RHF with H2 errors #119

mtfishman · 2022-01-21T21:03:36Z

I'm finding the RHF on H2 fails:

using Fermi

@molecule {
  H  0.0 0.0 0.0
  H  0.76 0.0 0.0
}
@set basis sto-3g
wfn = @energy rhf

with the output:

================================================================================
|                                 Hartree-Fock                                 |
|                                  Module  by                                  |
|                         G.J.R Aroeira and M.M. Davis                         |
================================================================================
Collecting necessary integrals...
Done in    0.57259 s
Using GWH Guess
Molecule:

H    0.000000000000    0.000000000000    0.000000000000
H    0.760000000000    0.000000000000    0.000000000000


Charge: 0   Multiplicity: 1   
Nuclear repulsion:    0.6962858038
 Number of AOs:                            2
 Number of Doubly Occupied Orbitals:       1
 Number of Virtual Spatial Orbitals:       1
nt: 6
 Guess Energy    -1.81166646326759

 Iter.            E[RHF]         ΔE       Dᵣₘₛ        t     DIIS     damp
--------------------------------------------------------------------------------
    1     -1.1153806594  -1.115e+00   0.000e+00     0.76    false      NaN
ERROR: LoadError: ArgumentError: matrix contains Infs or NaNs
Stacktrace:
  [1] chkuplofinite(A::Matrix{Float64}, uplo::Char)
    @ LinearAlgebra.LAPACK /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/lapack.jl:109
  [2] syevr!(jobz::Char, range::Char, uplo::Char, A::Matrix{Float64}, vl::Float64, vu::Float64, il::Int64, iu::Int64, abstol::Float64)
    @ LinearAlgebra.LAPACK /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/lapack.jl:5089
  [3] #eigen!#185
    @ /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/symmetriceigen.jl:4 [inlined]
  [4] #eigen#186
    @ /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/symmetriceigen.jl:9 [inlined]
  [5] #diagonalize#20
    @ ~/.julia/packages/Fermi/phTqJ/src/Backend/Arrays.jl:189 [inlined]
  [6] macro expansion
    @ ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:138 [inlined]
  [7] macro expansion
    @ ./timing.jl:299 [inlined]
  [8] macro expansion
    @ ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:133 [inlined]
  [9] macro expansion
    @ ./timing.jl:299 [inlined]
 [10] Fermi.HartreeFock.RHF(ints::Fermi.Integrals.IntegralHelper{Float64, Fermi.Integrals.SparseERI, Fermi.Orbitals.AtomicOrbitals}, C::FermiMDArray{Float64, 2}, Λ::FermiMDArray{Float64, 2}, Alg::Fermi.HartreeFock.RHFa)
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:132
 [11] Fermi.HartreeFock.RHF(ints::Fermi.Integrals.IntegralHelper{Float64, Fermi.Integrals.SparseERI, Fermi.Orbitals.AtomicOrbitals}, Alg::Fermi.HartreeFock.RHFa)
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:32
 [12] Fermi.HartreeFock.RHF(Alg::Fermi.HartreeFock.RHFa)
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:5
 [13] Fermi.HartreeFock.RHF()
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHF.jl:81
 [14] top-level scope
    @ ~/Dropbox (Simons Foundation)/workdir/Fermi.jl/hartree_fock_H2.jl:8
 [15] include(fname::String)
    @ Base.MainInclude ./client.jl:451
 [16] top-level scope
    @ REPL[1]:1
in expression starting at /home/mfishman/Dropbox (Simons Foundation)/workdir/Fermi.jl/hartree_fock_H2.jl:8

My setup is:

(@v1.7) pkg> st Fermi
      Status `~/.julia/environments/v1.7/Project.toml`
  [9237668d] Fermi v0.4.0

julia> versioninfo()
Julia Version 1.7.1
Commit ac5cc99908 (2021-12-22 19:35 UTC)
Platform Info:
  OS: Linux (x86_64-pc-linux-gnu)
  CPU: Intel(R) Xeon(R) E-2176M  CPU @ 2.70GHz
  WORD_SIZE: 64
  LIBM: libopenlibm
  LLVM: libLLVM-12.0.1 (ORCJIT, skylake)
Environment:
  JULIA_EDITOR = vim

Maybe I'm running it wrong.

