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Quasi-harmonic Approximations

Alessandro Erba

alessandro.erba@unito.it

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

Dulong-Petit Law (1)

In 1819, Dulong and Petit noted that the molar specific heat of all elementary solids

is very nearly 6.

In 1831 Neumann extended this law to say that each atom in the solid contributes 6

cal/g mol K to the specific heat of the solid.

approaches 6 cal/g mol K.

Dulong-Petit Law (2)

Although these laws are by no means exact, they strongly suggest that some

underlying physical principle might be responsible for the degree of success they

enjoy.

Dulong-Petit Law (3)

In 1871, Boltzmann showed how a classical model for a crystal based on the

equipartition of the energy could provide a simple explanation to the Dulong-Petit

law.

The original idea of equipartition was that, in thermal equilibrium, energy is shared

equally among all of its various forms.

Each degree of freedom contributes with kBT to the thermal internal energy of the

system.

Equipartition therefore implies that in thermal equilibrium, the oscillator has average

energy

Dulong-Petit Law (4)

In 1871, Boltzmann showed how a classical model for a crystal based on the

equipartition of the energy could provide a simple explanation to the Dulong-Petit

law.

Each atom in the solid can oscillate in three

independent directions, so the solid can be viewed

as a system of 3N independent simple harmonic

oscillators, where N denotes the number of atoms

in the lattice. Since each harmonic oscillator has

average energy kBT,

the average total energy of the solid is U = 3NkBT.

using the relation R = NakB, U = 3RT.

The constant volume specific heat is just the temepreature derivative of the internal

energy:

3R = 5.972 cal/mol K

Dulong-Petit Law (5)

In 1871, Boltzmann showed how a classical model for a crystal based on the

equipartition of the energy could provide a simple explanation to the Dulong-Petit

law.

3R = 5.972 cal/mol K

Dulong-Petit Law (5)

In 1871, Boltzmann showed how a classical model for a crystal based on the

equipartition of the energy could provide a simple explanation to the Dulong-Petit

law.

3R = 5.972 cal/mol K

Dulong-Petit Law (5)

equipartition of the energy could provide a simple explanation to the Dulong-Petit

law.

temperatures, due to quantum effects.

3R = 5.972 cal/mol K

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

Statistical Thermodynamics (1)

description of the microscopic states accessible to the fundamental constituents

of matter and the thermodynamic properties of the macroscopic system.

laws, what are the observable properties of a system containing a very large number

of such particles?

Statistical Thermodynamics (2)

longer than the typical relaxation times of microscopic events and thus

measures a dynamical time average over a multitude of accessible microscopic

states.

properties:

(time-dependent) (time-independent)

Statistical Thermodynamics (2)

longer than the typical relaxation times of microscopic events and thus

measures a dynamical time average over a multitude of accessible microscopic

states.

properties:

(time-dependent) (time-independent)

OFTEN IMPRACTICAL

Statistical Thermodynamics (3)

The ensamble approach is valid under the Ergodic Hypothesis (EH), which

assumes that this system exhibits the same average properties in space as a single

system exhibits in time:

The EH implies that in its dynamical evolution during a very long time, the system

explores all possible states:

Statistical Thermodynamics (4)

Different kinds of ensambles can be defined:

MICRO-CANONICAL ENSAMBLE

This ensamble is not very simply applicable to the systems we usually study in the

laboratory, which are in thermal equilibrium with their surroundings, but it is centrally

involved in molecular dynamics simulations.

Statistical Thermodynamics (4)

Different kinds of ensambles can be defined:

GRAND-CANONICAL ENSAMBLE

Statistical Thermodynamics (4)

Different kinds of ensambles can be defined:

CANONICAL ENSAMBLE

partcicles and it is central to Monte Carlo simulations.

Statistical Thermodynamics (5)

The Canonical Partition Function

Statistical Thermodynamics (5)

The Canonical Partition Function

Statistical Thermodynamics (5)

The Canonical Partition Function

Statistical Thermodynamics (5)

The Canonical Partition Function

Statistical Thermodynamics (6)

Different Degrees of Freedom

Statistical Thermodynamics (6)

Different Degrees of Freedom

freedom as independent, the canonical partition function can be factorized as:

So that

For an ideal solid, there are no translational and rotational degrees of freedom, so

the partition function reduces to:

Statistical Thermodynamics (6)

Different Degrees of Freedom

Given that the energy separation among electronic energy levels is much larger than

the thermal energy, the electronic contribution to the partition function is negligible:

And thus:

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

Molecular Vibrations (Harmonic)

The Harmonic Approximation assumes a truncation of the nuclear potential at

second-order (quadratic form) and implies that the nuclear motion can be

described in terms of 3N -6(5) independent quantum harmonic oscillators:

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

Vibrations in Solids (Harmonic)

Crystals contain a huge number of atoms, which implies a huge number of

vibrational degrees of freedom.

3N vibrational DOF

but now N

It seems impractical...

