Mathematics for Nanoscale Materials Research Atomic-to-Macroscale Connection

Anter El-Azab Mechanical Engineering Department Florida State University At the time this presentation was given, the author was with the Fundamental Science Directorate
Pacific Northwest National Laboratory

Second DOE Workshop on Multiscale Mathematics Denver, Colorado, July 20-22, 2004

Comments on statistical mechanics and homogenization theory Scale invariance (statistical homogeneity) and modeling of continua Breakdown of statistical homogeneity at nanoscale need for new framework A perspective on multiscale mathematics

Earliest Multiscale Mathematics Framework (1800s)Statistical Mechanics

Famous subjects of the 19th century: thermodynamics, fluid theory, solid mechanics. Key question: how to interpret macroscale properties of matter from understanding of the underlying molecular system. First multiscale formalismskinetic theory (Maxwell, Boltzmann, others). Boltzmann was the first to make connection to macroscale thermodynamics starting from micro-scale picture.

S = k ln
Role of Statistical Mechanics: Starting at statistics and dynamics of a discrete system, statistical mechanics offers a mathematical framework for deriving the governing (conservation) laws at the macroscale, the constitutive laws (closure of the conservation laws), and properties. Statistical mechanics offers an interpretation of macroscale fields and properties in terms of the characteristics of the underlying discrete system. Mathematics: Discrete dynamics (large phase space) continuous fields (PDE).

Heterogeneous Continua
Continuum-continuum connectionprediction of upper scale properties & governing equations

Coarse scale field

Fine scale field

Homogenization theory: capture fields and properties at higher scale, given those at mesoscale Multiscale theories: capture coarse and fine scale solutions simultaneously (HMM, VMM, ) Statistical homogeneity is important for homogenization theory. Medium is statistically homogenous if LD >> L RVE >> LMSF If statistical homogeneity is violated, the problems becomes an essentially multiscale problem

Scale Invariance (Properties of Continua)

For fixed thermodynamic state, specific properties of a medium do not depend on the size of the medium (mass density, elasticity, etc.)

Homogenization theory view Volume (ensemble) average is independent of size of RVE.

Statistical mechanics view: Scale invariance requires system to be in the thermodynamic limit (infinitely extended)a limit at which extensive properties such as mass, energy, entropy, etc., are all additive.

Nanoscale Matter Systemsexample : self assembled systems

(a) (b)

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40 nm

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130 nm

(c)

(d)

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130 nm

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130 nm

Nanoscale oxide structures produced by OPA-MBE (quantum dots, quantum rings, wires) Novel optical, electronic, magnetic, and catalytic properties.

Continuum descriptions do not suit materials in the nanoscale regime of dimensions due to the lack of statistical homogeneity

Statistical view of scales (where nanoscale systems fit?)

Molecular systems (Protein, clusters) 103-104 Framework Molecular mechanics

500 nm

Classical continua Avogadros number - 1023 Framework Continuum physics Statistical mechanics

Unexplored territory Aspects of both molecular and continuous systems, and strong scale dependence A multiscale framework must be used which framework (?)

Ultimately we will need to develop theoretical (conceptual) frameworks specific to the unexplored size ranges

Molecular view statistical homogeneity is the basis of continuum description of matter

Large ODE systems Molecular Mechanics (classical, quantum) (discrete)

Working with phase spaces

Statistical homogeneity

Statistical Mechanics (statistics, dynamics, interactions)

Phenomenological/Conceptual Framework Systems of PDE Field Theoretic Descriptions Continuum Thermodynamics

Discretization methods (discretized PDEs) ODEs algebraic systems

Compute

Statistical homogeneity permits molecular level mechanics modeling of continua

Statistical homogeneity: size of the region of interest (RVE) is significantly larger than the molecular units and smaller than the overall size of the material. RVE = computational cell Ensemble theory gives the rules for dynamics, evolution equations of the atomic system

Molecule RVE Macroscale crystals

What if statistical homogeneity breaks down? We get into the realm of non-extensive systems (ranges of interactions comparable with the size of the system (nanoscale materials, e.g., oxides, and also galaxies )

Nanoscale oxide

In ionic materials, coulomb forces need to be computed over the entire system

Large ODE systems

Molecular Mechanics (classical, quantum) (discrete)

The mathematics of dimensional reduction (projection)

Statistical homogeneity

Statistical Mechanics (statistics, dynamics, interactions)

Non-extensive system description

Phenomenological/Conceptual Framework Systems of PDE Field Theoretic Descriptions Continuum Thermodynamics

Discretization methods (discretized PDEs) ODEs algebraic systems

Coarse-grained description (ODEs Algebraic)

Compute

This is important business

Why is this business important? To model and solve pertinent problems correctly means to invent new theoretical formalisms This will include revisiting the methods of statistical mechanics, including ensemble theory, and adapting these methods to finite but large phase spaces (nanoscale regime ) This will also include bridging discrete and continuous mathematical models (ODE and PDE systems)

Molecular systems (Protein, clusters) 103-104

Unexplored territory Aspects of both molecular and continuous systems

Classical continua Avogadros number - 1023

Emerging Methods
Domain Decomposition Methods: define discrete and continuous regions a priori, plus matching conditions across interfaces Quasi-continuum Method: interpolation of atomic coordinates, adaptive meshing, constrained minimization Bridging Scale Method: attempts to obtain molecular level details in a continuum setting (discretecontinuum analogue of VMM)

These methods have been developed for crystalline materials only

The needs
Formalisms must work for crystalline and non-crystalline (amorphous) systems. Projection (dimensional reduction) done in the phase space, not in the real space only.
(q i , pi ); i = 1, 2, ..., N; N very large

Dynamics require reworking ensemble theory for non-extensive systems. Hamiltonian of the system, for example, represented directly in terms of the reduced phase space coordinates; also other variables (temperature, pressure, etc.). Principle of ensemble equivalence do not extend to non-extensive systems need a truly new conceptual framework.

Molecular Mechanics (classical, quantum) (discrete) Statistical Mechanics (statistics, dynamics, interactions)

The business of dimensional reduction (projection)

Non-extensive system description

Where does the opportunity lie?

For physicistsnew conceptual frameworks The opportunity for both mathematicians and domain specialists lie in establishing the formalism of dimensional reduction, studying their mathematical structure, proving their convergence and stability, within a newer statistical thermodynamic framework that is valid for non-extensive systems, etc. A major part of this will be achieved computationally. So computing will be used to establish theory, not just theoretical understanding. Coarse-grained description (ODEs Algebraic)

Compute