

|ip2i i| (2)

|i is an eigenket of (i = 1, 2, . . . , n , . . .), and p2i is theeigenvalue belonging to it. Physically Pi = p2i indicatesthe weight of finding|i in the ensemble. In accordancewith above statement,

|i

can be expressed by the linear

combination of eigenkets,|um,|un . . ., etc. belonging toany arbitrary observableof the ensemble. That is to say,

|i =n

cin|un (3)

wherecin = i|un is the probability amplitude ofnstateof . Let take the representation of by using the basickets of|n un. . .etc. One of a diagonal componentnnof the density matrix is written

nn = n|c

|iPii|n =i

Picinc

in (4)

which is an eigenvalue ofexpressed by using eigenvaluesof density matrix.

Now define an as

an =i

n|pi|i =i

picin. (5)

Then Wn = (anan) means the probability of finding amember of the ensemble in the n eigenstate of . If Nsystems are contained in the ensemble, a components ofdensity matrix is ensemble averaged value. For instance,

nn = 1

N

N=1

anan =anan. (6)

We use a single bar to denote a mean value which hasbeen obtained by the single process of averaging over therange of probabilities corresponding to quantum mechani-cal state of a single system, and to use a double bar to de-note a mean value which has been obtained by the processof averaging over the systems of an ensemble. Let diagonalcomponent of matrix be defined as R, for example,

Rn = nn = Wn = anan. (7)

Then the following relation holds in an ensemble.

|n =Rn|n. (8)

As a useful function of the density operator, it producesensemble average value of any observable. Taking A ob-servable as an example,

A=mn A

mnnm. (9)

This relation, matrix multiplication of the two matrices,is rewritten in the form

A= TrAP = TrP A. (10)

In order to see analogs between quantum mechanicalquantities and corresponding thermodynamic ones, we de-rive first the canonical density matrix. The condition, un-der which the systems will remain in equilibrium, i.e. ap-pear unaltered under the elapse of time, requires fromHeisenberg equation,

[H, ] = 0, (11)whereH is the Hamiltonian operator of the system. Inanother word must be a function ofH. The proof isgiven: we argue that the two separate systems are com-bined into composite system, whose Hamiltonian is justthe sum of the separate Hamiltonians. On the other hand,the density operator of the composite system is a productof the separate density operators of the two systems. Itfollows that the relationship between andHmust be ofthe functional form

= eX/eH/, (12)

where X and are parameters. Thus the density opera-tor is a function of Hamiltonian. Then canonical densityensemble fulfils a satisfactory condition of being in a equi-librium state. It is natural that

n

Rn =n

eXEn

= 1 (13)

whereEn is an internal energy of then complexion of theHamiltonian of the ensemble. The mean internal energyof an ensemble is written by using (10).

E= n

RnEn = n

eXEn

En. (14)

We consider now the ensemble average of Boltzmanns H

of both 1 and 2 phases. Definition ofHis given by

H=n

Rnln Rn. (15)

Namely, H is an ensemble-average of ln R. H of an en-semble can measure deviation from equilibrium and tendsto decrease with time, reaching finally a minimum value.By (13) and (15), an important relation is obtained

H=n

eXEn

X En

= X E

. (16)


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Furthermore, from (13)

eX/ =n

eEn/ =Z (17)

andX/= ln

n

eEn/ = ln Z (18)

where Z is the partition function. On the other hand,from (16)

H= X

E

X E

2 . (19)

From (13)

n

Rn = n

eXEn

= 0. (20)

If not only X and , but also relevant external coordi-nate qi is assumed to change slightly, E will be conse-quently altered, i.e. (20) becomes

n

eXEn

X

1

Enq1

q1+ En

q2q2+ . . .

X En2

= 0. (21)

For any state n, the generalized external forces Ai aredefined as

A1= Enq1 , A2=

Enq2 , . . . (22)

Naturally

A1=n

eXEn

A1, A2=n

eXEn

A2, . . . (23)

Then, (19) becomes

X

+

1

A1q1+ A2q2+ . . .

