Elastic interactions and complex patterns in binary systems

One of the many beauties of condensed matter physics is that it can reveal and illuminate how two systems or phenomena that at first appear to be quite different actually involve similar physics. This is an example of universality: for emergent phenomena, many details don't really matter. One example is the similarities between superconductivity and superfluidity. A consequence of universality is that the same concepts, techniques, toy models, and effective theories can be used to describe a wide range of systems.

The complex organometallic molecules, known by the misnomer "spin crossover" compounds, exhibit a rich range of phase transitions and types of spatial order. Key aspects of the physics are the following.

• Each transition metal ion can be in one of two possible states: low-spin or high-spin. 
• The size of each molecular complex depends on the spin state.
• Consequently, the molecules interact with their neighbours via elastic interactions.

A toy model that can describe this is expanding balls connected by springs. Various versions of this type of model are reviewed here. The simplest version is the chain model below.

It turns out there are other classes of systems described by similar models. As far as I am aware, this was first pointed out in Consequences of Lattice Mismatch for Phase Equilibrium in Heterostructured Solids Layne B. Frechette, Christoph Dellago, Phillip L. Geissler

That paper is motivated by experiments on the growth of semiconductor quantum dots, by ion exchange, such as when CdSe is bathed in an Ag-rich solution and Ag2Se is produced with heterostructures (i.e., patterns of Ag and Se ions) that are different from the bulk crystal.

They consider the balls and springs model above on a triangular lattice.

They also point out how similar physics is relevant to binary metal alloys, e.g, AgCu, citing 

Ising model for phase separation in alloys with anisotropic elastic interaction—I. Theory, P. Fratzl and O. Penrose

Those authors consider a square lattice with elastic interactions associated with bond stretching along the edges and diagonals of the squares and bending of the square angles.

Frechette et al. also mention experiments on thin films of  DNA modified metallic nanoparticles. Compared to atomic systems these can tolerate larger lattice-mismatch before the formation of defects due to lattice strain.

Other systems (not mentioned) described by similar Ising models are metal-hydrogen systems, where the Ising pseudospin signifies whether a hydrogen atom is present at a particular site in the metallic crystal.

Frechette et al. start with the ball and springs model and "integrate out" the springs to obtain an effective Hamiltonian, which is an Ising model.

The spatial range of the interaction between Ising spins is shown in the colour-shaded plot below.

The interaction has two components.

One is an infinite range "ferromagnetic" part, seen as the light blue below.

The second is a short-range interaction which is mostly "antiferromagnetic" (i.e., red), but extends over several lattice sites. (Note, this interaction will be frustrated on the triangular lattice).

Using this toy model, Frechette et al. can obtain complex patterns (heterostructures) similar to those seen in quantum dots grown by ion exchange.

There is some subtle (and confusing) physics associated with deriving the Ising model from the ball and springs model. 

Due to the long-range nature of elastic interactions, the boundary conditions matter. 

The infinite range part of the Ising interaction arises from dealing with the lattice constant for the crystal, depending on the net "magnetisation" of the "spins". But that is a story for another day.

Elastic frustration in molecular crystals

Crystals of large molecules exhibit diverse structures. In other words, the geometric arrangements of the molecules relative to one another are complex. Given a specific molecule, theoretically predicting its crystal structure is a challenge and is the basis of a competition.

One of the reasons the structures are rich and the theoretical problem is so challenging is that there are typically many different interactions between different molecules, including electrostatic, hydrogen bonding, pi-pi,...

Another challenge is to understand the elastic and plastic properties of the crystals.

Some of my UQ colleagues recently published a paper that highlights some of the complexity.

Origins of elasticity in molecular materials

Amy J. Thompson, Bowie S. K. Chong, Elise P. Kenny, Jack D. Evans, Joshua A. Powell, Mark A. Spackman, John C. McMurtrie, Benjamin J. Powell, and Jack K. Clegg

They used calculations based on Density Functional Theory (DFT) to separate the contributions to the elasticity from the different interactions between the molecules. The figure below shows the three dominant interactions in the family of crystals that they consider.

The figure below shows the energy of interaction between a pair of molecules for the different interactions.

Note the purple vertical bar, which is the value of the coordinate in the equilibrium geometry of the whole crystal. The width of the bar represents variations in both lengths that occur in typical elastic experiments.