Thanks,
Matt

gustavojra · 2022-01-21T21:08:51Z

Hi Matt,

It is a problem with DIIS not dealing well with small systems. It does need fixing, but I have been procrastinating on it. You can simply disable DIIS if the system is small (~5 electrons or so)

@set diis false

mtfishman · 2022-01-21T21:12:10Z

Ok, thanks. Glad to know it's not just me doing something silly. Unfortunately that doesn't seem to help. When I run:

using Fermi

@molecule {
  H  0.0 0.0 0.0
  H  0.76 0.0 0.0
}
@set basis sto-3g
@set diis false
wfn = @energy rhf

I get what looks like the same error.

gustavojra · 2022-01-21T21:13:41Z

Oh, interesting. If you use a larger basis such as cc-pvdz does the error persist?

mtfishman · 2022-01-21T21:15:11Z

Looks like cc-pvdz works with our without DIIS.

gustavojra · 2022-01-21T21:17:21Z

Can you try @set oda false for the sto-3g case? That damp NaN on the first iteration does not appear for me.

mtfishman · 2022-01-21T21:23:32Z

Ok, that's seems to work:

using Fermi

@molecule {
  H  0.0 0.0 0.0
  H  0.76 0.0 0.0
}
@set basis sto-3g
@set diis false
@set oda false
wfn = @energy rhf

outputs:

================================================================================
|                                 Hartree-Fock                                 |
|                                  Module  by                                  |
|                         G.J.R Aroeira and M.M. Davis                         |
================================================================================
Collecting necessary integrals...
Done in    0.00009 s
Using GWH Guess
Molecule:

H    0.000000000000    0.000000000000    0.000000000000
H    0.760000000000    0.000000000000    0.000000000000


Charge: 0   Multiplicity: 1   
Nuclear repulsion:    0.6962858038
 Number of AOs:                            2
 Number of Doubly Occupied Orbitals:       1
 Number of Virtual Spatial Orbitals:       1
 Guess Energy    -1.81166646326759

 Iter.            E[RHF]         ΔE       Dᵣₘₛ        t     DIIS     damp
--------------------------------------------------------------------------------
    1     -1.1153806594  -1.115e+00   0.000e+00     0.00    false     0.00
    2     -1.1153806594   0.000e+00   0.000e+00     0.00    false     0.00
    3     -1.1153806594   0.000e+00   0.000e+00     0.00    false     0.00
    4     -1.1153806594   0.000e+00   0.000e+00     0.00    false     0.00
    5     -1.1153806594   0.000e+00   0.000e+00     0.00    false     0.00
--------------------------------------------------------------------------------
    RHF done in  0.00s
    @Final RHF Energy          -1.115380659448 Eₕ

   • Orbitals Summary

    Orbital            Energy    Occupancy
          1     -0.5703627667       ↿⇂
          2      0.6508750828         

   ✔  SCF Equations converged 😄
--------------------------------------------------------------------------------
 ⇒ Fermi Restricted Hartree--Fock Wave function
 ⋅ Basis:                  sto-3g
 ⋅ Energy:                 -1.1153806594478526
 ⋅ Occ. Spatial Orbitals:  1
 ⋅ Vir. Spatial Orbitals:  1
Convergence: ΔE => 0.00e+00 Dᵣₘₛ => 0.00e+00

With diis true it errors with:

================================================================================
|                                 Hartree-Fock                                 |
|                                  Module  by                                  |
|                         G.J.R Aroeira and M.M. Davis                         |
================================================================================
Collecting necessary integrals...
Done in    0.00009 s
Using GWH Guess
Molecule:

H    0.000000000000    0.000000000000    0.000000000000
H    0.760000000000    0.000000000000    0.000000000000


Charge: 0   Multiplicity: 1   
Nuclear repulsion:    0.6962858038
 Number of AOs:                            2
 Number of Doubly Occupied Orbitals:       1
 Number of Virtual Spatial Orbitals:       1
 Guess Energy    -1.81166646326759

