Category:Bethe-Salpeter equations: Difference between revisions

The formalism of the Bethe-Salpeter equation (BSE) allows for accounting the electron-hole interaction in the polarizability, which make the BSE the state of the art approach for calculating the absorption spectra in solids.

Theory

BSE

In the BSE, the excitation energies correspond to the eigenvalues ${\displaystyle {\omega }_{\lambda }}$ of the following linear problem

${\displaystyle \left(\begin{array}{cc}\mathbf{𝐀}& \mathbf{𝐁}\\ {\mathbf{𝐁}}^{*}& {\mathbf{𝐀}}^{*}\end{array}\right)\left(\begin{array}{l}{\mathbf{𝐗}}_{\lambda }\\ {\mathbf{𝐘}}_{\lambda }\end{array}\right)={\omega }_{\lambda }\left(\begin{array}{cc}\mathbf{𝟏}& \mathbf{𝟎}\\ \mathbf{𝟎}& -\mathbf{𝟏}\end{array}\right)\left(\begin{array}{l}{\mathbf{𝐗}}_{\lambda }\\ {\mathbf{𝐘}}_{\lambda }\end{array}\right).}$

The matrices ${\displaystyle A}$ and ${\displaystyle A^{*}}$ describe the resonant and anti-resonant transitions between the occupied ${\displaystyle v,v^{\prime }}$ and unoccupied ${\displaystyle c,c^{\prime }}$ states

${\displaystyle A_{vc}^{v^{\prime }{c}^{\prime }}=({\epsilon }_v-{\epsilon }_c){\delta }_{v{v}^{\prime }}{\delta }_{c{c}^{\prime }}+⟨c{v}^{\prime }|V|v{c}^{\prime }⟩-⟨c{v}^{\prime }|W|c^{\prime }v⟩.}$

The energies and orbitals of these states are usually obtained in a ${\displaystyle G_0{W}_0}$ calculation, but DFT and Hybrid functional calculations can be used as well. The electron-electron interaction and electron-hole interaction are described via the bare Coulomb ${\displaystyle V}$ and the screened potential ${\displaystyle W}$.

The coupling between resonant and anti-resonant terms is described via terms ${\displaystyle B}$ and ${\displaystyle B^{*}}$

${\displaystyle B_{vc}^{v^{\prime }{c}^{\prime }}=⟨v{v}^{\prime }|V|c{c}^{\prime }⟩-⟨v{v}^{\prime }|W|c^{\prime }c⟩.}$

Due to the presence of this coupling, the Bethe-Salpeter Hamiltonian is non-Hermitian.

A common approximation to the BSE is the Tamm-Dancoff approximation (TDA), which neglects the coupling between resonant and anti-resonant terms, i.e., ${\displaystyle B}$ and ${\displaystyle B^{*}}$. Hence, the TDA reduces the BSE to a Hermitian problem

