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Analysis of bad convergence:
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For the Kremer's dimer system, it's clearly because of DEGENERACIES
among the model states. There is no straightforward solution to
this problem.
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@MatthewRHermes
MatthewRHermes committed Oct 29, 2024
1 parent c47fff8 commit 7e778a7
Showing 1 changed file with 140 additions and 142 deletions.
282 changes: 140 additions & 142 deletions debug/lassi/debug_lassis_targets_slow.py
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Original file line number Diff line number Diff line change
Expand Up @@ -53,89 +53,89 @@ def tearDownModule():

class KnownValues(unittest.TestCase):

def test_c2h4n4_3frag (self):
# str
mol = struct (2.0, 2.0, '6-31g', symmetry=False)
mol.output = 'c2h4n4_3frag_str.log'#'/dev/null'
mol.verbose = 5#0
mol.spin = 8
mol.build ()
mf = scf.RHF (mol).run ()
las = LASSCF (mf, (4,2,4), ((2,2),(1,1),(2,2)), spin_sub=(1,1,1))
mo_coeff = las.localize_init_guess ([[0,1,2],[3,4,5,6],[7,8,9]])
las.kernel (mo_coeff)
lsi = lassi.LASSIS (las).run ()
e_str = lsi.e_roots[0]
with self.subTest ('str converged'):
self.assertTrue (lsi.converged)
# equil
mol = struct (0.0, 0.0, '6-31g', symmetry=False)
mol.spin = 0
mol.output = 'c2h4n4_3frag_equil.log'#'/dev/null'
mol.verbose = 5#0
mol.build ()
mf = scf.RHF (mol).run ()
las = LASSCF (mf, (4,2,4), ((2,2),(1,1),(2,2)), spin_sub=(1,1,1))
mo_coeff = las.sort_mo ([7,8,16,18,22,23,24,26,33,34])
mo_coeff = las.localize_init_guess ([[0,1,2],[3,4,5,6],[7,8,9]], mo_coeff=mo_coeff)
las.kernel (mo_coeff)
lsi = lassi.LASSIS (las).run ()
e_equil = lsi.e_roots[0]
with self.subTest ('equil converged'):
self.assertTrue (lsi.converged)
# test
de = 1000 * (e_str - e_equil)
self.assertAlmostEqual (de, 208.21775437138967, 1)
#def test_c2h4n4_3frag (self):
# # str
# mol = struct (2.0, 2.0, '6-31g', symmetry=False)
# mol.output = '/dev/null'
# mol.verbose = 0
# mol.spin = 8
# mol.build ()
# mf = scf.RHF (mol).run ()
# las = LASSCF (mf, (4,2,4), ((2,2),(1,1),(2,2)), spin_sub=(1,1,1))
# mo_coeff = las.localize_init_guess ([[0,1,2],[3,4,5,6],[7,8,9]])
# las.kernel (mo_coeff)
# lsi = lassi.LASSIS (las).run ()
# e_str = lsi.e_roots[0]
# with self.subTest ('str converged'):
# self.assertTrue (lsi.converged)
# # equil
# mol = struct (0.0, 0.0, '6-31g', symmetry=False)
# mol.spin = 0
# mol.verbose = 0
# mol.output = '/dev/null'
# mol.build ()
# mf = scf.RHF (mol).run ()
# las = LASSCF (mf, (4,2,4), ((2,2),(1,1),(2,2)), spin_sub=(1,1,1))
# mo_coeff = las.sort_mo ([7,8,16,18,22,23,24,26,33,34])
# mo_coeff = las.localize_init_guess ([[0,1,2],[3,4,5,6],[7,8,9]], mo_coeff=mo_coeff)
# las.kernel (mo_coeff)
# lsi = lassi.LASSIS (las).run ()
# e_equil = lsi.e_roots[0]
# with self.subTest ('equil converged'):
# self.assertTrue (lsi.converged)
# # test
# de = 1000 * (e_str - e_equil)
# self.assertAlmostEqual (de, 208.21775437138967, 1)

