def _log_init(self):
'''Write a summary of the wavefunction to the screen logger'''
if log.do_medium:
log('Initialized: %s' % self)
if self.occ_model is not None:
self.occ_model.log()
log.blank()
def guess_core_hamiltonian(overlap, core, *orbs):
'''Guess the orbitals by diagonalizing a core Hamiltonian.
Parameters
----------
overlap : np.ndarray, shape=(nbasis, nbasis), dtype=float
The overlap operator.
core : np.ndarray, shape=(nbasis, nbasis), dtype=float
The core Hamiltonian. operator that resembles a Fock operator is fine. Usually,
one adds the kinetic energy and nuclear attraction integrals.
orb1, orb2, ... : Orbitals
A list of Orbitals objects (output arguments)
This method only modifies the expansion coefficients and the orbital energies.
'''
if log.do_medium:
log('Performing a core Hamiltonian guess.')
log.blank()
if len(orbs) == 0:
raise TypeError('At least one set of orbitals.')
# Compute orbitals.
orbs[0].from_fock(core, overlap)
# Copy to other Orbitals objects.
for i in xrange(1, len(orbs)):
orbs[i].coeffs[:] = orbs[0].coeffs
orbs[i].energies[:] = orbs[0].energies
def _log_init(self):
'''Write a summary of the wavefunction to the screen logger'''
if log.do_medium:
log('Initialized: %s' % self)
if self.occ_model is not None:
self.occ_model.log()
log.blank()
def guess_core_hamiltonian(overlap, core, *orbs):
'''Guess the orbitals by diagonalizing a core Hamiltonian.
Parameters
----------
overlap : np.ndarray, shape=(nbasis, nbasis), dtype=float
The overlap operator.
core : np.ndarray, shape=(nbasis, nbasis), dtype=float
The core Hamiltonian. operator that resembles a Fock operator is fine. Usually,
one adds the kinetic energy and nuclear attraction integrals.
orb1, orb2, ... : Orbitals
A list of Orbitals objects (output arguments)
This method only modifies the expansion coefficients and the orbital energies.
'''
if log.do_medium:
log('Performing a core Hamiltonian guess.')
log.blank()
if len(orbs) == 0:
raise TypeError('At least one set of orbitals.')
# Compute orbitals.
orbs[0].from_fock(core, overlap)
# Copy to other Orbitals objects.
for i in xrange(1, len(orbs)):
orbs[i].coeffs[:] = orbs[0].coeffs
orbs[i].energies[:] = orbs[0].energies
def _log_init(self):
if log.do_medium:
log('Initialized: %s' % self)
log.deflist([
('Numbers', self._rgrid_map.keys()),
('Records', self._map.keys()),
])
log.blank()
def _log_init(self):
if log.do_medium:
log('Initialized: %s' % self)
log.deflist([
('Numbers', self._rgrid_map.keys()),
('Records', self._map.keys()),
])
log.blank()
def guess_hamiltonian_core(system):
if log.do_medium:
log('Performing a hamiltonian core guess.')
log.blank()
if isinstance(system.wfn, RestrictedWFN):
guess_hamiltonian_core_cs(system)
elif isinstance(system.wfn, UnrestrictedWFN):
guess_hamiltonian_core_os(system)
else:
raise NotImplementedError
def guess_hamiltonian_core(system):
if log.do_medium:
log('Performing a hamiltonian core guess.')
log.blank()
if isinstance(system.wfn, RestrictedWFN):
guess_hamiltonian_core_cs(system)
elif isinstance(system.wfn, UnrestrictedWFN):
guess_hamiltonian_core_os(system)
else:
raise NotImplementedError
def _log_init(self):
if log.do_medium:
log('Initialized: %s' % self)
log.deflist([
('Size', self.size),
('Switching function', 'k=%i' % self._k),
])
log.blank()
# Cite reference
log.cite('becke1988_multicenter', 'the multicenter integration scheme used for the molecular integration grid')
log.cite('cordero2008', 'the covalent radii used for the Becke-Lebedev molecular integration grid')
def _log_init(self):
if log.do_medium:
log('Initialized: %s' % self)
log.deflist([
('Size', self.size),
('Switching function', 'k=%i' % self._k),
])
log.blank()
# Cite reference
biblio.cite('becke1988_multicenter', 'the multicenter integration scheme used for the molecular integration grid')
biblio.cite('cordero2008', 'the covalent radii used for the Becke-Lebedev molecular integration grid')
def guess_core_hamiltonian(overlap, *args, **kwargs):
'''Guess the orbitals by diagonalizing a core Hamiltonian
**Arguments:**
overlap
The overlap operator.
core1, core2, ...
