The document discusses exercises related to condensed matter theory. It covers calculating the Madelung constant for a 2D NaCl crystal structure, deriving an expression for the bulk modulus of NaCl, properties of the hexagonal lattice and its reciprocal lattice, and deriving an expression for the distance between adjacent parallel planes in a crystal lattice.
The document discusses exercises related to condensed matter theory. It covers calculating the Madelung constant for a 2D NaCl crystal structure, deriving an expression for the bulk modulus of NaCl, properties of the hexagonal lattice and its reciprocal lattice, and deriving an expression for the distance between adjacent parallel planes in a crystal lattice.
The document discusses exercises related to condensed matter theory. It covers calculating the Madelung constant for a 2D NaCl crystal structure, deriving an expression for the bulk modulus of NaCl, properties of the hexagonal lattice and its reciprocal lattice, and deriving an expression for the distance between adjacent parallel planes in a crystal lattice.
The document discusses exercises related to condensed matter theory. It covers calculating the Madelung constant for a 2D NaCl crystal structure, deriving an expression for the bulk modulus of NaCl, properties of the hexagonal lattice and its reciprocal lattice, and deriving an expression for the distance between adjacent parallel planes in a crystal lattice.
2024 Applied Theoretical Physics Due: 06.05.2024 Prof. Dr. J. Dzubiella
Exercise 2 for ’Condensed Matter Theory’, SuSe 2024
Email: joachim.dzubiella@physik.uni-freiburg.de Tutorials: Mr. Sven Pattloch; Dr. Sébastien Groh
2.1 Madelung Constant (4 points)
The Madelung constant, A, is used to quantify the elec-
trostatic energy of a single ion in an infinitely large perfect crystal. The Madelung constant is defined as X −sign(qi qj ) rij A= where pij = . (1) pij r0 i̸=j
In the above equation, the primed sum is a double sum
over all particles, rij is the distance between ions i and j, and r0 is the distance between first nearest neighbors. The −sign(qi qj ) indicates the sign of each term of the sum, Figure 1: 2D NaCl crystal struc- and it is +1 if the ions have opposite electric charges, and ture. cations and anions are in −1 if they have an equal charge. blue and red, respectively. r0 is Consider a 2D NaCl crystal structure with cations (A) and the distance between first nearest anions (B) as shown in Figure 1. The charge of the cations neighbors. and anions are qA = +Z and qB = −Z, respectively.
a) Propose a Bravais lattice and a basis to describe the primitive cell of the 2D NaCl crystal structure. b) Calculate the Madelung constant of ion i numerically, e.g., using Python by considering neighboring ions up to the nth coordination shell. The latter can be defined by all particles within a sphere of radius n·r0 . Consider different values of n and try to obtain a converged result for large n. Can you estimate an error? Compare the calculated Madelung constant to value from the literature.
2.2 Bulk modulus (5 points)
In standard thermodynamics, the isothermal bulk modulus is defined as:
∂P κ = −V (2) ∂V T
where P is the pressure, V the volume, and T the fixed temperature, and the lattice energy of N ion pairs for NaCl is now approximated by e2 B X 1 U (r) = N − A+ n , (3) 4πϵ0 r r pnij i̸=j
where A = 1.748 is the Madelung constant and pij = rij /r with rij and r being the distance between ions i and j and the separating distance between first nearest neighbors, respectively. a) Use the lattice energy per ion pair, u(r) = U/N , for NaCl, to express the bulk modulus κ as a function of u(r) and its derivatives with respect to r in the limit of vanishing temperature. ∂U
Hint: The pressure reduces to P = − ∂V T,{Ni } for T = 0 K, because entropic effects vanish. Express volume changes by the changes in the lattice distances. b) Finally, express κ in equilibrium as a function of A and the equilibrium nearest distance r0 . Hint: The dependencies between B, r0 and A can be found from the energy minimization principle in equilibrium.
2.3 Reciprocal of the hexagonal lattice (6 points)
b) What is the close-packing fraction of (hard spheres) in this unit cell? c) Show that the reciprocal lattice of the hexagonal Bravais√ lattice is also a hexagonal lattice with lattice constants crec = 2π/c and arec = 4π/ 3a, rotated through 30 about the ◦
z-axis with respect to the direct (i.e., real-space) lattice. Which ratio c/a of the hexagonal Bravais lattice leads to the same ratio crec /arec of the reciprocal lattice. d) What is the relation between the volumes of the primitive cells in real and reciprocal space? e) The Bravais lattice generated by three primitive vectors of equal length a, making an equal angle, θ, with one another is known as the trigonal Bravais lattice. Show that the reciprocal of a trigonal Bravais is also trigonal, with angle θ∗ given by cos θ∗ = − cos θ/[1 + cos θ], and a primitive vector length, a∗ given by a∗ = (2π/a)(1 + 2 cos θ cos θ∗ )−1/2 .
2.4 Distance between adjacent parallel planes (5 points)
Consider a plane (hkl), in a crystal lattice which intersects the crystal axis at x1⃗a1 , x2⃗a2 , and x3⃗a3 where xi ∈ Q.
⃗ = h⃗b1 + k⃗b2 + l⃗b3 is perpendicular to this
a) Demonstrate that the reciprocal lattice vector G plane. b) Demonstrate that the distance between two adjacent parallel planes of the lattice is dhkl = ⃗ 2π/|G|. a c) For a simple cubic lattice of unit length a, demonstrate that dhkl = √ h2 +k2 +l2 .