 Iter.            E[RHF]         ΔE       Dᵣₘₛ        t     DIIS     damp
--------------------------------------------------------------------------------
    1     -1.1153806594  -1.115e+00   0.000e+00     0.00    false     0.00
    2     -1.1153806594   0.000e+00   0.000e+00     0.00    false     0.00
    3     -1.1153806594   0.000e+00   0.000e+00     0.00    false     0.00
ERROR: LoadError: LinearAlgebra.SingularException(2)
Stacktrace:
  [1] checknonsingular
    @ /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/factorization.jl:19 [inlined]
  [2] checknonsingular
    @ /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/factorization.jl:21 [inlined]
  [3] #lu!#146
    @ /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/lu.jl:82 [inlined]
  [4] #lu#153
    @ /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/lu.jl:279 [inlined]
  [5] lu (repeats 2 times)
    @ /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/lu.jl:278 [inlined]
  [6] \(A::Matrix{Float64}, B::Vector{Float64})
    @ LinearAlgebra /buildworker/worker/package_linux64/build/usr/share/julia/stdlib/v1.7/LinearAlgebra/src/generic.jl:1142
  [7] extrapolate(M::Fermi.DIIS.DIISManager{Float64, Float64}; add_res::Bool)
    @ Fermi.DIIS ~/.julia/packages/Fermi/phTqJ/src/Core/DIIS.jl:83
  [8] extrapolate
    @ ~/.julia/packages/Fermi/phTqJ/src/Core/DIIS.jl:61 [inlined]
  [9] macro expansion
    @ ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:182 [inlined]
 [10] macro expansion
    @ ./timing.jl:299 [inlined]
 [11] macro expansion
    @ ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:133 [inlined]
 [12] macro expansion
    @ ./timing.jl:299 [inlined]
 [13] Fermi.HartreeFock.RHF(ints::Fermi.Integrals.IntegralHelper{Float64, Fermi.Integrals.SparseERI, Fermi.Orbitals.AtomicOrbitals}, C::FermiMDArray{Float64, 2}, Λ::FermiMDArray{Float64, 2}, Alg::Fermi.HartreeFock.RHFa)
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:132
 [14] Fermi.HartreeFock.RHF(ints::Fermi.Integrals.IntegralHelper{Float64, Fermi.Integrals.SparseERI, Fermi.Orbitals.AtomicOrbitals}, Alg::Fermi.HartreeFock.RHFa)
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:32
 [15] Fermi.HartreeFock.RHF(Alg::Fermi.HartreeFock.RHFa)
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHFa.jl:5
 [16] Fermi.HartreeFock.RHF()
    @ Fermi.HartreeFock ~/.julia/packages/Fermi/phTqJ/src/Methods/HartreeFock/RHF/RHF.jl:81
 [17] top-level scope
    @ ~/Dropbox (Simons Foundation)/workdir/Fermi.jl/hartree_fock_H2.jl:10
 [18] include(fname::String)
    @ Base.MainInclude ./client.jl:451
 [19] top-level scope
    @ REPL[6]:1
in expression starting at /home/mfishman/Dropbox (Simons Foundation)/workdir/Fermi.jl/hartree_fock_H2.jl:10

gustavojra · 2022-01-21T22:06:43Z

Okay, great. It's a good reminder to add numerical checks for these extrapolations schemes. They should be well behaved for larger systems though.

gustavojra added good first issue Good for newcomers HartreeFock concerning HF methods labels Jan 21, 2022

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RHF with H2 errors #119

RHF with H2 errors #119

mtfishman commented Jan 21, 2022

gustavojra commented Jan 21, 2022

mtfishman commented Jan 21, 2022

gustavojra commented Jan 21, 2022

mtfishman commented Jan 21, 2022

gustavojra commented Jan 21, 2022

mtfishman commented Jan 21, 2022

gustavojra commented Jan 21, 2022

RHF with H2 errors #119

RHF with H2 errors #119

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mtfishman commented Jan 21, 2022

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mtfishman commented Jan 21, 2022

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mtfishman commented Jan 21, 2022

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