A number of operators that add up to the core Hamiltonian. Any set
of operators whose sum resembles a Fock operator is fine. Usually,
one passes the kinetic energy and nuclear attraction integrals.
exp1, exp2, ...
A list of wavefunction expansion objects (output arguments)
This method only modifies the expansion coefficients and the orbital
energies.
'''
if len(kwargs) != 0:
raise TypeError('Unknown keyword arguments: %s' % kwargs.keys())
if log.do_medium:
log('Performing a core Hamiltonian guess.')
log.blank()
core = []
exps = []
for arg in args:
if isinstance(arg, TwoIndex):
core.append(arg)
elif isinstance(arg, Expansion):
exps.append(arg)
else:
raise TypeError('argument of unsupported type: %s' % arg)
if len(core) == 0:
raise TypeError(
'At least one term is needed for the core Hamiltonian.')
if len(exps) == 0:
raise TypeError('At least one wavefunction expansion is needed.')
# Take sum of operators for core hamiltonian
hamcore = core[0].copy()
for term in core[1:]:
hamcore.iadd(term)
# Compute orbitals.
exps[0].from_fock(hamcore, overlap)
# Copy to other expansions.
for i in xrange(1, len(exps)):
exps[i].coeffs[:] = exps[0].coeffs
exps[i].energies[:] = exps[0].energies
def guess_core_hamiltonian(overlap, *args, **kwargs):
'''Guess the orbitals by diagonalizing a core Hamiltonian
**Arguments:**
overlap
The overlap operator.
core1, core2, ...
A number of operators that add up to the core Hamiltonian. Any set
of operators whose sum resembles a Fock operator is fine. Usually,
one passes the kinetic energy and nuclear attraction integrals.
exp1, exp2, ...
A list of wavefunction expansion objects (output arguments)
This method only modifies the expansion coefficients and the orbital
energies.
'''
if len(kwargs) != 0:
raise TypeError('Unknown keyword arguments: %s' % kwargs.keys())
if log.do_medium:
log('Performing a core Hamiltonian guess.')
log.blank()
core = []
exps = []
for arg in args:
if isinstance(arg, TwoIndex):
core.append(arg)
elif isinstance(arg, Expansion):
exps.append(arg)
else:
raise TypeError('argument of unsupported type: %s' % arg)
if len(core) == 0:
raise TypeError('At least one term is needed for the core Hamiltonian.')
if len(exps) == 0:
raise TypeError('At least one wavefunction expansion is needed.')
# Take sum of operators for core hamiltonian
hamcore = core[0].copy()
for term in core[1:]:
hamcore.iadd(term)
# Compute orbitals.
exps[0].from_fock(hamcore, overlap)
# Copy to other expansions.
for i in xrange(1, len(exps)):
exps[i].coeffs[:] = exps[0].coeffs
exps[i].energies[:] = exps[0].energies
def log(self, coeffs):
eref = min(state.energy for state in self.stack[:self.nused])
if eref is None:
log(' DIIS history normsq coeff id')
for i in xrange(self.nused):
state = self.stack[i]
log(' DIIS history %12.5e %12.7f %8i' % (state.normsq, coeffs[i], state.identity))
else:
log(' DIIS history normsq energy coeff id')
for i in xrange(self.nused):
state = self.stack[i]
log(' DIIS history %12.5e %12.5e %12.7f %8i' % (state.normsq, state.energy-eref, coeffs[i], state.identity))
log.blank()
def log(self, coeffs):
eref = min(state.energy for state in self.stack[:self.nused])
if eref is None:
log(' DIIS history norm coeff id')
for i in xrange(self.nused):
state = self.stack[i]
log(' DIIS history %12.5e %12.7f %8i' % (state.norm, coeffs[i], state.identity))
else:
log(' DIIS history norm energy coeff id')
for i in xrange(self.nused):
state = self.stack[i]
log(' DIIS history %12.5e %12.5e %12.7f %8i' % (state.norm, state.energy-eref, coeffs[i], state.identity))
log.blank()
def log_energy(self):
'''Write an overview of the last energy computation on screen'''
log('Contributions to the energy:')
log.hline()
log(' Energy term Value')
log.hline()
for term in self.terms:
energy = self.system.extra['energy_%s' % term.label]
log('%50s %20.12f' % (term.label, energy))
log('%50s %20.12f' % ('nn', self.system.extra['energy_nn']))
log('%50s %20.12f' % ('total', self.system.extra['energy']))
log.hline()
log.blank()
def log(self):
"""Write an overview of the last computation on screen."""