Vibrations in Solids (Harmonic)

We can start by describing the relative motion of atoms in the reference cell:

Vibrations in Solids (Harmonic)

Atoms in different lattice cells can vibrate with a certain phase shift with

respect to each other (phonon dispersion).

Vibrations in Solids (Harmonic)

Atoms in different lattice cells can vibrate with a certain phase shift with

respect to each other (phonon dispersion).

Vibrations in Solids (Harmonic)

Atoms in different lattice cells can vibrate with a certain phase shift with

respect to each other (phonon dispersion).

Wave-vector k = 2/

or equivalently

A point in the

first Brollouin zone

A. Erba MSSC2016 Torino (Italy), September 2016

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

Einstein's Model for the Specific Heat

In 1907, Einstein showed how the quantization concept that explained Planck's

distribution law for blackbody radiation also explained the low-temperature behavior

of the heat capacities of the solid elements:

Einstein's Model for the Specific Heat

In 1907, Einstein showed how the quantization concept that explained Planck's

distribution law for blackbody radiation also explained the low-temperature behavior

of the heat capacities of the solid elements:

Einstein's Model for the Specific Heat

In 1907, Einstein showed how the quantization concept that explained Planck's

distribution law for blackbody radiation also explained the low-temperature behavior

of the heat capacities of the solid elements:

Debye's Model for the Specific Heat

In 1912, Debye develops his model for estimating the phonon contribution to the

specific heat in solids. He basically assumes a linear dependence of phonon

frequencies on wave-vector k:

Debye's Model for the Specific Heat

In 1912, Debye develops his model for estimating the phonon contribution to the

specific heat in solids. He basically assumes a linear dependence of phonon

frequencies on wave-vector k:

Debye's Model for the Specific Heat

In 1912, Debye develops his model for estimating the phonon contribution to the

specific heat in solids. He basically assumes a linear dependence of phonon

frequencies on wave-vector k:

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

Direct Space Approach to Phonon Dispersion

How can we compute the actual phonon dispersion? We follow a direct space

approach:

Direct Space Approach to Phonon Dispersion

How can we compute the actual phonon dispersion? We follow a direct space

approach:

Direct Space Approach to Phonon Dispersion

We need to solve the harmonic Schrdinger equation for the nuclear motions. The

usual way is to factorize it into separate ones, each associated to a wavevector k.

The Hessian matrix is Fourier transformed into a set of dynamical matrices:

The elements of the diagonal matrix provide the vibrational frequencies of the

phonons with wavevector k, while the columns of the eigenvectors matrix give the

corresponding normal coordinates:

Direct Space Approach to Phonon Dispersion

is then expressed as:

the nuclear motion are then completely characterized:

Direct Space Approach to Phonon Dispersion

The partition function takes the form:

Q or, equivalently Q Q Q

By substituting this expression into the statistical-thermodynamic definitions of the

thermodynamic functions we get:

Harmonic Thermodynamic Properties

HARMONIC

Specific Heat

108 k points

MgO

64 k points

8 k points

4 k points

1 k point

J. Chem. Phys., 142, 044114 (2015)

Harmonic Thermodynamic Properties

Specific Heat

Specific Heat

Entropy 124115 (2014)

Diamond

Phys. Chem. Chem. Phys., 17, 11670-11677 (2015)

Drawbacks of the Harmonic Approximation

Dynamics of the system:

HARMONIC APPROXIMATION

- Spectroscopic properties (IR and Raman spectra);

- From phonon density of states, Inelastic Neutron Scattering (INS) spectra;

- Thermodynamic properties such as Entropy and constant-volume Specific Heat;

- Anisotropic Displacement Parameters (ADPs) and EXAFS Mean Square Relative

Displacements (MSRD)

- Debye-Waller and Dynamic X-ray Structure Factors

- ....

BUT...

- Elastic constants independent of temperature;

- Equality of constant-pressure and constant-volume specific heats;

- Infinite thermal conductivity;

- ...

Beyond the Harmonic Approximation

Dynamics of the system:

- VSCF, VPT, VCI, TOSH, ...

QUASI-HARMONIC APPROXIMATION

- Allows to evaluate thermal expansion;

- Allows to compute constant-pressure specific heat;

- Allows to compute isothermal and adiabatic bulk moduli;

- ...

Beyond the Harmonic Approximation

Dynamics of the system:

- VSCF, VPT, VCI, TOSH, ...

QUASI-HARMONIC APPROXIMATION

- Allows to evaluate thermal expansion;

- Allows to compute constant-pressure specific heat;

- Allows to compute isothermal and adiabatic bulk moduli;

- ...

Outline

the energy)

function, independent degrees of freedom)

- Quantum models for the heat capacity of solids (Einstein's and Debye's models)

constant-pressure properties, isothermal bulk modulus)

QHA

The harmonic expression for the Helmholtz free energy is retained and an explicit

dependence of vibration frequencies on volume is introduced:

expansion coefficient is defined as:

QHA: Validity Domain

Is the QHA valid at all temperatures? Generally NOT. It depends on the system and on

pressure.