X E

2 = 0. (24)

From (19) and (21)

H= E

X E

2

= E

+

1

A1q1+ A2q2+ . . .

. (25)

In a case that the external forces are not applied to thesystem, (25) becomes

H= E

. (26)

On the other hand, thermodynamic theory states that thechange of entropy Sis expressed as

S= E

T +

1

T (A1q1+ A2q2+ . . .) , (27)

Fig. 3. Thermal variation of internal energy E, Helmholtzs

free energy X, and Boltzmanns H function of crystals.

where Eis the internal energy. The similarity between (25)and (27) indicates correlations of entropy S and tem-

perature T with statistical mechanical quantitiesHand , viz.

S

H, and T

/, (28)

where the mark means correlate. A constant withthe dimension of energy over temperature has to be intro-duced to allow for difference in units. From (15)

X=E+ H. (29)

On the other hand, a thermodynamical relation reads

A= E T S (30)

whereA is the Helmholtz free energy. Then we can markthe correlation

A X. (31)In accordance with (18),Xis related with partition func-tion as

X= Tln Z= Tlnn

eEn

T . (32)

3.2 Perturbation theory of first order phase transition

We regard the dynamical state of our crystal to be sepa-rated into two quantum mechanical ensembles correspond-ing to 1 and 2 phases. In Figure3temperature dependence

of mean internal energy of both ensembles E1, andE2 aredrawn. Assume that E1> E2 atT= 0 and both increase


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gradually with increase of temperature. Xof both ensem-bles coincide with each internal energy at T = 0, anddecrease with increase ofT,X2< X1 in the low tempera-ture region, but both curves intersect at Tt and X2> X1

afterward. H1 and H2 take in each ensemble minimumvalue under each E1 and E2 energy. Their temperaturevariations are shown in Figure3. It is important to notethat the two partition functions Z1 andZ2 become equalat Tt, where the 1 ensemble becomes a special state by

joining the 2 ensemble. TotalH of this ensemble changesreversibly into H1 under the partition function. Let thefinal state of 1 ensemble be named as M ensemble orphase.

The original eigenkets ofH1 are designated as 1, . . .n, . . .etc, which are taken as a basis for representation ofthe density matrix of M ensemble. With regard to an ar-

bitrary eigenstaten, say, ofH1, the Schrodinger equationholds as can be inferred from (8).

H1n = Rnn. (33)

The story so far holds under the condition that eigen-

states of H1 and H2 are perfectly orthonormal. Now wefeel it probable and so assume that there exists interac-tion between them which produces eventually a perturb-

ing energyV for the final state H1 or M phase. This ideamay relate to the macroscopic phenomenon of free energyplanes of both phases becoming thicker as the tempera-ture approachesTt as has already been stated. Then (33)

becomes H1n = Rnn (34)

whereH1= H1+ V / (35)

andRn = Rn+ R

(1)n .

Here it is noted that the eigenfunctions ofHand H opera-tors form a complete set. Thus the eigenkets(

i)n (i= 1, 2)

ofH are degenerated with n with a common eigenvalueofRn. Then n is written as

n =i

i(i)n +

b=n

Cnbi

i(i)b (36)

here (i)n are orthonormal eigenfunctions. i and i are

relative weights among (i)n and

(i)b , and Cnb is the in-

teraction coefficient between n and (i)b . By using (34)

and (36), the equation in the perturbed state reads

H1+ V /

i

i(i)n +

b=n

Cnbi

i(i)b

=

Rn+ R(1)n

i

i(i)n +b=n

Cnbi

i(i)b . (37)

The equation of first order in smallness in (37) is written

H1b=n

Cnbi

i(i)b + V /

i

i(i)n =

Rnb=n

Cnbi

i(i)b + R(1)n

i

i(i)n . (38)

In order to express this equation by using Heisenberg rep-

resentation, take the scaler product of(j)b with (38). The

first order shift equation becomes

H1(j)n

b=n

Cnbi

i(i)b +

(j)n V/

i

i(i)n =

(j)n Rnb=n

Cnbi

i(i)b +

(j)n R

(1)n

i

i(i)n . (39)

By the condition that(i)n|(j)b =nbij (39) becomesi

i

(j)n

V / (i)b =jR(1)n . (40)This is a two-dimensional eigenvalue equation. As there isa two-fold degeneracy, a simplified abbreviation is used.