log('Contributions to the energy:')
log.hline()
log(' term Value')
log.hline()
for term in self.terms:
energy = self.cache['energy_%s' % term.label]
log('%50s %20.12f' % (term.label, energy))
for key, energy in self.external.iteritems():
log('%50s %20.12f' % (key, energy))
log('%50s %20.12f' % ('total', self.cache['energy']))
log.hline()
log.blank()
def log_energy(self):
'''Write an overview of the last energy computation on screen'''
log('Contributions to the energy:')
log.hline()
log(' Energy term Value'
)
log.hline()
for term in self.terms:
energy = self.system.extra['energy_%s' % term.label]
log('%50s %20.12f' % (term.label, energy))
log('%50s %20.12f' % ('nn', self.system.extra['energy_nn']))
log('%50s %20.12f' % ('total', self.system.extra['energy']))
log.hline()
log.blank()
def __init__(self, system, grid, local, slow, lmax, moldens=None):
'''
**Arguments:**
system
The system to be partitioned.
grid
The integration grid
local
Whether or not to use local (non-periodic) grids.
slow
When ``True``, also the AIM properties are computed that use the
AIM overlap operators.
lmax
The maximum angular momentum in multipole expansions.
**Optional arguments:**
moldens
The all-electron density grid data.
'''
JustOnceClass.__init__(self)
self._system = system
self._grid = grid
self._local = local
self._slow = slow
self._lmax = lmax
# Caching stuff, to avoid recomputation of earlier results
self._cache = Cache()
# Caching of work arrays to avoid reallocation
if moldens is not None:
self._cache.dump('moldens', moldens)
# Initialize the subgrids
if local:
self._init_subgrids()
# Some screen logging
self._init_log_base()
self._init_log_scheme()
self._init_log_memory()
if log.do_medium:
log.blank()
def __init__(self, system, grid, local, slow, lmax, moldens=None):
'''
**Arguments:**
system
The system to be partitioned.
grid
The integration grid
local
Whether or not to use local (non-periodic) grids.
slow
When ``True``, also the AIM properties are computed that use the
AIM overlap operators.
lmax
The maximum angular momentum in multipole expansions.
**Optional arguments:**
moldens
The all-electron density grid data.
'''
JustOnceClass.__init__(self)
self._system = system
self._grid = grid
self._local = local
self._slow = slow
self._lmax = lmax
# Caching stuff, to avoid recomputation of earlier results
self._cache = Cache()
# Caching of work arrays to avoid reallocation
if moldens is not None:
self._cache.dump('moldens', moldens)
# Initialize the subgrids
if local:
self._init_subgrids()
# Some screen logging
self._init_log_base()
self._init_log_scheme()
self._init_log_memory()
if log.do_medium:
log.blank()
def _init_log_memory(self):
if log.do_medium:
# precompute arrays sizes for certain grids
nbyte_global = self.grid.size*8
nbyte_locals = np.array([self.get_grid(i).size*8 for i in xrange(self.natom)])
# compute and report usage
estimates = self.get_memory_estimates()
nbyte_total = 0
log('Coarse estimate of memory usage for the partitioning:')
log(' Label Memory[GB]')
log.hline()
for label, nlocals, nglobal in estimates:
nbyte = np.dot(nlocals, nbyte_locals) + nglobal*nbyte_global
log('%30s %10.3f' % (label, nbyte/1024.0**3))
nbyte_total += nbyte
log('%30s %10.3f' % ('Total', nbyte_total/1024.0**3))
log.hline()
log.blank()
def _init_log_memory(self):
if log.do_medium:
# precompute arrays sizes for certain grids
nbyte_global = self.grid.size*8
nbyte_locals = np.array([self.get_grid(i).size*8 for i in xrange(self.natom)])
# compute and report usage
estimates = self.get_memory_estimates()
nbyte_total = 0
log('Coarse estimate of memory usage for the partitioning:')
log(' Label Memory[GB]')
log.hline()
for label, nlocals, nglobal in estimates:
nbyte = np.dot(nlocals, nbyte_locals) + nglobal*nbyte_global
log('%30s %10.3f' % (label, nbyte/1024.0**3))
nbyte_total += nbyte
log('%30s %10.3f' % ('Total', nbyte_total/1024.0**3))
log.hline()
log.blank()
def project_orbitals_mgs(system, old_wfn, old_obasis, eps=1e-10):
'''Project orbitals from the ``old_wfn`` (wrt ``old_basis``) on the wfn of the ``system`` object with the modified Gram-Schmidt algorithm.
