Hello Pablo, thanks for the opportunity to test the calculations with geminals ansatz.Pablo_Lopez_Rios wrote:Patch now available in current beta.
Best,
Pablo
I chose the simplest systems and performed the calculations in the qchem program.
1. Li-atom in cc-pVDZ basis, WFN consists of 1 geminal orbitals and an orbital filled with an unpaired electron, so QCHEM input/output and CASINO input/output in attachment.
Unfortunately CASINO cannot accept an unpaired electron on second orbital and returns an error: Kinetic energy test failed: analytical derivatives misbehave.Final energy = -7.432605555957891
Energy decomposition, spin= TRUE
Nuclear Attr. Energy = 0.0000000000
One-El. Pot. Energy = -17.1450277592
One-El. Kin. Energy = 7.4317293525
Tot. Intra-gem Energy = -9.2971415985
Inter-gem Coul. Energy = 2.6905114013
Inter-gem Exch. Energy = -0.8259753588
Correlation Energy = -0.0004001996
VAR verifying total -7.432605555957891 error: -0.000000000000001
Geminal occupations, energies and coefficients.
Geminal 1 E = -3.387669043962796
2.00[s],
0.99996729 -0.00464321 -0.00464307 -0.00464305 -0.00048555 -0.00031930 -0.00031926 -0.00031921 -0.00031917 -0.00031659 -0.00001423 -0.00001403 0.00001401.
Occupations and energies of unpaired orbitals.
1.00[s],
-2.18040047
2. Be-atom in cc-pVDZ basis, WFN consists of 2 geminals strongly ortogonal, so QCHEM input/output and CASINO input/output in attachment.
each virtual orbital belongs either to the first or second geminal, this results in orthogonality, and I manually distributed virtual orbitals based on the QCHEM output file, however, the energy does not coincide with that found in QCHEM output file.Final energy = -14.617016246569332
Energy decomposition, spin= TRUE
Nuclear Attr. Energy = 0.0000000000
One-El. Pot. Energy = -33.6940528313
One-El. Kin. Energy = 14.6150473252
Tot. Intra-gem Energy = -16.5188194534
Inter-gem Coul. Energy = 1.9430696836
Inter-gem Exch. Energy = -0.0412664768
Correlation Energy = -0.1214694892
VAR verifying total -14.617016246569332 error: 0.000000000000017
Geminal occupations, energies and coefficients.
Geminal 1 E = -11.707720511899904
2.00[s],
0.99999849 -0.00100242 -0.00100221 -0.00100180.
Geminal 2 E = -1.007492527867571
1.82[s],
0.95271649 -0.17380094 -0.17379549 -0.17379340 -0.03715659 -0.00818632 -0.00818536 -0.00818511 -0.00818199 -0.00818198
I will be very grateful if you describe the algorithm for constructing a wave function (GEMINAL section) for two orthogonal geminal.
if changes were made to a separate git branch it would be much easier to test, without breaking master branch.
Best Vladimir