(j)n

V / (i)n =hji . (41)Then (40) can be written

1h11+ 2h12= 1R(1)n

1h21+ 2h22= 2R(1)n . (42)

For realV,hji can be represented by an Hermitian matrix

with eigenvalues R(1)ni, which can be obtained by solving

the determinant,h11 R(1)n h12

h21 h21 R(1)n

= 0. (43)Two eigenvalues are obtained,

R(1)n1 =

12

(h11+ h22) 12 (h11 h22) + 4h2121/2

,

andR(1)n2 =

12

(h11+ h22) + 12

(h11 h22) + 4h212

1/2.

(44)(42) can be expressed in terms of two matrix equations forthe two eigenvaluesRni and vector matrices (1i, 2i).

h11 h12h12 h22

1121

=R(1)n1

1121

, (45)

and h11 h12h12 h22

1222

=R(1)n2

1222

. (46)

In other words,hji matrices have the principal vectors r1(11, 21) and r2 (12, 22), belonging to eigenvalues ofR

(1)n1 and R

(1)n2 respectively. A general figure representing


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Fig. 4. Mohr circle construction of the representation quadricof perturbing energy matrix at Tt.

hijxixj = 1 in the rectangular coordinate system (x1, x2)

is a quadric, i.e. an ellipse in the present case. The prin-cipal vectors r1 and r2 of an ellipse are added to producea superposed vector r= 1r1+ 2r2 which correspond tothe dynamical state of M ensemble, direction of r is, ofcourse, different from those of r1, and r2, and the lengthis determined by distribution coefficients 1 and 2.

3.3 Thermal change of distribution coefficientsaround Tt

It would be of primary importance to evaluate the dis-tribution coefficients in the structure of the M phase at

Tt. H1 andH operators have degerate eigenfunctions nand(

i)n atTt. However, it can be considered that the two

eigenfunctions (1)n and (2)n ofH are entirely indistin-

guishable in the M phase since two equal partition func-tions exist there. As the result, it would be correct toregard thath11, h22 andh12 are represented by the samecomponent h0 say. The lengths and inclination angles of r1 and + 90

of r2 of the principal axes can be ob-tained by using the Mohr circle construction as shown in

Figure 4a, where R(1)n1 = 2h0 and R(1)n2 = 0 from (44).

The lengths of the principal axes defined by h01 and h02 are

marked at 2h0 and zero positions in x1 axis. The princi-pal axes of the ellipse derived from this construction areshown in Figure4b. They become a straight line with halflength of 2h0 and = 45

. Therefore the total inclination

Fig. 5. Mohr circle construction of the representation quadricof perturbing energy matrix slightly aboveTl.

angle of the vector r, i.e. = + is 45, where

is the angle formed by the principal axes of the ellipse,viz. = tan1 h02/h01 = 0. Thus 1= cos45

= 1/2 and1= sin45

= 1/

2.In view of the physical continuity, it would be cor-

rect to infer that the weak perturbing energy V begins toappear from slightly lower temperature Tl than Tt, andafterward it fades away in slightly higher temperatureTh,the width of the total interval Tof the M phase includ-ing Tt being usually very small.

Around Tl, (2)n will be dominant over

(1)n which is

almost negligible. We can take that h11 =h01 0, h22 =h02, h12 0, and 0. The Mohr circle construction isshown in Figure5a in enlarged scale. The resultant ellipse

is indicated in Figure5b, where = 0 and= tan1

=90. Therefore = = 90. Thus 1 = cos 0, and2= sin

= 1.In the temperature interval between Tl and Tt, V in-

creases appreciably, so h11 becomes discernible, while h22decreases. Therefore the distance between h11 and h22is shortened as shown in Figure 6a for the Mohr cir-cle construction, where the principal axes h01, h

02, and

2 are marked. The resultant ellipse is indicated in Fig-ure6b by the principal axes. is larger than 45. Thus1= cos

= cos(+ ), and 2= sin = sin(+ ).