def test_c2h4n4_2frag (self):
# str
mol = struct (2.0, 2.0, '6-31g', symmetry=False)
mol.output = 'c2h4n4_2frag_str.log'#'/dev/null'
mol.verbose = 5#0
mol.spin = 8
mol.build ()
mf = scf.RHF (mol).run ()
las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
las = las.state_average ([0.5,0.5],
spins=[[1,-1],[-1,1]],
smults=[[2,2],[2,2]],
charges=[[0,0],[0,0]],
wfnsyms=[[0,0],[0,0]])
mo = las.set_fragments_((list (range (5)), list (range (5,10))))
las.kernel (mo)
mo_coeff = las.mo_coeff
las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
las.lasci_(mo_coeff)
lsi = lassi.LASSIS (las).run ()
e_str = lsi.e_roots[0]
with self.subTest ('str converged'):
self.assertTrue (lsi.converged)
# equil
mol = struct (0.0, 0.0, '6-31g', symmetry=False)
mol.spin = 0
mol.output = 'c2h4n4_2frag_equil.log'#'/dev/null'
mol.verbose = 5#0
mol.build ()
mf = scf.RHF (mol).run ()
las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
las = las.state_average ([0.5,0.5],
spins=[[1,-1],[-1,1]],
smults=[[2,2],[2,2]],
charges=[[0,0],[0,0]],
wfnsyms=[[0,0],[0,0]])
mo = las.sort_mo ([7,8,16,18,22,23,24,26,33,34])
mo = las.set_fragments_((list (range (5)), list (range (5,10))), mo)
las.kernel (mo)
mo_coeff = las.mo_coeff
las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
las.lasci_(mo_coeff)
lsi = lassi.LASSIS (las).run ()
e_equil = lsi.e_roots[0]
with self.subTest ('equil converged'):
self.assertTrue (lsi.converged)
# test
de = 1000 * (e_str - e_equil)
self.assertAlmostEqual (de, 191.185141573740, 1)
#def test_c2h4n4_2frag (self):
# # str
# mol = struct (2.0, 2.0, '6-31g', symmetry=False)
# mol.output = '/dev/null'
# mol.verbose = 0
# mol.spin = 8
# mol.build ()
# mf = scf.RHF (mol).run ()
# las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
# las = las.state_average ([0.5,0.5],
# spins=[[1,-1],[-1,1]],
# smults=[[2,2],[2,2]],
# charges=[[0,0],[0,0]],
# wfnsyms=[[0,0],[0,0]])
# mo = las.set_fragments_((list (range (5)), list (range (5,10))))
# las.kernel (mo)
# mo_coeff = las.mo_coeff
# las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
# las.lasci_(mo_coeff)
# lsi = lassi.LASSIS (las).run ()
# e_str = lsi.e_roots[0]
# with self.subTest ('str converged'):
# self.assertTrue (lsi.converged)
# # equil
# mol = struct (0.0, 0.0, '6-31g', symmetry=False)
# mol.spin = 0
# mol.verbose = 0
# mol.output = '/dev/null'
# mol.build ()
# mf = scf.RHF (mol).run ()
# las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
# las = las.state_average ([0.5,0.5],
# spins=[[1,-1],[-1,1]],
# smults=[[2,2],[2,2]],
# charges=[[0,0],[0,0]],
# wfnsyms=[[0,0],[0,0]])
# mo = las.sort_mo ([7,8,16,18,22,23,24,26,33,34])
# mo = las.set_fragments_((list (range (5)), list (range (5,10))), mo)
# las.kernel (mo)
# mo_coeff = las.mo_coeff
# las = lasscf_async.LASSCF (mf, (5,5), ((3,2),(2,3)))
# las.lasci_(mo_coeff)
# lsi = lassi.LASSIS (las).run ()
# e_equil = lsi.e_roots[0]
# with self.subTest ('equil converged'):
# self.assertTrue (lsi.converged)
# # test
# de = 1000 * (e_str - e_equil)
# self.assertAlmostEqual (de, 191.06467851275966, 1)

