Electron attachment and detachment energies can be accurately described by many-body perturbation theory (MBPT) methods. In particular, the GW approximation (GWA) to the self-energy is a MBPT method that has seen recent interest in its application to molecules due to a promising cost/accuracy ratio.
The GW module implemented in NWChem takes a DFT mean-field approximation to the Green’s function, G0, in order to solve the quasiparticle equation at the one-shot G0W0 or at various levels of the eigenvalue self-consistent GW approach (evGW). Since the mean-field orbitals are kept fixed in all these approaches, the results depend on the actual starting point G0 (hence, they depend on the exchange-correlation functional chosen for the underlying DFT calculation). For example, it has been known that a large fraction of exact exchange is needed for the accurate prediction of core-level binding energies at the one-shot G0W0 level.
For further theoretical insights and details about the actual implementation in NWChem, please refer to the paper by Mejia-Rodriguez et al1.
GW input is provided using the compound directive
GW ... END
The actual GW calculation will be performed when the input module encounters the TASK directive.
TASK DFT GW
DFT must be specified as the underlying QM theory before
GW. The charge, geometry, and
DFT options are all specified as
In addition to an atomic orbital basis set, the GW module requires
an auxiliary basis set to be provided in order to fit the four-center
electron repulsion integrals. The auxliary basis set can have either the
cd basis or
ri basis names (see also DFT). Three combinations can be obtained:
- If a
ri basisis given without a
cd basis, the ground-state DFT will be performed without density fitting, and the GW task will use the
ri basisto fit the integrals.
- If a
cd basisis given without a
ri basis, both DFT and GW tasks will be performed using the
cd basisto fit the integrals.
- If both
ri basisare present, the
cd basiswill be used for the DFT task, while the
ri basiswill be used for the GW task.
GW Input directive¶
There are sub-directives which allow for customized GW calculations. The most general GW input block directive will look like:
GW RPA CORE EVGW [<integer eviter default 4>] EVGW0 [<integer eviter default 4>] FIRST <integer first_orbital default 1> METHOD [ [analytic] || [cdgw <integer grid_points default 200>] ] ETA <real infinitesimal default 0.001> SOLVER [ [newton <integer maxiter default 10> ] || [graph] ] STATES [ [ alpha || beta ] [occ <integer number default 1>] [vir <integer default 0>] ] CONVERGENCE <real threshold default 0.005> [<string units default ev>] END
The following sections describe these keywords.
RPA triggers the computation of the RPA correlation energy.
This adds a little overhead to the CD-GW approach.
CORE and FIRST¶
CORE keyword forces to start counting the
FIRST molecular orbital upwards.
FIRST keyword has no meaning without
EVGW and EVGW0¶
EVGW keyword trigger the partial self-consistnet evGW approach,
where both the Green’s function G and the screened Coulomb W are updated
by using the quasiparticle energies from the previous step in their
EVGW0 triggers the evGW0 approach, where
only the Green’s function G is updated with the quasiparticle energies
of the previous iterations. W0 is kept fixed.
Both partial self-consistent cycles run for
eviter number of cycles.
The use of
EVGW0 will trigger the use of a scissor-shift
operator for all states not updated in the evGW cycle.
Two different techniques to obtain the diagonal self-energy matrix elements are implemented in NWChem.
analytic method builds and diagonalizes the full Casida RPA matrix
in order to obtain the screened Coulomb matrix elements. The Casida RPA
matrix grows very rapidly in size (Nocc × Nvir)
and ultimately yields a N6 scaling due to the diagonalization step.
It is therefore recommended to link the ELPA
and turn on its use by setting
SET dft:scaleig e
cdgw method uses the Contour-Deformation technique in order to
avoid the N6 diagonalization step. The diagonal self-energy
matrix elements Ʃnn are obtained via a numerical
integration on the imaginary axis and the integrals over closed contours
on the first and third quadrants of the complex plane. The
value controls the density of the modified Gauss-Legendre grid used
in the numerical integration over the imaginary axis.
cdgw methods are suitable for core and
The magnitude of the imaginary infinitesimal can be controlled using the
ETA. The default value of
0.001 should work rather well
for valence calculations, but
CORE calculations might need a
larger value, sometimes between
0.005 or even
Two methods to solver the quasiparticle equations are implemented in NWChem.
newton method uses a modified Newton approach to find the fixed-point
of the quasiparticle equations. The Newton method tries to bracket the
solution and switches to a golden section method whenever the Newton step goes
beyond the bracketing values.
graph method uses a frequency grid in order to bracket the solution
between two consecutive grid points. The number of grid points is controlled
heuristically depending on the
and on the presence, or not, of nearby states in a cluster
of energy (see below).