In the temperature range between Tt andTh, the sim-ilar construction is indicated in Figure7a, where the rel-ative positions of h11 and h22 are reversed.

= + becomes smaller than 45 as found in Figure 7b. Thus1= cos

= cos(+ ) and 2= sin = sin(+ ).


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Fig. 6. Mohr circle construction of the representation quadricof perturbing energy matrix betweenTl andTt.

Fig. 7. Mohr circle construction of the representation quadricof perturbing energy matrix betweenTt andTh.

Fig. 8. Mohr circle construction of the representation quadricof perturbing energy matrix slightly belowTh.

At temperature immediately below Th, the similar con-struction is indicated in Figure8a, whereh11= h01,h22=

h020, and = 0. The ellipse becomes a straight line asshown in Figure8b. As = + = 0, 1 = cos

= 1,and 2= sin

= 0.It needs to stress again the significant result just ob-

tained that a dynamical state of the M phase represented

by any eigenket of perturbed H1is the superposition of the

two eigenkets ofH in the unperturbed state. The salientfact is that the M ensemble is accordingly a new phase andits structure is essentially different from those of 1 and 2phases but explicitly related to them. This is the uniqueevidence of the dynamical state of the M phase verified bythe quantum mechanical idea; showing good contrast withthat from thermodynamical one. According to the latter,the pure 1 and 2 phases must coexist independently inthe M phase, and do not produce a new phase having itsunique structure.

The thermal change of the distribution coefficients1and 2in a temperature interval Tof the M phase are in-dicated in Figure9.It is very important that the crystal ofthe M phase exhibits perceptibly changing structure in ac-cordance with the temperature dependence of1 and2.

3.4 Temperature variation of the specific heat

For assessing the validity of the present theory, we willexamine first whether or not it explains the extraordinarythermal dependence of specific heat Cp that has already


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Fig. 9. Temperature variation of relative weight1 and2 ofeigenfunctions of Hamiltonian of 1 and 2 ensembles.

Fig. 10. Derivation of temperature change of specific heatCp. vs. T, (b)d /dT vs. T, (c) dE/d vs. T, (d)Cp vs. T, (e)Cp vs. T for T 0.

been mentioned. For brevity, let the mechanical work doneby the crystals be unconsidered. Then Cp is expressed as

Cp =dE

dT =

dE

dd

dT, (47)

where = cos1 1= sin1 2.

The thermal dependence of can be estimated qual-itatively from the processes of constructing Mohr circles.The result is shown in Figure 10a. which is 90 at Tl(Fig. 5), decreases as T increases, levels off 45 at Tt ascan be readily recognized from Figure4a, finally vanishes

at Th. From this figure d/dT can be evaluated as de-picted in Figure10b. It is noticeable that the two negativepeaks are formed between Tl and Tt and between Tt andTh, nearly symmetrical with respect to the ordinate atTt.

The thermal variation ofdE/d

in the range ofT ofthe M phase can be evaluated in the following.

(i) Tl < T < Tt.

The thermal change of internal energy Eof the Mphase is expressed as

E= 1E1 (1 2) E2= E1cos + E2sin E2.

HencedE

d = E1sin + E2cos , (48)

which manifests a negative peak of

E1 at Tl and

becomes 1/2(E2 E1) at Tt.(ii) Tt < T < Th

E= (1 1) E1 2E2

=E1

E1cos + E2sin

.

