ترغب بنشر مسار تعليمي؟ اضغط هنا

Unphysical Discontinuities in GW Methods

304   0   0.0 ( 0 )
 نشر من قبل Pierre-Fran\\c{c}ois Loos Dr
 تاريخ النشر 2018
  مجال البحث فيزياء
والبحث باللغة English




اسأل ChatGPT حول البحث

We report unphysical irregularities and discontinuities in some key experimentally-measurable quantities computed within the GW approximation of many-body perturbation theory applied to molecular systems. In particular, we show that the solution obtained with partially self-consistent GW schemes depends on the algorithm one uses to solve self-consistently the quasi-particle (QP) equation. The main observation of the present study is that each branch of the self-energy is associated with a distinct QP solution, and that each switch between solutions implies a significant discontinuity in the quasiparticle energy as a function of the internuclear distance. Moreover, we clearly observe ripple effects, i.e., a discontinuity in one of the QP energies induces (smaller) discontinuities in the other QP energies. Going from one branch to another implies a transfer of weight between two solutions of the QP equation. The case of occupied, virtual and frontier orbitals are separately discussed on distinct diatomics. In particular, we show that multisolution behavior in frontier orbitals is more likely if the HOMO-LUMO gap is small.



قيم البحث

اقرأ أيضاً

In this work we show the advantages of using the Coulomb-hole plus screened-exchange (COHSEX) approach in the calculation of potential energy surfaces. In particular, we demonstrate that, unlike perturbative $GW$ and partial self-consistent $GW$ appr oaches, such as eigenvalue-self-consistent $GW$ and quasi-particle self-consistent $GW$, the COHSEX approach yields smooth potential energy surfaces without irregularities and discontinuities. Moreover, we show that the ground-state potential energy surfaces (PES) obtained from the Bethe-Salpeter equation, within the adiabatic connection fluctuation dissipation theorem, built with quasi-particle energies obtained from perturbative COHSEX on top of Hartree-Fock (BSE@COHSEX@HF) yield very accurate results for diatomic molecules close to their equilibrium distance. When self-consistent COHSEX quasi-particle energies and orbitals are used to build the BSE equation the results become independent of the starting point. We show that self-consistency worsens the total energies but improves the equilibrium distances with respect to BSE@COHSEX@HF. This is mainly due to changes in the screening inside the BSE.
Spectral methods provide an elegant and efficient way of numerically solving differential equations of all kinds. For smooth problems, truncation error for spectral methods vanishes exponentially in the infinity norm and $L_2$-norm. However, for non- smooth problems, convergence is significantly worse---the $L_2$-norm of the error for a discontinuous problem will converge at a sub-linear rate and the infinity norm will not converge at all. We explore and improve upon a post-processing technique---optimally convergent mollifiers---to recover exponential convergence from a poorly-converging spectral reconstruction of non-smooth data. This is an important first step towards using these techniques for simulations of realistic systems.
One-particle Greens function methods can model molecular and solid spectra at zero or non-zero temperatures. One-particle Greens functions directly provide electronic energies and one-particle properties, such as dipole moment. However, the evaluatio n of two-particle properties, such as $langle{S^2}rangle$ and $langle{N^2}rangle$ can be challenging, because they require a solution of the computationally expensive Bethe--Salpeter equation to find two-particle Greens functions. We demonstrate that the solution of the Bethe--Salpeter equation can be complitely avoided. Applying the thermodynamic Hellmann--Feynman theorem to self-consistent one-particle Greens function methods, we derive expressions for two-particle density matrices in a general case and provide explicit expressions for GF2 and GW methods. Such density matrices can be decomposed into an antisymmetrized product of correlated one-electron density matrices and the two-particle electronic cumulant of the density matrix. Cumulant expressions reveal a deviation from ensemble representability for GW, explaining its known deficiencies. We analyze the temperature dependence of $langle{S^2}rangle$ and $langle{N^2}rangle$ for a set of small closed-shell systems. Interestingly, both GF2 and GW show a non-zero spin contamination and a non-zero fluctuation of the number of particles for closed-shell systems at the zero-temperature limit.
Using the simple (symmetric) Hubbard dimer, we analyze some important features of the $GW$ approximation. We show that the problem of the existence of multiple quasiparticle solutions in the (perturbative) one-shot $GW$ method and its partially self- consistent version is solved by full self-consistency. We also analyze the neutral excitation spectrum using the Bethe-Salpeter equation (BSE) formalism within the standard $GW$ approximation and find, in particular, that i) some neutral excitation energies become complex when the electron-electron interaction $U$ increases, which can be traced back to the approximate nature of the $GW$ quasiparticle energies; ii) the BSE formalism yields accurate correlation energies over a wide range of $U$ when the trace (or plasmon) formula is employed; iii) the trace formula is sensitive to the occurrence of complex excitation energies (especially singlet), while the expression obtained from the adiabatic-connection fluctuation-dissipation theorem (ACFDT) is more stable (yet less accurate); iv) the trace formula has the correct behavior for weak (ie, small $U$) interaction, unlike the ACFDT expression.
We describe a finite-field approach to compute density response functions, which allows for efficient $G_0W_0$ and $G_0W_0Gamma_0$ calculations beyond the random phase approximation. The method is easily applicable to density functional calculations performed with hybrid functionals. We present results for the electronic properties of molecules and solids and we discuss a general scheme to overcome slow convergence of quasiparticle energies obtained from $G_0W_0Gamma_0$ calculations, as a function of the basis set used to represent the dielectric matrix.
التعليقات
جاري جلب التعليقات جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
mircosoft-partner

هل ترغب بارسال اشعارات عن اخر التحديثات في شمرا-اكاديميا