${\displaystyle A{X}_{\lambda }={\omega }_{\lambda }{X}_{\lambda }.}$

In reciprocal space, the matrix ${\displaystyle A}$ is written as

${\displaystyle A_{vc\mathbf{𝐤}}^{v^{\prime }{c}^{\prime }{\mathbf{𝐤}}^{\prime }}=({\epsilon }_v-{\epsilon }_c){\delta }_{v{v}^{\prime }}{\delta }_{c{c}^{\prime }}{\delta }_{{\mathbf{𝐤}\mathbf{𝐤}}^{\prime }}+\frac{2}{\mathrm{\Omega }}\sum _{\mathbf{𝐆}\ne 0}{\overline{V}}_{\mathbf{𝐆}}(\mathbf{𝐪})⟨c\mathbf{𝐤}|e^{i\mathbf{𝐆}\mathbf{𝐫}}|v\mathbf{𝐤}⟩⟨v^{\prime }{\mathbf{𝐤}}^{\prime }|e^{-i\mathbf{𝐆}\mathbf{𝐫}}|c^{\prime }{\mathbf{𝐤}}^{\prime }⟩-\frac{2}{\mathrm{\Omega }}\sum _{{\mathbf{𝐆},\mathbf{𝐆}}^{\prime }}{W}_{{\mathbf{𝐆},\mathbf{𝐆}}^{\prime }}(\mathbf{𝐪},\omega ){\delta }_{{\mathbf{𝐪},\mathbf{𝐤}\mathbf{-}\mathbf{𝐤}}^{\prime }}⟨c\mathbf{𝐤}|e^{i(\mathbf{𝐪}\mathbf{+}\mathbf{𝐆})}|c^{\prime }{\mathbf{𝐤}}^{\prime }⟩⟨v^{\prime }{\mathbf{𝐤}}^{\prime }|e^{-i(\mathbf{𝐪}\mathbf{+}\mathbf{𝐆})}|v\mathbf{𝐤}⟩,}$

where ${\displaystyle \mathrm{\Omega }}$ is the cell volume, ${\displaystyle \overline{V}}$ is the bare Coulomb potential without the long-range part

${\displaystyle {\overline{V}}_{\mathbf{𝐆}}(\mathbf{𝐪})=\{\begin{array}{ll}0& \text{ if }G=0\\ V_{\mathbf{𝐆}}(\mathbf{𝐪})=\frac{4\pi }{|\mathbf{𝐪}+\mathbf{𝐆}{|}^2}& \text{ else }\end{array},}$

and the screened Coulomb potential ${\displaystyle W_{\mathbf{𝐆},{\mathbf{𝐆}}^{\prime }}(\mathbf{𝐪},\omega )=\frac{4\pi {ϵ}_{\mathbf{𝐆},{\mathbf{𝐆}}^{\prime }}^{-1}(\mathbf{𝐪},\omega )}{|\mathbf{𝐪}+\mathbf{𝐆}||\mathbf{𝐪}+{\mathbf{𝐆}}^{\prime }|}.}$

Here, the dielectric function ${\displaystyle {ϵ}_{\mathbf{𝐆},{\mathbf{𝐆}}^{\prime }}(\mathbf{𝐪})}$ describes the screening in ${\displaystyle W}$ within the random-phase approximation (RPA)

${\displaystyle {ϵ}_{\mathbf{𝐆},{\mathbf{𝐆}}^{\prime }}^{-1}(\mathbf{𝐪},\omega )={\delta }_{\mathbf{𝐆},{\mathbf{𝐆}}^{\prime }}+\frac{4\pi }{|\mathbf{𝐪}+\mathbf{𝐆}{|}^2}{\chi }_{\mathbf{𝐆},{\mathbf{𝐆}}^{\prime }}^{\mathrm{R}\mathrm{P}\mathrm{A}}(\mathbf{𝐪},\omega ).}$

Although the dielectric function is frequency-dependent, the static approximation ${\displaystyle W_{\mathbf{𝐆},{\mathbf{𝐆}}^{\prime }}(\mathbf{𝐪},\omega =0)}$ is considered a standard for practical BSE calculations.

The macroscopic dielectric which account for the excitonic effects is found via eigenvalues ${\displaystyle {\omega }_{\lambda }}$ and eigenvectors ${\displaystyle X_{\lambda }}$ of the BSE

${\displaystyle {ϵ}_M(\mathbf{𝐪},\omega )=1+\underset{\mathbf{𝐪}\to 0}{\lim }v(q)\sum _{\lambda }{|\sum _{c,v,k}⟨c\mathbf{𝐤}|e^{i\mathbf{𝐪}\mathbf{𝐫}}|v\mathbf{𝐤}⟩X_{\lambda }^{cv\mathbf{𝐤}}|}^2\times (\frac{1}{{\omega }_{\lambda }-\omega -i\delta }+\frac{1}{{\omega }_{\lambda }+\omega +i\delta }).}$

How to

• BSE calculations

References