HencedE

d =E1sin

E2cos , (49)

which becomes a negative peak ofE2 at Th. Thetemperature dependence ofdE/d is depicted in Fig-ure10c. Finally the temperature dependence ofCp is

obtained by making the product ofd/dTand dE/d

at each temperature. The appearance is shown in Fig-ure10d. Cp shows clearly two peaks nearly symmet-rical with respect to the ordinate at Tt. As T isshortened, the two peaks approach together and fi-nally overlap to appear a nearly single peak as shownin Figure 10e. Thus the present theory resolves thereason why the specific heat manifests sometimes twosplit peaks, while sometimes apparently a single peakatTt.

3.5 Temperature dependence of extensive physicalproperties

Consider an extensive physical property ofA as in chap-ter 3.1. The macroscopically observed value of A in the

M phase is an ensemble averaging A, which is expressed

in (10). ThereforeAMat any temperature in the M phaseis expressed as

AM = TrMA (50)

whereMis the density matrix of the M phase.

The figure of AM cannot be inferred from A of the1 and 2 phases except cases of approaching closely thesephases, because the structure of the M phase differs from


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Fig. 11. Temperature dependence of an external physical

propertyAM in M phase.

either 1 and 2 phases. The characteristic feature ofAM isthat it consists of the two parts separated at Tt. They arerelated by inversion symmetry, because values ofV of the1 and 2 phases are nearly related by reflection symmetry atTt, and 1/2 and 2/1 of both parts are also operated

by the same symmetry. An arbitrary example of AM is

drawn in Figure11a. In cases thatT is small,AMwouldappear to change abruptly at Tt as shown in Figure11b.

Summing-up, the present theory explains most of aber-rant experimental phenomena occurring at FOPT, on

which long issues have been expended as described inChapter 2.

4 Typical examples with discernible M phase

4.1 Dichlorobenzophenone (DBP)

Dichlorobenzophenone manifests very interesting FOPTphenomena. X-ray studies were made mainly by Mitkevichet al. [7] and Zuninga et al. [8]. The crystal shows defi-nite hysteresis of transitions at about 186 K (cooling) and

192 K (heating). The space groups of 1 and 2 phases areI2/candC2/crespectively. The temperature variations oflattice constants are shown in Figure12.It is conspicuousthat those ofa and are closely similar to Figurer 11a,but others seem experimentally inaccurate.

An important evidence of the FOPT of this crystal wasrevealed from NQR spectroscopy. Although single Cl linespectrum in each 1 and 2 phase is observed, four spectrawere measured in the intermediate phase[9]. It is knownthat the NQR spectrum outlines the microscopic environ-ment of the resonant nuclei. In a commensurate systemthe number of NQR lines is determined by the nonequiv-alent nuclear sites in the unit cells.

Mitkevich et al. [7] reported that the intermediatestate must be a mixture of the quasi-C and quasi-I lat-tices. Zuninga et al. [8] showed that it was monoclinic

Fig. 12. Temperature dependence of lattice parameters ofdichlorobenzophenone (after Herbstein [2]).

Fig. 13. Temperature dependence of specific heat ofdichlorobenzophenone (after Herbstein [2]).

but primitive and that new superlattice reflections ap-pear. They insisted that this structure is still a sort ofcoexistence of domains of I- and and C-centering zonesof alternated cells CICI. . . As a conclusion, one cannotdescribe the intermediate state beyond noting that thereseem to be four independent Cl atoms and that the struc-ture appears to be modulated.

The temperature variation of specific heat was mea-sured by Ecolivet et al.[10] as shown in Figure13, where


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Fig. 14. Calorimetric and dilatometric behavior of NaNO2.(a) specific heat vs.T, (b) volume vs.T(after Sakiyama[11]).

splitting of peaks is clearly seen. The overall situation isdescribed by Mitkevich[7]: the phase transition occurs asa sequence of two separate FOPTs with an intermediatestate between 1 and 2 phases. We should like to point outthat the intermediate phase of DBP is undoubtedly the Mphase and its behaviors agree considerably well with ourprediction from the quantum theory.