**Arguments:**
system
The system with the new orbital basis. It must have a
wavefunction object compatible with the old wavefunction (restricted
versus unrestricted).
old_wfn
The old (mean-field) wavefunction object
old_obasis
The orbital basis for the old wavefunction
**Optional arguments:**
eps
A threshold for the renormalization in the Gram-Schmidt procedure.
See ``project_orbitals_mgs_low`` for details.
'''
if log.do_medium:
log('Projecting the wavefunction on a new basis.')
log.blank()
if isinstance(old_wfn, RestrictedWFN):
assert isinstance(system.wfn, RestrictedWFN)
if 'exp_alpha' not in system.wfn._cache:
system.wfn.init_exp('alpha')
project_orbitals_mgs_low(old_obasis, system.obasis, old_wfn.exp_alpha,
system.wfn.exp_alpha, eps)
else:
assert isinstance(system.wfn, UnrestrictedWFN)
if 'exp_alpha' not in system.wfn._cache:
system.wfn.init_exp('alpha')
system.wfn.init_exp('beta')
project_orbitals_mgs_low(old_obasis, system.obasis, old_wfn.exp_alpha,
system.wfn.exp_alpha, eps)
project_orbitals_mgs_low(old_obasis, system.obasis, old_wfn.exp_beta,
system.wfn.exp_beta, eps)
system.wfn.clear_dm()
def _log_init(self):
'''Write some basic information about the system to the screen logger.'''
if log.do_medium:
log('Initialized: %s' % self)
log.deflist([('Number of atoms', self.natom)] +
[('Number of %s' % periodic[n].symbol,
(self.numbers == n).sum())
for n in sorted(np.unique(self.numbers))] + [
('Linalg Factory', self._lf),
('Orbital basis', self._obasis),
('Wavefunction', self._wfn),
('Checkpoint file', self._chk),
])
if len(self._cache) > 0:
log('The following cached items are present: %s' %
(', '.join(self._cache.iterkeys())))
if len(self._extra) > 0:
log('The following extra attributes are present: %s' %
(', '.join(self._extra.iterkeys())))
log.blank()
def log(self):
log(' Nr Pop Chg Energy Ionization Affinity'
)
log.hline()
for number, cases in sorted(self.all.iteritems()):
for pop, energy in sorted(cases.iteritems()):
energy_prev = cases.get(pop - 1)
if energy_prev is None:
ip_str = ''
else:
ip_str = '% 18.10f' % (energy_prev - energy)
energy_next = cases.get(pop + 1)
if energy_next is None:
ea_str = ''
else:
ea_str = '% 18.10f' % (energy - energy_next)
log('%3i %3i %+3i % 18.10f %18s %18s' %
(number, pop, number - pop, energy, ip_str, ea_str))
log.blank()
def log(self):
log(' Nr Pop Chg Energy Ionization Affinity')
log.hline()
for number, cases in sorted(self.all.iteritems()):
for pop, energy in sorted(cases.iteritems()):
energy_prev = cases.get(pop-1)
if energy_prev is None:
ip_str = ''
else:
ip_str = '% 18.10f' % (energy_prev - energy)
energy_next = cases.get(pop+1)
if energy_next is None:
ea_str = ''
else:
ea_str = '% 18.10f' % (energy - energy_next)
log('%3i %3i %+3i % 18.10f %18s %18s' % (
number, pop, number-pop, energy, ip_str, ea_str
))
log.blank()
def project_orbitals_mgs(system, old_wfn, old_obasis, eps=1e-10):
'''Project orbitals from the ``old_wfn`` (wrt ``old_basis``) on the wfn of the ``system`` object with the modified Gram-Schmidt algorithm.
