sergey l. bud’ko...second-order phase transitions –continuous in the first derivative –exhibit...

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Novel Materials and Ground States Thermal analysis – heat capacity 590B F09 Sergey L. Bud’ko Detour – phase transitions of 2 ½ order Heat capacity (Сергей Леокадьевич Будько)

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Page 1: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Thermal analysis –

heat capacity

590B F09

Sergey L. Bud’ko

Detour –

phase transitions of 2 ½

order

Heat capacity

(Сергей Леокадьевич Будько)

Page 2: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

2 ½

order phase transition

First-order phase transitions–exhibit a discontinuity in the first derivative

of the free energy with a thermodynamic variable.

Second-order phase transitions–continuous in the first derivative–exhibit discontinuity in a second derivative

of the free energy.

Paul Ehrenfest:

Page 3: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

2 ½

order phase transitionaka: electronic topological transition (ETT), Lifshitz

transition

also:

Page 4: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

2 ½

order phase transition

electronic DOS

parameter:

thermodynamic potential

T=0, no scattering

Page 5: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

2 ½

order phase transition

low temperature, no scattering

ALSO other control parameters

Li-Mg alloy

Page 6: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

2 ½

order phase transition

LSCO high-Tc

SC

QCP in heavy fermions

New box –

the same good old taste

Page 7: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity

Cp

= (dQ/dT)p

= T(∂S/∂T)p

Q –

heat, S -

entropy

Cv

= (dQ/dT)v

= T(∂S/∂T)v

Cp

– Cv

= TVβ2/kT

β

volume thermal expansion, kT

isothermal volume compressibility

For solids Cp

~ Cv

Usually we measure Cp

Page 8: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

* Useful knowledge for useful (structural) materials –

how easy to cool down

* To learn something about electrons and phonons

T -> 0:

Cp

= γT + βT3

(no magnetism)

γ

~ N(0)(1 + λ) -

electronic density of states

λ

-

measure of e-e

(and e-ph) interactions, m*/m0

= (1 + λ)

γ

> 400 mJ/mol K2

“heavy fermions”

an enormous, separate research field that entertains number of us

ΘD

= (1944/β)1/3

-

Debye temperature

(use right units)

tells you something about stiffness of the lattice, helps to understand BCS superconductors [Tc

~ ΘD

exp(-1/N(0)V)]

Page 9: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Lattice heat capacity –

Debye and Einstein

Einstein –

single frequency

Debye –

elastic continuum

(T << ΘD

)

(T >> ΘD

)

Page 10: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Lattice heat capacity –

Debye and Einstein

Debye

Einstein

One can also use realistic phonon DOS and calculate Cp

Einstein Debye

Blackman “realistic”

Page 11: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

•To learn something about magnons

Ferro (ferri) magnets

isotropic

anisotropic

Antiferromagnets

isotropic

anisotropic

And need to remember contributions from electrons and phonons: Cp

= γT + βT3

Page 12: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

•To learn something about superconductors

Cs

~ exp(-1.76Tc

/T) BCS

Page 13: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

•To learn something about superconductors

BCS value (3.53)

phenomenological (1970s)α-model:2Δ0

/kB

Tc

fitting parameter;temperature dependence of SC gap –

BCS;can calculate thermodynamic properties.

Page 14: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

•To learn something about superconductors MgB2

Two-gap superconductor

Page 15: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

•To learn something about superconductors MgB2

Two-gap superconductor

Page 16: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

•To learn something about superconductors

BCS superconductors with paramagnetic impurities

BCS

PM impurities La-Gd

jump in specific heat

Page 17: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?

•To learn something about superconductorsIron-arsenides

ΔCp

~ Tc3

Smart person might be able to make sense out of this

Page 18: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?•To learn something about crystal electric field (Schottky

anomaly)

maximum:

Page 19: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?•To learn something about spin glasses

Scaling hypothesis

Page 20: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?•To learn something about spin glasses

1/T

Tmax

~ 1.5 Tf

Page 21: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

WHY?•To learn something about magnetic transitions

HoNi2

B2

C

Also can play entropy game and evaluate degeneracy of the ground

state

ΔSm

= R ln N

Page 22: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•relaxation (QD PPMS)

simple

more realistic

fit with two exponents

Page 23: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•relaxation (QD PPMS)

calibrated heater and thermometer

sophisticated temperature control and fitting software

need to measure addenda (platform + grease) every time

need to calibrate heater and thermometer in magnetic field

need to shape your sample

vertical 3He platform may oscillate in magnetic field

remember about torque

assembly is fragile

measurements take long time

not good for 1st

order phase transitions

Page 24: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation

τ1

sample to bath;

τ2

response time of the sample

if

τ2

<< 1/w << τ1

Page 25: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation

after Andreas Rydh

Page 26: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation Commercial chips

with membrane

(this is a commercial thermal conductivity gauge)

Page 27: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation Commercial chips

with membrane

you are invited to play with it…

Page 28: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation

after Andreas Rydh

differential cell

Page 29: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation

after Andreas Rydh

differential cell

need to have (at least primitive) thin film technology and lithography

Page 30: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation

fast

scalable, good for small sample

accurate (relative measurements)

easy to put on rotator

can use e.g. in pressure cells

hard to get absolute values

Page 31: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation –

under pressure

Page 32: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Heat capacity –

HOW?•ac modulation –

under pressure

Bridgman cell-heater and thermometer are at ambient pressure

for DAC –

laser heating with thermocouple as sensor

Page 33: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground Statesafter Andreas Rydh

Page 34: Sergey L. Bud’ko...Second-order phase transitions –continuous in the first derivative –exhibit discontinuity in a second derivative of the free energy. Paul Ehrenfest: Novel

Novel Materials and Ground States

Reading: Quantum Design Manual and refs therein

E.S.R. Gopal, Specific heats at low temperatures.

A.Tari, Specific heat of matter at low temperatures.

T.H.K. Barron and G.K. White, Heat capacity and thermal expansion at low temperatures.

Review of Scientific Instruments –

search on “heat capacity…”