Error handling with REKS

Oscillation of energy during SCC

[Input: recipes/reks/oscillation_energy/]

The oscillation of SA-REKS energy in the SCC process may appear as follows:

646       -8.9586042135       0.0000229869     0.621642    0.00993712
647       -8.9586272004      -0.0000229869     0.601626    0.00993712
648       -8.9586042135       0.0000229869     0.621642    0.00993712
649       -8.9586272004      -0.0000229869     0.601626    0.00993712
650       -8.9586042135       0.0000229869     0.621642    0.00993712
651       -8.9586272004      -0.0000229869     0.601626    0.00993712
652       -8.9586042135       0.0000229869     0.621642    0.00993712
653       -8.9586272004      -0.0000229869     0.601626    0.00993712
654       -8.9586042135       0.0000229869     0.621642    0.00993712

These oscillations mostly arise from the degeneracy of the frontier orbitals. As the difference between frontier orbitals gets smaller, it becomes harder to determine the order of the frontier orbitals during the SCC process. As a result, oscillating phenomena appear in these cases. To solve this, the user can increase the shift value by setting Shift in REKS block, which increases the separation in energy between the lower and upper orbital, stabilising the convergence. Smoother variational convergence of the SA-REKS energy can occur in the SCC process:

  111       -8.9586871392      -0.0000000004     0.610476    0.00000117
  112       -8.9586871395      -0.0000000003     0.610474    0.00000110
  113       -8.9586871398      -0.0000000003     0.610473    0.00000103
  114       -8.9586871401      -0.0000000003     0.610471    0.00000097

--------------------------------------------------
 Final SA-REKS(2,2) energy:      -8.95868714

 State     Energy      FON(1)    FON(2)   Spin
  PPS   -8.97337341   1.220943  0.779057  0.00
  OSS   -8.94400087   1.000000  1.000000  0.00
 Trip   -8.97307659   1.000000  1.000000  1.00
--------------------------------------------------

Thus, one can check the FONs for the PPS state become \(n_a\) ~1.2 and \(n_b\) ~0.8 in this example. As the orbital energies of the active orbitals are close each other, the user should increase the shift value as well as the number of MaxSCCIterations.

Oscillation of SA-REKS energy can also occur with the following irregular pattern:

  84      -11.5656112187       0.0000347081     0.535896    0.00170908
  85      -11.5616527044       0.0039585143     0.533173    0.01062304
fa =  0.471347, MO swap between a(  14) and b(  15) occurs
  86      -11.5390645462       0.0225881582     0.442694    0.05641408
fa =  0.460378, MO swap between a(  14) and b(  15) occurs
  87      -11.5618504576      -0.0227859114     0.420756    0.00750593
fa =  0.481839, MO swap between a(  14) and b(  15) occurs
  88      -11.5564810194       0.0053694382     0.463678    0.02941886
  89      -11.4916836033       0.0647974162     0.993664    0.50049487
  90      -11.5138647944      -0.0221811911     0.999927    0.21955679

Selection energy functional to be minimised

[Input: recipes/reks/benzene/]

A benzene molecule has two degenerate \(\pi\) orbitals and two degenerate \(\pi^*\) orbitals. Thus, if one want to calculate this case, then the active space should include two \(\pi\) and two \(\pi^*\) orbitals. Hence, a (2,2) active space may be insufficient to investigate this system, but the ground state can be optimised with DFTB/SSR(2,2). Since there is an ambiguity in deciding the active space, the OSS state cannot be correctly generated. Thus, only single-state REKS is recommended for C6H6, and the resulting energy of the PPS state is given as:

--------------------------------------------------
  Final REKS(2,2) energy:     -12.56867223

 State     Energy      FON(1)    FON(2)   Spin
  PPS  -12.56867223   2.000000  0.000000  0.00
--------------------------------------------------

Note that the orbital energy of the upper frontier orbital (in this case, the 16th orbital) in the band.out file is not correctly provided since there is an ambiguous part in the single-state REKS method when the Fock matrix is constructed as follows:

14    -6.700  2.00000
15    -6.700  2.00000
16    -7.583  0.00000
17    -1.399  0.00000

This problem only occurs in single-state REKS, thus the band energies are correctly calculated for the SA-REKS or SSR methods.

According to the system, there may exist instability for the lowest excited singlet state, which corresponds to the OSS state. In this case, including only the PPS state to minimised the energy functional is recommended, then the geometry will be optimised successfully.

Failure of CP-REKS equations

[Input: recipes/reks/acetylene/]

In general, a preconditioned conjugate-gradient algorithm is used to solve CP-REKS equations. It calculates quickly and accurately for most molecules, but it may fail to calculate a preconditioner due to the system symmetry. The stable geometry of an acetylene is planar and shows a high symmetry, thus a singularity appears as in this case as follows:

ERROR!
-> A singularity exists in preconditioner for PCG, set Preconditioner = No

In this case, using conjugate-gradient without a preconditioner helps to solve CP-REKS equations. The CP-REKS equations are then successfully solved as follows:

----------------------------------------------------------------------------------
 Solving CP-REKS equation for  1 state vector...
----------------------------------------------------------------------------------
  CG solver: Constructing Y initial guess
  CG solver: Iteration    1    eps =    0.000000000000
  Convergence reached in CG solver after    1 iterations
  CG solver: Calculating converged R, Z, Q2 matrix
----------------------------------------------------------------------------------

Therefore, the user can check the geometry and symmetry when these errors occur.