GW approximation explained

The GW approximation (GWA) is an approximation made in order to calculate the self-energy of a many-body system of electrons.^{[1] [2] [3]} The approximation is that the expansion of the self-energy Σ in terms of the single particle Green's function G and the screened Coulomb interaction W (in units of

\hbar =1 )\Sigma = iGW - GWGWG + … can be truncated after the first term:\Sigma ≈ iG W In other words, the self-energy is expanded in a formal Taylor series in powers of the screened interaction W and the lowest order term is kept in the expansion in GWA.

Theory

The above formulae are schematic in nature and show the overall idea of the approximation. More precisely, if we label an electron coordinate with its position, spin, and time and bundle all three into a composite index (the numbers 1, 2, etc.), we have

\Sigma( 1 , 2 ) = iG( 1 , 2 )W( 1 ^{+,2)} - \int d 3 \int d 4 G( 1 , 3 )G( 3 , 4 )G( 4 , 2 )W( 1 , 4 )W( 3 , 2 ) + ... where the "+" superscript means the time index is shifted forward by an infinitesimal amount. The GWA is then\Sigma( 1 , 2 ) ≈ iG( 1 , 2 )W( 1 ^{+,2)}

To put this in context, if one replaces W by the bare Coulomb interaction (i.e. the usual 1/r interaction), one generates the standard perturbative series for the self-energy found in most many-body textbooks. The GWA with W replaced by the bare Coulomb yields nothing other than the Hartree–Fock exchange potential (self-energy). Therefore, loosely speaking, the GWA represents a type of dynamically screened Hartree–Fock self-energy.

In a solid state system, the series for the self-energy in terms of W should converge much faster than the traditional series in the bare Coulomb interaction. This is because the screening of the medium reduces the effective strength of the Coulomb interaction: for example, if one places an electron at some position in a material and asks what the potential is at some other position in the material, the value is smaller than given by the bare Coulomb interaction (inverse distance between the points) because the other electrons in the medium polarize (move or distort their electronic states) so as to screen the electric field. Therefore, W is a smaller quantity than the bare Coulomb interaction so that a series in W should have higher hopes of converging quickly.

r _{s} . (We only present a scaling argument and will not compute numerical prefactors that are order unity.) Here are the key steps:

• The kinetic energy of an electron scales as

1 /r ^{2} _{s}

• The average electron-electron repulsion from the bare (unscreened) Coulomb interaction scales as

1 /r _{s} (simply the inverse of the typical separation)

• The electron gas dielectric function in the simplest Thomas–Fermi screening model for a wave vector

q is\epsilon(q) = 1 + λ ^{2/q} ^{2} where λ is the screening wave number that scales as r ^{-1 / 2} _{s}

• Typical wave vectors

q scale as 1 /r _{s} (again typical inverse separation)

• Hence a typical screening value is

\epsilon \sim 1 + r _{s}

• The screened Coulomb interaction is

W(q) = V(q)/\epsilon(q)

Thus for the bare Coulomb interaction, the ratio of Coulomb to kinetic energy is of order

r _{s} which is of order 2-5 for a typical metal and not small at all: in other words, the bare Coulomb interaction is rather strong and makes for a poor perturbative expansion. On the other hand, the ratio of a typical W to the kinetic energy is greatly reduced by the screening and is of order r _{s/(1+r} _{s)} which is well behaved and smaller than unity even for large r _{s} : the screened interaction is much weaker and is more likely to give a rapidly converging perturbative series.

Software implementing the GW approximation

• ABINIT - plane-wave pseudopotential method
• BerkeleyGW - plane-wave pseudopotential method
• CP2K - Gaussian-based low-scaling all-electron and pseudopotential method
• ELK - full-potential (linearized) augmented plane-wave (FP-LAPW) method
• FHI-aims - numeric atom-centered orbitals method
• Fiesta - Gaussian all-electron method
• GAP - an all-electron GW code based on augmented plane-waves, currently interfaced with WIEN2k
• GPAW
• Molgw - small gaussian basis code
• NanoGW - real-space wave functions and Lanczos iterative methods
• PySCF
• Quantum ESPRESSO - Wannier-function pseudopotential method
• Questaal - Full Potential (FP-LMTO) method
• SaX - plane-wave pseudopotential method
• Spex - full-potential (linearized) augmented plane-wave (FP-LAPW) method
• TURBOMOLE - Gaussian all-electron method
• VASP - projector-augmented-wave (PAW) method
• West - large scale GW
• YAMBO code - plane-wave pseudopotential method

Sources

• The key publications concerning the application of the GW approximation
• Picture of Lars Hedin, inventor of GW
• GW100 - Benchmarking the GW approach for molecules.

References

1. Lars . Hedin. 73720887. New Method for Calculating the One-Particle Green's Function with Application to the Electron-Gas Problem. 10.1103/PhysRev.139.A796. Phys. Rev.. 139. 1965. A796–A823. 3A. 1965PhRv..139..796H .
2. Aulbur. Wilfried G.. Jönsson. Lars. Wilkins. John W.. Quasiparticle Calculations in Solids. Solid State Physics. 54. 2000. 1–218. 0081-1947. 10.1016/S0081-1947(08)60248-9. 9780126077544.
3. Aryasetiawan. F. Gunnarsson. O. The GW method. Reports on Progress in Physics. 61. 3. 1998. 237–312. 0034-4885. 10.1088/0034-4885/61/3/002. cond-mat/9712013. 1998RPPh...61..237A. 119000468.

Further reading

• Electron Correlation in the Solid State, Norman H. March (editor), World Scientific Publishing Company
• Ferdi. Aryasetiawan. Correlation effects in solids from first principles.