4.2 NaNO2

NaNO2 was found to undergo FOPT around 163 C by

Sawada et al. [11]; the low temperature Im2mphase is fer-roelectric, and the high temperature Immmphase is para-electric. Tanisaki [12] reported the presence of a new inter-mediate phase in the temperature region of 163164 Cfrom X-ray studies. Sakiyama et al. [13] made calorimet-ric and powder dilatometic studies. They found splittingof heat capacity around 163 C as shown in Figure14a,and unusual volume vs. temperature curve in Figure14b.It seems that the behavior of volume is approximately sim-ilar to Figure11a except abrupt change at 163 C. It canbe said that the presence of double peaks of Cp and of

Fig. 15. DSC curve of 1-Ethyl-3-(4-methylpentanoyl)(afterHerbstein [2]).

apparent thermal tendency of volume support the genera-tion of M phase. Besides, Yamada et al. [14] propsed thatthe M phase has unique structure, antiferroelectric with asinusoidal modulation of NO2 ions.

4.3 1-Ethyl-3-(4-methylpentanoyl)urea

Crystal melting is the most magnificent FOPT, accord-

ingly attracts great interest. Hashizume et al. [15] carefullystudied FOPT of 1-Ethyl-3-(4-methylpentanoyl)urea bycalorimetric and X-ray methods. Their DSC curve of thiscrystal is shown in Figure15.There are two splitted peaksat around 369 K and 384 K (melting). We can immediatelyrecognize that these peaks represent the characteristicsplitting of Cp in the M phase. Hashizume et al. ana-lyzed thermal structure change by precisely temperature-resolved diffraction method at every 2 K in the range348374 K.

Hashizume et al.[15] found that the crystal is isostruc-tural with space group of P1 before and after 363 K,but abrupt change of lattice constants occur from type Iunit cells to type II unit cells. Structural change is re-markable; molecular structure of the I region changes intosupramolecular structure of II. The change of the inter-molecular geometries defined by (I)(V) say is shownin Figure 16. It is especially worth-noting that thesupramolecular structure (M phase) makes rapid thermalchange as expected by the theory. This experiment mayprovide the first proof of characteristic change of M phasestructure.

4.4 VO2

When an insulator-to-metal transition is induced in corre-lated insulators or Mott insulators by doping or heating,the resulting conducting state is known radically different


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Fig. 16. Temperature dependence of the various inter-molecular contacts and packing geometries of 1-Ethyl-3-(4-methylpentanoyl)urea (after Hashizume [15]).

from that characterized by free electrons in conventionalmetals. Qazilbash et al. [16] studied prototypical corre-lated insulator VO2 in which the metallic state can beinduced by only increasing temperature.

Using scanning near-field infrared microscope, theyfound nucleation of nanoscale metallic puddles in the hostof the low temperature monoclinic phase slightly belowthe transition temperature ofTt 342 K. Puddles growand connect with themselves within narrow temperatureregion of T 2 K. The insulator-to-metal transitionis followed by severely sudden fading and percolative ap-proach to 360 K, whence the crystal becomes perfectlyrutile type conducting phase. Qazilbash et al. [16] alsoperformed detailed far-infrared spectroscopy on the samespecimen over all the transition temperature range. Thenature of nanostructural puddles regions were separatedtheoretically from that of the host phase by use of aneffective medium theory[17,18]. It is,of course, a naturalprediction that the effective optical constants of these het-erogeneous system are an average of the optical constantsof the insulating and rutile metallic regions weighted by

respective volume fractions. However, they reached veryimportant conclusions. This simple evaluation of opticalconstants of the insulating phase and of the rutile metallicphase at 360 K does not produce a satisfactory descriptionof the far-field infrared data near the onset of insulator-to-metal transition of VO2. This discrepancy indicates thatthe infrared properties of the nanoscaled metallic puddles,once they appear at 342 K, may be different from thoseof the high-temperature rutile metal.

The resistance-temperature curve showing theinsulator-to-metal transition is indicated in Figure 17.The monoclinic insulator to rutile metal transition isunambiguously interleaved by the strongly correlatedmetal within T

2.2 K. Qazilbash et al. point out

that the behavior of insulator-to-metal transition of VO2displays clearly Mott transition feature.