Regardless of the solver, the energies of the states are always
classified in clusters with a maximum extension of
1.5 eV. For
a given cluster of energies, the
newton method will start with the state closer to the Fermi level
and use its solution as guess for the rest of the states in the cluster.
graph method will look for the solution of all the states
in a given cluster at once with a frequency grid with range large
enough to encompass all the cluster ±
STATES controls for which particular state
the GW quasiparticle equations are to be solved. The
keyword might appear twice, one for the alpha spin channel
and one for the beta channel. The beta channel keyword is
meaningless for restricted closed-shell DFT calculations
MULT 1 without
ODFT in the
DFT input block).
The number of occupied states will be counted starting from the
state closest to the Fermi level (HOMO) unless the keyword
CORE is present. The virtual states will always
be counted from the state closest to the Fermi level upwards.
A -1 following either
vir stands for all
states in the respective space.
The converegnce threshold of the quasiparticle equations can
be controlled with the keyword
CONVERGENCE and might be
given either in
eV or Hartree
Sample Input File¶
- A GW calculation requesting the core-level binding energies of all 1s states (6 Fluorines and 6 Carbons) using the CD-GW method.
title "CDGW C6F6 core" start echo memory 2000 mb geometry C -0.21589696 1.38358991 0.00000000 C -1.30618181 0.50480033 0.00000000 C -1.09023026 -0.87871037 0.00000000 C 0.21590562 -1.38360671 0.00000000 C 1.30610372 -0.50476737 0.00000000 C 1.09020243 0.87883094 0.00000000 F -0.42025331 2.69273557 0.00000000 F -2.54211642 0.98238922 0.00000000 F -2.12174279 -1.71033945 0.00000000 F 0.42026196 -2.69275237 0.00000000 F 2.54203111 -0.98237286 0.00000000 F 2.12188428 1.71024875 0.00000000 end basis "ao basis" spherical * library cc-pvdz end basis "cd basis" spherical * library cc-pvdz-ri end dft xc xpbe96 0.55 hfexch 0.45 cpbe96 1.0 direct end gw core eta 0.01 method cdgw solver newton 15 states alpha occ 12 end task dft gw
- A valence GW calculation to obtain the vertical ionization potential and the vertical electron affinity of the water molecule using the analytic method.
start geometry O -0.000545 1.517541 0.000000 H 0.094538 0.553640 0.000000 H 0.901237 1.847958 0.000000 end basis "ao basis" spherical h library def2-svp o library def2-svp end basis "cd basis" spherical h library def2-universal-jkfit o library def2-universal-jkfit end dft mult 1 xc pbe96 grid fine direct end gw states alpha occ 1 vir 1 end task dft gw
- An evGW0 calculation with 10 iterations using the analytic method. All occupied energies, but only 10 virtual ones, are updated using GW. The rest of the virtual states are shifted using the so-called scissor operator.
start geometry O -0.000545 1.517541 0.000000 H 0.094538 0.553640 0.000000 H 0.901237 1.847958 0.000000 end basis "ao basis" spherical h library def2-svp o library def2-svp end basis "cd basis" spherical h library def2-universal-jkfit o library def2-universal-jkfit end dft mult 1 xc pbe96 grid fine direct end gw evgw0 10 states alpha occ -1 vir 10 end task dft gw
Mejia-Rodriguez, D.; Kunitsa, A.; Aprà, E.; Govind, N. Scalable Molecular GW Calculations: Valence and Core Spectra. Journal of Chemical Theory and Computation 2021, 17 (12), 7504–7517. https://doi.org/10.1021/acs.jctc.1c00738. ↩