What is striking to me is the large difference between the positions of the potential minima for the individual interactions and the minima for the combined interactions.

This is an example of frustration: it is not possible to simultaneously minimise the energy of all the individual pairwise interactions. They are competing with one another.

A toy model illustrates the essential physics. I came up with this model partly motivated by similar physics that occurs in "spin-crossover" materials.

The upper (lower) spring has equilibrium length a (b) and spring constant k (k'). In the harmonic approximation, the total elastic energy is

The equilibrium separation of the two molecules is given by

which is intermediate between a + 2R and b. This illustrates the elastic frustration. Neither of the springs (bonds) is at its optimum length.

The system is stable provided that k + k' is positive. Thus, it is not necessary that both k and k' be positive. The possibility that one of the k's is negative is relevant to reality. Thompson et al. showed that the individual molecular interaction energies are described by Morse potentials. If one is far enough from the minimum of the potential, the local curvature can be negative. 

Shape memory alloys

Recently I bought a small wire of NiTinol to have fun with and use in demonstrations to kids. This video gives a spectacular demonstration and attempts to explain how it works. I did not know about their use in stents for heart surgery.

I am still struggling to understand exactly how shape-memory alloys work. According to Wikipedia

The shape memory effect occurs because a temperature-induced phase transformation reverses deformation...Typically the martensitic (low-temperature) phase is monoclinic or orthorhombic . Since these crystal structures do not have enough slip systems for easy dislocation motion, they deform by twinning—or rather, detwinning.

Martensite is thermodynamically favored at lower temperatures, while austenite (B2 cubic) is thermodynamically favored at higher temperatures. Since these structures have different lattice sizes and symmetry, cooling austenite into martensite introduces internal strain energy in the martensitic phase. To reduce this energy, the martensitic phase forms many twins—this is called "self-accommodating twinning" and is the twinning version of geometrically necessary dislocations. 

In different words, I think the essential idea may be the following. In most metals large strains are accomodated by topological defects such as dislocations. These become entangled leading to work hardening and irreversible changes is macroscopic shapes. Shape memory alloys are different because of the low symmetry unit cell. The most natural defects are twinning domain walls and they are not topological and so their formation is reversible.

I am looking forward to reading the book chapter Shape memory alloys by Vladimir Buljak, Gianluca Ranzi

Another fascinating phenomena that is related to shape-memory is "superelasticity", which I discussed in an earlier post on organic molecular crystals, and has recently been reviewed.

I welcome clarification  of the essential physics.

Springy stringy molecular crystals

Perfect crystals are elastic. When a stress is applied and then removed the crystal will bounce back to its original shape. However, in reality no crystal is perfect. If the applied stress is too large the crystal will fracture. Understanding fracture is a big deal in materials science and involves some fascinating physics, including the role of topological defects. 

There are two distinct properties: elasticity and plasticity. They are associated with temporary and permanent changes in shape in response to an applied stress.

They are quantified by the elastic stiffness and the tensile strength, respectively. They reflect material properties at quite different length scales. 

A beautiful and accessible short introduction is 

Stressed out crystals

Bart Kahr & Michael D. Ward 

This is a commentary of some work by a few of my UQ chemistry colleagues, who have made and studied a molecular crystal that is incredibly flexible, as seen in this movie.

Atomic resolution of structural changes in elastic crystals of copper(II) acetylacetonate

Anna Worthy, Arnaud Grosjean, Michael C. Pfrunder, Yanan Xu, Cheng Yan, Grant Edwards, Jack K. Clegg & John C. McMurtrie 

A particular advance is that they use a synchrotron to perform spatially resolved X-ray crystallography to determine how the crystal structure varies spatially within a bent crystal. 

The material of interest has quasi-one-dimensional antiferromagnetic interactions and has been studied theoretically by my condensed matter theory colleagues.

Mechanomagnetics in Elastic Crystals: Insights from [Cu(acac)2]

Elise P. Kenny, Anthony C. Jacko, Ben J. Powell

But there is more...

A recent Science paper describes ice fibers that were particularly flexible.

Elastic ice microfibers

Peizhen Xu, Bowen Cui, Yeqiang Bu, Hongtao Wang, Xin Guo, Pan Wang, Y. Ron Shen, Limin Tong