def test_kremer_cr2_model (self):
xyz='''Cr -1.320780000000 0.000050000000 -0.000070000000
Expand Down Expand Up @@ -172,8 +172,7 @@ def test_kremer_cr2_model (self):
H 3.367270000000 -0.612150000000 -1.514110000000'''
basis = {'C': 'sto-3g','H': 'sto-3g','O': 'sto-3g','N': 'sto-3g','Cr': 'cc-pvdz'}
mol = gto.M (atom=xyz, spin=6, charge=3, basis=basis,
verbose=5, output='kremer.log')
#verbose=0, output='/dev/null')
verbose=5, output='debug_lassis_targets_slow.kremer_cr2_model.log')
mf = scf.ROHF(mol)
mf.chkfile = 'test_lassis_targets_slow.kremer_cr2_model.chk'
mf.kernel ()
Expand All @@ -198,64 +197,63 @@ def test_kremer_cr2_model (self):
self.assertTrue (lsi.converged)
self.assertAlmostEqual (yamaguchi (lsi.e_roots, lsi.s2, 6), -12.45, 2)

def test_alfefe (self):
xyz='''O -2.2201982441 0.3991903003 1.6944716989
O -1.6855532446 -1.7823063217 1.4313995072
C -2.2685178651 -0.8319550379 1.983951274
H -2.9133420167 -1.0767285885 2.8437868053
O 1.3882880809 2.0795561562 -1.3470856753
O -0.7599088595 2.5809236347 -0.849227704
C 0.3465674686 2.753895325 -1.438835699
H 0.3723796145 3.6176996598 -2.1230911503
O 1.0469609081 -2.6425342 0.9613246722
O -0.3991903003 2.2201982441 1.6944716989
O 1.7823063217 1.6855532446 1.4313995072
C 0.8319550379 2.2685178651 1.983951274
H 1.0767285885 2.9133420167 2.8437868053
O -2.0795561562 -1.3882880809 -1.3470856753
O -2.5809236347 0.7599088595 -0.849227704
C -2.753895325 -0.3465674686 -1.438835699
H -3.6176996598 -0.3723796145 -2.1230911503
Fe -0.3798741893 -1.7926033629 -0.2003377303
O 0.6422231803 -2.237796553 -1.8929145176
Fe 1.7926033629 0.3798741893 -0.2003377303
O 2.237796553 -0.6422231803 -1.8929145176
O 2.6425342 -1.0469609081 0.9613246722
Al -1.2362716421 1.2362716421 0.350650148
O -0.0449501954 0.0449501954 0.0127621413
C 1.645528685 -1.645528685 -2.3571124654
H 2.0569062984 -2.0569062984 -3.2945712916
C 2.1609242811 -2.1609242811 1.2775841868
H 2.7960805433 -2.7960805433 1.9182443024'''
basis = {'C': 'sto-3g','H': 'sto-3g','O': 'sto-3g','Al': 'cc-pvdz','Fe': 'cc-pvdz'}
mol = gto.M (atom=xyz, spin=9, charge=0, basis=basis, max_memory=10000,
verbose=5, output='alfefe.log')
#verbose=0, output='/dev/null')
mf = scf.ROHF(mol)
mf.init_guess='chk'
mf.chkfile='test_lassis_targets_slow.alfefe.chk'
mf = mf.density_fit()
mf.max_cycle=100
mf.kernel()
las = LASSCF (mf, (5,5), ((5,1),(5,0)), spin_sub=(5,6))
try:
las.load_chk_()
las.kernel ()
except (OSError, TypeError, KeyError) as e:
ncas, nelecas, mo_coeff = avas.kernel (mf, ['Fe 3d'], openshell_option=3)
mo_coeff = las.localize_init_guess (([17],[19]), mo_coeff)
las.kernel (mo_coeff)
with self.subTest ('LASSCF convergence'):
self.assertTrue (las.converged)
with self.subTest ('same LASSCF result'):
self.assertAlmostEqual (las.e_tot, -3955.98148841553, 6)
mf.chkfile = None # prevent the spins flips down there from messing things up
