The GW approximation is a Green’s function-based method that calculates charged excitation energies, i.e. ionizations potentials (IPs) and electron affinities (EAs). PySCF implements the G0W0 approximation, in which the self-energy is built with mean-field orbitals and orbital energies. Therefore, the results depend on the mean-field starting point, which can be Hartree-Fock or density functional theory. As described below, PySCF has three implementations of the GW approximation, all of which are “full-frequency”.
An example GW calculation is shown below:
#!/usr/bin/env python ''' A simple example to run a GW calculation ''' from pyscf import gto, dft, gw mol = gto.M( atom = 'H 0 0 0; F 0 0 1.1', basis = 'ccpvdz') mf = dft.RKS(mol) mf.xc = 'pbe' mf.kernel() nocc = mol.nelectron//2 # By default, GW is done with analytic continuation gw = gw.GW(mf) # same as gw = gw.GW(mf, freq_int='ac') gw.kernel(orbs=range(nocc-3,nocc+3)) print(gw.mo_energy)
In this example, the
orbs keyword argument is
provided to select which GW orbital energies are requested. By default,
all orbital energies (occupied and unoccupied) will be calculated, which
will increase the cost and may have errors, depending on the method
of frequency integration.
The frequency integration needed for the GW approximation can be done in three
ways, controlled by the
freq_int keyword argument: by analytic continuation
freq_int='ac'), contour deformation (CD,
freq_int='exact'). The first two are much more affordable
and typically provide sufficient accuracy. GW-AC supports spin-restricted and
spin-unrestricted calculations; GW-CD and GW-Exact only support spin-restricted
calculations. Details of the GW-AC and GW-CD implementations in PySCF can be
found in Ref. .
Integration via analytic continuation is implemented in the
that is accessed with
freq_int='ac', which is also
GW module. GW-AC has \(N^4\) scaling and is recommended for
valence states only.
The analytic continuation can be done using a Pade
approximation (default, more reliable) or a two-pole model, controlled by the
GW-AC supports frozen core orbitals for reducing computational cost,
controlled by the
frozen attribute (number of frozen core MOs neglected in GW-AC
calculation). Frozen core orbitals are not supported by other GW methods currently.
There are two ways to compute GW orbital energies, controlled by the
linearized=False (default) solves the quasiparticle equation through a Newton solver
linearized=True employs a linearization approximation:
mygw = gw.GW(mf) # same as freq_int='ac' or GWAC module # mygw.ac = 'pade' # default mygw.ac = 'twopole' mygw.frozen = 1 # default is None mygw.linearized = False # default mygw.kernel(orbs=range(nocc-3,nocc+3))
Integration via contour deformation is implemented in the
that is accessed with
GW-CD has \(N^4\) scaling and is slower, but more robust, than GW-AC.
GW-CD is particularly recommended for accurate core and high-energy states:
mygw = gw.GW(mf, freq_int='cd').run(orbs=[0,1])
Exact frequency integration can be carried out analytically and is implemented
GWExact module that is accessed with
freq_int='exact'. Exact integration
requires complete diagonalization of the RPA matrix, which has \(N^6\)
scaling. However, all orbital energies can be readily obtained without error:
mygw = gw.GW(mf, freq_int='exact').run()
By default, GW-Exact, like the other GW implementations, use the direct random-phase
approximation (dRPA) to screen the Coulomb interaction.
Within GW-Exact, any alternative time-dependent mean-field theory (TDHF, TDDFT, etc.) can
be also used. The instance of an executed
tdscf method can be provided as a
#!/usr/bin/env python ''' GW calculation with exact frequency integration and TDDFT screening instead of dRPA ''' from pyscf import gto, dft, gw mol = gto.M( atom = 'H 0 0 0; F 0 0 1.1', basis = 'ccpvdz') mf = dft.RKS(mol) mf.xc = 'pbe' mf.kernel() from pyscf import tdscf nocc = mol.nelectron//2 nmo = mf.mo_energy.size nvir = nmo-nocc td = tdscf.TDDFT(mf) td.nstates = nocc*nvir td.verbose = 0 td.kernel() gw = gw.GW(mf, freq_int='exact', tdmf=td) gw.kernel() print(gw.mo_energy)
Tianyu Zhu and Garnet Kin-Lic Chan. All-electron gaussian-based g0w0 for valence and core excitation energies of periodic systems. J. Chem. Theory Comput., 17(2):727–741, 2021.