CASTEP can calculate the optical properties of solids that are due to electronic transitions.
In general, the difference in the propagation of an electromagnetic wave through vacuum and some other material can be described by a complex refractive index, N:
Eq. CASTEP 48
In vacuum N is real, and equal to unity. For transparent materials it is purely real, the imaginary part being related to the absorption coefficient by:
Eq. CASTEP 49
The absorption coefficient indicates the fraction of energy lost by the wave when it passes through the material, so that the intensity at the distance x from the surface is I(x)=I(0)exp(-2πηx), where I(0) is the intensity of the incident light.
The reflection coefficient can be obtained for the simple case of normal incidence onto a plane surface by matching both the electric and magnetic fields at the surface:
Eq. CASTEP 50
However, when performing calculations of optical properties it is common to evaluate the complex dielectric constant and then express other properties in terms of it. The complex dielectric constant, ε(ω), is given by:
Eq. CASTEP 51
and hence the relation between the real and imaginary parts of the refractive index and dielectric constant is:
Eq. CASTEP 52
Another frequently used quantity for expressing optical properties is the optical conductivity, σ(ω):
Eq. CASTEP 53
Optical conductivity is usually used to characterize metals, however CASTEP is aimed more toward the optical properties of insulators and semiconductors. The main difference between the two is that intraband transitions play important role in the IR part of the optical spectra of metals and these transitions are not considered at all in CASTEP.
A further property that can be calculated from the complex dielectric constant is the energy loss function. It describes the energy lost by an electron passing through a homogeneous dielectric material and is given by:
Eq. CASTEP 54
Experimentally, the most accessible optical parameters are the absorption, η(ω), and the reflection, R(ω), coefficients. In principle, given the knowledge of both of these, the real and imaginary parts of N can be determined, through Eq. CASTEP 49 and Eq. CASTEP 50. Eq. CASTEP 51 allows expression in terms of the complex dielectric constant. However, in practice, the experiments are more complicated than the case of normal incidence considered above. Polarization effects must be accounted for and the geometry can become quite complex (for example, transmission through multilayered films or incidence at a general angle).
CASTEP supports spin-polarized calculations of optical properties for magnetic systems. Only transitions between the states with the same spin are allowed. For a more general discussion of the analysis of optical data see Palik (1985).
The interaction of a photon with the electrons in the system is described in terms of time dependent perturbations of the ground state electronic states. Currently CASTEP provides two approaches to optical properties calculations; one is based on standard DFT Kohn-Sham orbitals and the other uses more accurate but much more time-consuming time-dependent DFT (TD-DFT) theory.
CASTEP calculates the imaginary part of the dielectric constant, which is given by:
Eq. CASTEP 55
where u is the vector defining the polarization of the incident electric field.
This expression is similar to Fermi's Golden rule for time dependent perturbations, and ε2(ω) can be thought of as detailing the real transitions between occupied and unoccupied electronic states. Since the dielectric constant describes a causal response, the real and imaginary parts are linked by a Kramers-Kronig transform. This transform is used to obtain the real part of the dielectric function, ε1(ω).
The matrix elements of the position operator that are required to describe the electronic transitions in Eq. CASTEP 55 may normally be written as matrix elements of the momentum operator allowing straightforward calculation in reciprocal space. However, this depends on the use of local potentials (Read and Needs, 1991), while in CASTEP nonlocal potentials are more often used. The corrected form of the matrix elements is:
Eq. CASTEP 56
Ultrasoft pseudopotentials produce an additional contribution to optical matrix elements that is also included in CASTEP results.
The intraband contribution to the optical properties affects mainly the low energy infrared part of the spectra. It can be described sufficiently accurately via an semiempirical Drude term in the optical conductivity:
Eq. CASTEP 57
in terms of the plasma frequency ωP and damping parameter γD which depends on many details of the material and is usually obtained from experiment. The Drude damping parameter describes the broadening of the spectra due to effects not included in the calculation. Examples of processes that contribute to this broadening are electron-electron scattering (including Auger processes), electron-phonon scattering, and electron-defect scattering. This last contribution is usually the most important. As a result an a priori determination of the broadening would require knowledge as to the concentrations and kinds of defects present in the sample under study.