AE, M. Shahrokhi, R. Moradian and R. Dovesi,

J. Chem. Phys., 142, 044114 (2015)

QHA: Validity Domain

Is the QHA valid at all temperatures? Generally NOT. It depends on the system and on

pressure.

AE, M. Shahrokhi, R. Moradian and R. Dovesi,

J. Chem. Phys., 142, 044114 (2015)

QHA: Validity Domain

Is the QHA valid at all temperatures? Generally NOT. It depends on the system and on

pressure.

AE, M. Shahrokhi, R. Moradian and R. Dovesi,

J. Chem. Phys., 142, 044114 (2015)

EXPLICIT

QHA ANHARMONIC

TERMS

Structural and Elastic Properties

AE, M. Shahrokhi, R. Moradian and R. Dovesi,

J. Chem. Phys., 142, 044114 (2015)

MgO

Isothermal bulk modulus:

Structural and Elastic Properties

AE, J. Chem. Phys., 141, 124115 (2014)

Diamond

Structural and Elastic Properties

Phys. Chem. Chem. Phys., 17, 11670-11677 (2015)

Corundum Al2O3

Anisotropic Thermal Expansion

AE, J. Maul, M. De la Pierre and R. Dovesi,

J. Chem. Phys., 142, 204502 (2015)

Forsterite Mg2SiO4

Combining Temperature and Pressure

2900 km

depth

Pressures up to

~140 GPa

Temperatures between

~800 K and 1200 K

Combining Temperature and Pressure

AE, J. Maul, R. Demichelis and R. Dovesi, AE, J. Maul, M. De la Pierre and

Phys. Chem. Chem. Phys., 17, 11670-11677 (2015) R. Dovesi, J. Chem. Phys., 142,

204502 (2015)

Combining Temperature and Pressure

AE, J. Maul, R. Demichelis and R. Dovesi, AE, J. Maul, M. De la Pierre and

Phys. Chem. Chem. Phys., 17, 11670-11677 (2015) R. Dovesi, J. Chem. Phys., 142,

204502 (2015)

P-V-T Relation

P-V-T

Corundum Al2O3

Phys. Chem. Chem. Phys., 17, 11670-11677 (2015)

P-V-T Relation

In situ X-ray diffraction:

P-V-T

T. Katsura, A. Shatskiy, M. G. M. Manthilake, S.

Zhai, H. Fukui, D. Yamazaki, T. Matsuzaki, A.

Yoneda, E. Ito, A. Kuwata et al., Phys. Earth Planet.

Inter. 174, 86 (2009).

Forsterite Mg2SiO4

J. Chem. Phys., 142, 204502 (2015)

Constant-pressure Specific Heat

The QHA allows to compute constant-pressure thermodynamic quantities:

constant-P

constant-V

Theor. Chem. Acc. - Special Issue Chitel2015, 135, 36 (2016)

Constant-pressure Specific Heat

QHA

Specific Heat

216 atoms

128 atoms

16 atoms

8 atoms MgO

2 atoms

J. Chem. Phys., 142, 044114 (2015)

Constant-pressure Specific Heat

Specific Heat

Specific Heat

Entropy 124115 (2014)

Phys. Chem. Chem. Phys., 17, 11670-11677 (2015)

Department of Chemistry

University of Torino

your kind attention.

Thermal Features of Molecular Crystals

High energy-density materials represent a challenge to Urea:

Materials for non-linear optics state-of-the-art quantum- Intra-molecular

chemical methods covalent interactions

Intra-chain

electrostatic

interactions

Inter-/Intra-chain

H-bonds

Grimme's DFT-D3

Dispersive

TZVP basis sets

interactions

Anisotropic thermo-elasticity via quasi-static calculations

Thermodynamic properties via harmonic and quasi-harmonic calculations

Thermal Expansion

a,b c

Anisotropic Thermal Expansion

a,b c

Thermodynamics

a,b c

Thermo-elasticity

HARMONIC

Thermo-elasticity

HARMONIC

CORRECT

Thermo-elasticity

HARMONIC

QUASI-STATIC

CORRECT

Thermo-elasticity

HARMONIC

QUASI-STATIC

CORRECT

ADIABATIC CORRECTION

Thermo-elasticity

HARMONIC

QUASI-STATIC

CORRECT

Commun., 52, 1820-1823 (2016)

ADIABATIC CORRECTION

Thermo-elasticity

HARMONIC

QUASI-STATIC

CORRECT

Commun., 52, 1820-1823 (2016)

ADIABATIC CORRECTION

Thermo-elasticity

HARMONIC

QUASI-STATIC

CORRECT

Commun., 52, 1820-1823 (2016)

ADIABATIC CORRECTION

Thermo-elasticity

HARMONIC

QUASI-STATIC

CORRECT

Commun., 52, 1820-1823 (2016)

ADIABATIC CORRECTION

Department of Chemistry

University of Torino

your kind attention.

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