Fig. 17. The phase diagram of VO2 and the resistance vs.temperature curve showing the insulator-to-metal transition(after Qazilbash et al.[16]).

It seems likely to us that insulator-to-metal transi-tion corresponds to the formation of the M phase, sincethe structure of transforming phase is entirely differentfrom those of 1 and 2 phases, and the shape of tempera-ture variation of resistance (Fig.17) resembles Figure11a.The percolative regime over relatively long temperaturerange cannot be precisely understood but appear to besubsidiary effect. Then it may be inferred that the Motttransition of VO2 attributes to the M phase formation.

Baum et al. [19] reported the temperature change ofatomic positions of VO2 by using femtosecond electrondiffraction. This specimen at room temperature was ir-radiated near-infrared pulses whose one pulse energy isenough to drive a phase transition. They were successful

in delineating consecutive atomic shifts within 1 ps. Theprimary shift is relaxing VV pair bonds along the a axisin the low temperature phase without accompanying sub-stantial lattice expansion. Another shift of V atoms takesplace along the c axis direction with slow sound wave ve-locity of 9.2 ns of time constant, thus completing the tran-sition to the rutile structure. This shift is accompanied byshear motion of the lattice.

It is of specific interest that the direction of the firstantibonding shift is rectangular to shear forming shift.Therefore it may be that the antibonding motion is drivenby perturbing energy and fulfills primary prerequisite forthe Mott transition. This temporal experiments of FOPT

is different object from the present study but very use-ful for getting dynamical knowledges of FOPT on atomiclevels.

5 Discussion

The present theory reaches a new interpretation on appar-ently aberrant phenomena occurring at FOPTs of crys-tals. At a FOPT an intermediate M phase is generated asa dynamic state of superposing eigenfunction of averageHamiltonian eigenfunctions of low and high temperaturephases. The primary requisite for the M phase formation is

a weak interaction between two eigenstates ofH1 andH2.However, we feel it necessary to notice that such a kindof effect is not specifically limited in FOPT in crystals.


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A similar effect gives rise to other significant phenomena.For instance, such interactions always exist between eigen-states of optical impermeability in a crystal, thus produc-ing optical activity in the crystals. However, optical ac-

tivity can be found only in 15 noncentrosymmetric classesdue to nullification of the effect by the symmetry opera-tions in other classes. The emergency of incommensuratestate of some ferroelectric crystals indicates an additionalexample. We [20] found that its origin is lifting of a specificlattice vibrational mode degenerating with its conjugatestar as a result of time-reversal symmetry.

Correct clarification of the atomistic mechanisms ofgenerating M phases is highly desirable since it providesinsight into origins of phase transition mechanisms thathave remained uninvestigated. The crystal structure inthe M phase, as partly described in chapter 4, certainlydemonstrates the difference from a simple coexistence of 1and 2 phases even in previous investigations; for exam-

ple, structural modulation and supramolecular structureformation of 1-Ethyl-3-(4-methylpentanoyl)urea may bemostly decisive.

The recent experiments on VO2by Qazilbash et al.[16]reveal an especially significant aspect of the M phase ina correlated insulator. It emerges and proceeds throughthe process of nucleation-and-growth. However, the grow-ing domains are not high temperature phase but thenanoscale M phase. Therefore the mechanism appears dif-ferent from the nucleation-and-growth model proposed byMnyukh[4]. It is a very interesting that domains of VO2appear in the host phase but their structure differs fromthat of high temperature form.

The author expresses his sincere gratitude to Prof. S.C.Abrahams, who provided him with the impetus of beginningthe present work.

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16. M.M. Qazilbash, M. Brehm, Byung-Gyu, P.C. Ho, G.O.Andreev, Bong-Jun Kim, SunJin, Yun, A.V. Balatsky,M.B. Maple, F. Keilmann, H.T. Kim, D.N. Bosov, Science318, 1750 (2007)

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Quantum Mechanical Approach of Phase Transformation

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