**Arguments:**
system
The system with the new orbital basis. It must have a
wavefunction object compatible with the old wavefunction (restricted
versus unrestricted).
old_wfn
The old (mean-field) wavefunction object
old_obasis
The orbital basis for the old wavefunction
**Optional arguments:**
eps
A threshold for the renormalization in the Gram-Schmidt procedure.
See ``project_orbitals_mgs_low`` for details.
'''
if log.do_medium:
log('Projecting the wavefunction on a new basis.')
log.blank()
if isinstance(old_wfn, RestrictedWFN):
assert isinstance(system.wfn, RestrictedWFN)
if 'exp_alpha' not in system.wfn._cache:
system.wfn.init_exp('alpha')
project_orbitals_mgs_low(old_obasis, system.obasis, old_wfn.exp_alpha, system.wfn.exp_alpha, eps)
else:
assert isinstance(system.wfn, UnrestrictedWFN)
if 'exp_alpha' not in system.wfn._cache:
system.wfn.init_exp('alpha')
system.wfn.init_exp('beta')
project_orbitals_mgs_low(old_obasis, system.obasis, old_wfn.exp_alpha, system.wfn.exp_alpha, eps)
project_orbitals_mgs_low(old_obasis, system.obasis, old_wfn.exp_beta, system.wfn.exp_beta, eps)
system.wfn.clear_dm()
def __call__(self, ham, lf, overlap, occ_model, *exps):
"""Find a self-consistent set of orbitals.
Parameters
----------
ham : EffHam
An effective Hamiltonian.
lf : LinalgFactor
The linalg factory to be used.
overlap : TwoIndex
The overlap operator.
occ_model : OccModel
Model for the orbital occupations.
exp1, exp2, ... : Expansion
The initial orbitals. The number of dms must match ham.ndm.
"""
# Some type checking
if ham.ndm != len(exps):
raise TypeError('The number of initial orbital expansions does not match the Hamiltonian.')
# Impose the requested occupation numbers
occ_model.assign(*exps)
# Check the orthogonality of the orbitals
for exp in exps:
exp.check_normalization(overlap)
if log.do_medium:
log('Starting plain SCF solver. ndm=%i' % ham.ndm)
log.hline()
log('Iter Error')
log.hline()
focks = [lf.create_two_index() for i in xrange(ham.ndm)]
dms = [lf.create_two_index() for i in xrange(ham.ndm)]
converged = False
counter = 0
while self.maxiter is None or counter < self.maxiter:
# convert the orbital expansions to density matrices
for i in xrange(ham.ndm):
exps[i].to_dm(dms[i])
# feed the latest density matrices in the hamiltonian
ham.reset(*dms)
# Construct the Fock operator
ham.compute_fock(*focks)
# Check for convergence
error = 0.0
for i in xrange(ham.ndm):
error += exps[i].error_eigen(focks[i], overlap)
if log.do_medium:
log('%4i %12.5e' % (counter, error))
if error < self.threshold:
converged = True
break
# If requested, add the level shift to the Fock operator
if self.level_shift > 0:
for i in xrange(ham.ndm):
lshift = overlap.copy()
lshift.idot(dms[i])
lshift.idot(overlap)
# The normal behavior is to shift down the occupied levels.
lshift.iscale(-self.level_shift)
focks[i].iadd(lshift)
# Diagonalize the fock operators to obtain new orbitals and
for i in xrange(ham.ndm):
exps[i].from_fock(focks[i], overlap)
# If requested, compensate for level-shift. This compensation
# is only correct when the SCF has converged.
if self.level_shift > 0:
exps[i].energies[:] += self.level_shift*exps[i].occupations
# Assign new occupation numbers.
occ_model.assign(*exps)
# counter
counter += 1
if log.do_medium:
log.blank()
if not self.skip_energy:
ham.compute_energy()
if log.do_medium:
ham.log()
if not converged:
raise NoSCFConvergence
return counter
def converge_scf_cs(ham, maxiter=128, threshold=1e-8, skip_energy=False):
'''Minimize the energy of the wavefunction with basic closed-shell SCF
**Arguments:**
ham
A Hamiltonian instance.
**Optional arguments:**
maxiter
The maximum number of iterations. When set to None, the SCF loop
will go one until convergence is reached.
threshold
The convergence threshold for the wavefunction.
skip_energy
When set to True, the final energy is not computed.
**Raises:**
NoSCFConvergence
if the convergence criteria are not met within the specified number
of iterations.