las2 = LASSCF (mf, (5,5), ((1,5),(5,0)), spin_sub=(5,6))
las2.lasci_(las.mo_coeff)
lsi = lassi.LASSIS (las2).run ()
with self.subTest('LASSI convergence'):
self.assertTrue (lsi.converged)
self.assertAlmostEqual (yamaguchi (lsi.e_roots, lsi.s2, 9), -4.40, 2)
#def test_alfefe (self):
# xyz='''O -2.2201982441 0.3991903003 1.6944716989
# O -1.6855532446 -1.7823063217 1.4313995072
# C -2.2685178651 -0.8319550379 1.983951274
# H -2.9133420167 -1.0767285885 2.8437868053
# O 1.3882880809 2.0795561562 -1.3470856753
# O -0.7599088595 2.5809236347 -0.849227704
# C 0.3465674686 2.753895325 -1.438835699
# H 0.3723796145 3.6176996598 -2.1230911503
# O 1.0469609081 -2.6425342 0.9613246722
# O -0.3991903003 2.2201982441 1.6944716989
# O 1.7823063217 1.6855532446 1.4313995072
# C 0.8319550379 2.2685178651 1.983951274
# H 1.0767285885 2.9133420167 2.8437868053
# O -2.0795561562 -1.3882880809 -1.3470856753
# O -2.5809236347 0.7599088595 -0.849227704
# C -2.753895325 -0.3465674686 -1.438835699
# H -3.6176996598 -0.3723796145 -2.1230911503
# Fe -0.3798741893 -1.7926033629 -0.2003377303
# O 0.6422231803 -2.237796553 -1.8929145176
# Fe 1.7926033629 0.3798741893 -0.2003377303
# O 2.237796553 -0.6422231803 -1.8929145176
# O 2.6425342 -1.0469609081 0.9613246722
# Al -1.2362716421 1.2362716421 0.350650148
# O -0.0449501954 0.0449501954 0.0127621413
# C 1.645528685 -1.645528685 -2.3571124654
# H 2.0569062984 -2.0569062984 -3.2945712916
# C 2.1609242811 -2.1609242811 1.2775841868
# H 2.7960805433 -2.7960805433 1.9182443024'''
# basis = {'C': 'sto-3g','H': 'sto-3g','O': 'sto-3g','Al': 'cc-pvdz','Fe': 'cc-pvdz'}
# mol = gto.M (atom=xyz, spin=9, charge=0, basis=basis, max_memory=10000, verbose=0,
# output='/dev/null')
# mf = scf.ROHF(mol)
# mf.init_guess='chk'
# mf.chkfile='test_lassis_targets_slow.alfefe.chk'
# mf = mf.density_fit()
# mf.max_cycle=100
# mf.kernel()
# las = LASSCF (mf, (5,5), ((5,1),(5,0)), spin_sub=(5,6))
# try:
# las.load_chk_()
# las.kernel ()
# except (OSError, TypeError, KeyError) as e:
# ncas, nelecas, mo_coeff = avas.kernel (mf, ['Fe 3d'], openshell_option=3)
# mo_coeff = las.localize_init_guess (([17],[19]), mo_coeff)
# las.kernel (mo_coeff)
# with self.subTest ('LASSCF convergence'):
# self.assertTrue (las.converged)
# with self.subTest ('same LASSCF result'):
# self.assertAlmostEqual (las.e_tot, -3955.98148841553, 6)
# mf.chkfile = None # prevent the spins flips down there from messing things up
# las2 = LASSCF (mf, (5,5), ((1,5),(5,0)), spin_sub=(5,6))
# las2.lasci_(las.mo_coeff)
# lsi = lassi.LASSIS (las2).run ()
# with self.subTest('LASSI convergence'):
# self.assertTrue (lsi.converged)
# self.assertAlmostEqual (yamaguchi (lsi.e_roots, lsi.s2, 9), -4.40, 2)


if __name__ == "__main__":
Expand Down

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