NATURALO: Difference between revisions

Revision as of 15:48, 4 November 2020

NATURALO = [integer]
Default: NATURALO = 0

Description: calculate RPA natural orbitals.

This flag should be used in combination with ALGO = G0W0R or ALGO = scGW0R. The VASP code diagonalizes the RPA density matrix and writes the final natural orbitals to the WAVECAR file. The one-electron occupancies on the WAVECAR file can also be updated to the eigenvalues of the RPA density matrix. For ALGO = G0W0R, the interacting Green's function is approximated as

${\displaystyle G = G_0 + G_0 \Sigma G_0 }$

whereas for ALGO = scGW0R the Dyson equation is solved

${\displaystyle G = G_0 + G \Sigma G_0. }$

In both cases, the RPA density matrix is determined as $\gamma= \lim_{\tau \to 0^-} G(\tau)$ . More details on the use of RPA natural orbitals can be found in Ref. ^[1].

The following settings are currently supported

NATURALO=0 calculate the density matrix, diagonalize the matrix and write the natural orbitals and eigenvalues of the density matrix to the file WAVECAR.

NATURALO=1 calculate the density matrix, diagonalize the matrix only in the sub-block of unoccupied states, and write the occupied Kohn Sham orbitals, as well as the natural orbitals corresponding to unoccupied states to the file WAVECAR. The unoccupied orbitals are ordered according to their occupancies. This should be only used for gapped systems (insulators and semiconductors). The one-electron occupancies are not updated from their KS values (they will remain 1 for occupied Kohn-Sham orbitals and 0 for natural orbitals representing the virtual manifold).

NATURALO =negative value. Similar to NATURALO=1 but additionally conserves ABS|NATURALO| unoccupied Kohn-Sham states. This is expedient, for subsequent GW and BSE calculations to conserve few unoccupied orbitals to their Kohn-Sham state.

If 10 is added (e.g. NATURALO=10, NATURALO=11) the density matrix is diagonalizes using a perturbative Loewdin algorithm that attempts to keep the orbital order strictly conserved: E.g. the natural orbital matching closest the Kohn-Sham orbital will be determined and stored.

NATURALO=2 (or 12) is similar to 0, but the one-electron occupancies are not updated. In rare cases this might lead to inconsistencies, if the orbital order changes between DFT and the RPA density matrix (i.e. a previously occupied DFT orbitals posses a smaller occupation in the RPA density matrix than some unoccupied Kohn-Sham orbitals and are moved into the unoccupied block). This problem can be reduced using NATURALO=12, as described above. This flag in combination with ALGO = scGW0R, can be used to evaluate the GW-singles contribution to the correlation energy.^[2] One can deduct the GW singles energies from the energies after

Energies after update of density matrix
Hartree-Fock free energy of the ion-electron system (eV)

Experience has shown that there is very little difference between the natural orbitals obtained using ALGO = G0W0R and ALGO = scGW0R. We strongly recommend to use the more efficient and better tested algorithm ALGO = G0W0R (with the exception of GW-singles). Furthermore, perform careful tests for NOMEGA: the RPA total energy converges much faster then the natural orbitals. Using a too small NOMEGA can yield natural orbitals that are non-optimal, leading to very slow convergence of correlated calculations with respect to the number of natural orbitals.

Related Tags and Sections

ALGO for response functions and RPA calculations
for an overview ACFDT/RPA calculations

References

[ramberger2019rpa-1] B. Ramberger, Z. Sukurma, T. Schäfer, G. Kresse, J. Chem. Phys. 151, 214106 (2019).

[Klimessingles-2] Jiří Klimeš, et al., J. Chem. Phys. 143, 102816 (2015).

[1]

[2]

