Green's function methods;
ionisation potential;
total energy;
KOOPMANS THEOREM;
ELECTRON-GAS;
NONEQUILIBRIUM PROCESSES;
CORRELATION ENERGIES;
WAVE-FUNCTIONS;
GROUND-STATE;
ATOMS;
MOLECULES;
EXTENSION;
TRANSPORT;
D O I:
10.1063/1.3089567
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
We perform GW calculations on atoms and diatomic molecules at different levels of self-consistency and investigate the effects of self-consistency on total energies, ionization potentials, and particle number conservation. We further propose a partially self-consistent GW scheme in which we keep the correlation part of the self-energy fixed within the self-consistency cycle. This approximation is compared to the fully self-consistent GW results and to the GW(0) and the G(0)W(0) approximations. Total energies, ionization potentials, and two-electron removal energies obtained with our partially self-consistent GW approximation are in excellent agreement with fully self-consistent GW results while requiring only a fraction of the computational effort. We also find that self-consistent and partially self-consistent schemes provide ionization energies of similar quality as the G(0)W(0) values but yield better total energies and energy differences.