For materials that do not display full cubic symmetry, the optical properties will display some anisotropy. This can be included in the calculations by taking the polarization of the electromagnetic field into account. As mentioned above, the unit vector u defines the polarization direction of the electric field. When evaluating the dielectric constant there are three options:
As discussed below, the relative position of the conduction to valence bands is erroneous when the Kohn-Sham eigenvalues are used. In an attempt to fix this problem, inherent in DFT, a rigid shift of the conduction band with respect to the valence band is allowed. This procedure of artificially increasing the band gap is know as a scissor operator.
The level of approximation used here does not take any local field effects into account. These arise from the fact that the electric field experienced at a particular site in the system is screened by the polarizability of the system itself. So, the local field is different from the applied external field (that is, the photon electric field). This can have a significant effect on the spectra calculated (see the example of bulk silicon calculation below) but it is prohibitively expensive to calculate for general systems at present.
In order to calculate any spectral properties it is necessary to identify the Kohn-Sham eigenvalues with quasiparticle energies. Although there is no formal connection between the two, the similarities between the Schrödinger-like equation for the quasiparticles and the Kohn-Sham equations allow the two to be identified. For semiconductors, it has been shown computationally (by comparing GW and DFT band structures) that most of the difference between Kohn-Sham eigenvalues and the true excitation energies can be accounted for by a rigid shift of the conduction band upward with respect to the valence band (Godby et al., 1992). This is attributed to a discontinuity in the exchange-correlation potential as the system goes from (N)-electrons to (N+1)-electrons during the excitation process. There can, in some systems, be considerable dispersion of this shift across the Brillouin zone, and the scissor operator used here will be insufficient.
In connection with the absence of local field effects, excitonic effects are not treated in the present formalism. This will be of particular importance for ionic crystals (for example NaCl) where such effects are well known.
This parameter defines the energy range covered in the calculation, and it also determines the accuracy of the Kramers-Kronig transform. It is clear from Figure 1 that ε2(ω) converges rapidly with the number of conduction bands included.
The value of the energy cutoff that was used in the original SCF calculation of the ground state electron density is an important factor that determines the accuracy of the calculated optical properties. A bigger basis set provides more accurate self-consistent charge density and more variational freedom when searching for wavefunctions of unoccupied states. Figure 2 shows that while it is important to converge the calculation with respect to the planewave cutoff to obtain the correct energies for the spectral features, the shape of those features is reached rapidly.
The accuracy of the ground state electron density depends on the number of k-points used in the SCF run as well as on the basis set quality. Figure 3 reveals that the optical properties converge rapidly with the number of k-points used in the SCF run, which implies low sensitivity to the details of the charge density.
It is important to use a sufficient number of k-points in the Brillouin zone when running optical matrix element calculations. The matrix element changes more rapidly within the Brillouin zone than electronic energies themselves. Therefore, one requires more k-points to integrate this property accurately than are needed for an ordinary SCF calculation. Figure 4 clearly demonstrates the importance of converging the Brillouin zone integration for the optical properties with respect to the k-point density. Both energies and spectral features are strongly affected by the accuracy of this integration.
TD-DFT is a formally exact treatment of electronic excited states. The implementation in CASTEP follows the work of Hutter (2003), which takes a linear response approach to computing excitation energies directly. A benefit of this method is that the response wavefunctions for excited states are calculated and can then be used to derive further properties such as optical matrix elements and atomic forces. In the case of atomic forces, a geometry optimization or molecular dynamics run can be performed for a chosen excitation.
Hutter reformulated the equations of time-dependent Hartree-Fock in the Tamm-Dancoff approximation applied to TD-DFT (Hirata and Head-Gordon, 1999) so that they could be efficiently implemented in a plane-wave basis set. This self-consistent eigenvalue problem is solved in CASTEP by the user’s choice of conjugate gradient or block-Davidson minimizers. The result is a set of electronic excitation energies and linear response wavefunctions.
A technical report on the implementation details of the TD-DFT minimizers can be found at http://www.hector.ac.uk/cse/distributedcse/reports/castep02/.
A second report on the implementation of excited state forces can be found at http://www.hector.ac.uk/cse/distributedcse/reports/castep03/.
Theory in CASTEP