@@ Line 6: / Line 6: @@
 This flag should be used in combination with {{TAG|ALGO}} = G0W0R or {{TAG|ALGO}} = scGW0R.  The VASP code diagonalizes the RPA density
 matrix and writes the final natural orbitals to the {{TAG|WAVECAR}} file.
-The one-electron occupancies on the {{TAG|WAVECAR}} file can be also updated to the eigenvalues
+The one-electron occupancies on the {{TAG|WAVECAR}} file can also be updated to the eigenvalues of the RPA density matrix. For {{TAG|ALGO}} = G0W0R, the interacting Green's function is approximated as
-of the RPA density matrix. For {{TAG|ALGO}} = G0W0R, the interacting Green's function is approximated as
 <math>
@@ Line 19: / Line 18: @@
 </math>
-In both cases, the RPA density matrix is determined as <math> \gamma= \lim_{\tau \to 0^-} G(\tau) </math>. More details on the use of RPA natural orbitals can be found in <ref name="ramberger2019rpa"/>
+In both cases, the RPA density matrix is determined as <math> \gamma= \lim_{\tau \to 0^-} G(\tau) </math>. More details on the use of RPA natural orbitals can be found in Ref. <ref name="ramberger2019rpa"/>.
 The following settings are currently supported
@@ Line 25: / Line 24: @@
 * {{TAG|NATURALO}}=0 calculate the density matrix, diagonalize the matrix and write the natural orbitals and eigenvalues of the density matrix to the file {{TAG|WAVECAR}}.
-* {{TAG|NATURALO}}=1 calculate the density matrix, diagonalize the matrix only in the sub-block of unoccupied states, and write the occupied Kohn Sham orbitals, as well as the natural orbitals corresponding to unoccupied states to the file {{TAG|WAVECAR}}. The unoccupied orbitals are ordered according to their occupancies.
+* {{TAG|NATURALO}}=1 calculate the density matrix, diagonalize the matrix only in the sub-block of unoccupied states, and write the occupied Kohn Sham orbitals, as well as the natural orbitals corresponding to unoccupied states to the file {{TAG|WAVECAR}}. The unoccupied orbitals are ordered according to their occupancies. This should be only used for gapped systems (insulators and semiconductors). The one-electron occupancies are not updated from their KS values (they will remain 1 for occupied Kohn-Sham orbitals and 0 for natural orbitals representing the virtual manifold).
-This should be only used for gapped systems (insulators and semiconductors). The one-electron occupancies are not updated from their KS values (they will remain 1 and 0).
-* {{TAG|NATURALO}}=negative value: Similar to  {{TAG|NATURALO}}=1 but additionally conserve |{{TAG|NATURALO}}| unoccupied Kohn-Sham states. This is expedient, for subsequent GW and BSE calculations  to conserve few unoccupied orbitals to their Kohn-Sham state.
+* {{TAG|NATURALO}} =negative value. Similar to  {{TAG|NATURALO}}=1 but additionally conserves ABS|{{TAG|NATURALO}}| unoccupied Kohn-Sham states. This is expedient, for subsequent GW and BSE calculations  to conserve few unoccupied orbitals to their Kohn-Sham state.
-* If 10 is added (e.g. {{TAG|NATURALO}}=10, {{TAG|NATURALO}}=11) the density matrix is diagonalizes using a perturbative Loewdin algorithm that attempts to keep the orbital order strictly conserved: E.g. the natural orbital matching closest the Nth Kohn-Sham orbital will be determined and stored.
+* If 10 is added (e.g. {{TAG|NATURALO}}=10, {{TAG|NATURALO}}=11) the density matrix is diagonalizes using a perturbative Loewdin algorithm that attempts to keep the orbital order strictly conserved: E.g. the natural orbital matching closest the Kohn-Sham orbital will be determined and stored.
-* {{TAG|NATURALO}}=2 (or 12) is similar to 0, but the one-electron occupancies are not updated. In rare cases this might lead to inconsistencies, if the orbital order changes between DFT and the RPA density matrix (i.e. a previously occupied DFT orbitals posses a smaller occupation in the RPA density matrix than some unoccupied Kohn-Sham orbitals and are moved into the unoccupied block). Use this with care and only for gapped systems. This flag in combination with {{TAG|ALGO}} = scGW0R, can be used to evaluate the  GW-singles contribution to the correlation energy.<ref name="Klimessingles"/> One can deduct the singles energies from the energies after
+* {{TAG|NATURALO}}=2 (or 12) is similar to 0, but the one-electron occupancies are not updated. In rare cases this might lead to inconsistencies, if the orbital order changes between DFT and the RPA density matrix (i.e. a previously occupied DFT orbitals posses a smaller occupation in the RPA density matrix than some unoccupied Kohn-Sham orbitals and are moved into the unoccupied block). This problem can be reduced using {{TAG|NATURALO}}=12, as described above. This flag in combination with {{TAG|ALGO}} = scGW0R, can be used to evaluate the GW-singles contribution to the correlation energy.<ref name="Klimessingles"/> One can deduct the GW singles energies from the energies after
   Energies after update of density matrix
   Hartree-Fock free energy of the ion-electron system (eV)
-Experience has shown that there is very little difference between the orbitals obtained using {{TAG|ALGO}} = G0W0R and {{TAG|ALGO}} = scGW0R. We strongly recommend to use the more efficient and better tested algorithm {{TAG|ALGO}} = G0W0R. Furthermore, perform careful tests for {{TAG|NOMEGA}}: the RPA total energy converges much faster then the natural orbitals. Using a too small {{TAG|NOMEGA}} can yields natural orbitals that are non-optimal, leading to very slow convergence of correlated calculations with respect to the number of natural orbitals.
+Experience has shown that there is very little difference between the natural orbitals obtained using {{TAG|ALGO}} = G0W0R and {{TAG|ALGO}} = scGW0R. We strongly recommend to use the more efficient and better tested algorithm {{TAG|ALGO}} = G0W0R (with the exception of GW-singles). Furthermore, perform careful tests for {{TAG|NOMEGA}}: the RPA total energy converges much faster then the natural orbitals. Using a too small {{TAG|NOMEGA}} can yield natural orbitals that are non-optimal, leading to very slow convergence of correlated calculations with respect to the number of natural orbitals.
@@ Line 48: / Line 46: @@
 <references>
 <ref  name="ramberger2019rpa">[https://doi.org/10.1063/1.5128415   B. Ramberger, Z. Sukurma, T. Schäfer, G. Kresse,  J. Chem. Phys. 151, 214106 (2019).]</ref>
-<ref name="Klimessingles">[ https://doi.org/10.1063/1.4962188  Jiří Klimeš,  et al., J. Chem. Phys.  143, 102816 (2015).]</ref>
+<ref name="Klimessingles">[https://doi.org/10.1063/1.4962188  Jiří Klimeš,  et al., J. Chem. Phys.  143, 102816 (2015).]</ref>
 </references>
 ----
 [[Category:INCAR]][[Category:Many-Body Perturbation Theory]] [[Category:GW]] [[Category:ACFDT]][[Category:Performance]][[Category:Parallelization]][[Category:Low-scaling GW and RPA]][[Category:VASP6]]