**Returns:** the number of iterations
'''
if log.do_medium:
log('Starting restricted closed-shell SCF')
log.hline()
log('Iter Error(alpha)')
log.hline()
# Get rid of outdated stuff
ham.clear()
lf = ham.system.lf
wfn = ham.system.wfn
overlap = ham.system.get_overlap()
fock = lf.create_one_body()
converged = False
counter = 0
while maxiter is None or counter < maxiter:
# Construct the Fock operator
fock.clear()
ham.compute_fock(fock, None)
# Check for convergence
error = lf.error_eigen(fock, overlap, wfn.exp_alpha)
if log.do_medium:
log('%4i %12.5e' % (counter, error))
if error < threshold:
converged = True
break
# Diagonalize the fock operator
wfn.clear() # discard previous wfn state
wfn.update_exp(fock, overlap)
# Let the hamiltonian know that the wavefunction has changed.
ham.clear()
# Write intermediate results to checkpoint
ham.system.update_chk('wfn')
# counter
counter += 1
if log.do_medium:
log.blank()
if not skip_energy:
ham.compute()
if log.do_medium:
ham.log_energy()
if not converged:
raise NoSCFConvergence
return counter
def setup_mean_field_wfn(system, charge=0, mult=None, restricted=None, temperature=0):
'''Initialize a mean-field wavefunction and assign it to the given system.
**Arguments:**
system
A System instance.
**Optional Arguments:**
charge
The total charge of the system. Defaults to zero.
mult
The spin multiplicity. Defaults to lowest possible. Use 'free' to
let the SCF algorithm find the spin multiplicity with the lowest
energy. (Beware of local minima.)
temperature
The electronic temperature used for the Fermi smearing.
restricted
Set to True or False to enforce a restricted or unrestricted
wavefunction. Note that restricted open shell is not yet
supported. When not set, restricted is used when mult==1 and
unrestricted otherwise.
If a wavefunction of the correct type is already present, it will be
configured with the requested charge and multiplicity.
'''
if system._obasis is None:
raise RuntimeError('A wavefunction can only be initialized when a basis is specified.')
# Determine charge, spin, mult and restricted
if charge is None:
charge = 0
nel = system.numbers.sum() - charge
if isinstance(nel, int):
if mult is None:
mult = nel%2+1
elif mult != 'free' and ((nel%2 == 0) ^ (mult%2 != 0)):
raise ValueError('Not compatible: number of electrons = %i and spin multiplicity = %i' % (nel, mult))
else:
if mult is None:
if restricted is True:
mult = 1.0
else:
raise ValueError('In case of an unrestricted wfn and a fractional number of electrons, mult must be given explicitly or must be set to \'free\'.')
if mult != 'free' and mult < 1:
raise ValueError('mult must be strictly positive.')
if restricted is True and mult != 1:
raise ValueError('Restricted==True only works when mult==1. Restricted open shell is not supported yet.')
if restricted is None:
restricted = mult==1
# Show some thing on screen.
if log.do_medium:
log('Wavefunction initialization, without initial guess.')
log.deflist([
('Charge', charge),
('Multiplicity', mult),
('Number of e', nel),
('Restricted', restricted),
])
log.blank()
# Create a model for the occupation numbers
if temperature == 0:
if restricted:
occ_model = AufbauOccModel(nel/2, nel/2)
elif mult=='free':
occ_model = AufbauSpinOccModel(nel)
else:
occ_model = AufbauOccModel((nel + (mult-1))/2, (nel - (mult-1))/2)
else:
if restricted:
occ_model = FermiOccModel(nel/2, nel/2, temperature)
elif mult=='free':
raise NotImplementedError
#occ_model = FermiSpinOccModel(nel)
else:
occ_model = FermiOccModel((nel + (mult-1))/2, (nel - (mult-1))/2, temperature)
if system._wfn is not None:
# Check if the existing wfn is consistent with the arguments
if not isinstance(system.wfn, MeanFieldWFN):
raise ValueError('A wavefunction is already present and it is not a mean-field wavefunction.')
elif system.wfn.nbasis != system.obasis.nbasis:
raise ValueError('The number of basis functions in the wfn is incorrect.')
elif restricted ^ isinstance(system.wfn, RestrictedWFN):
raise ValueError('The wfn does not match the restricted argument.')
# Assign occ_model
system.wfn.occ_model = occ_model
# If the wfn contains an expansion, update the occupations and remove
# density matrices. Otherwise clean up
if 'exp_alpha' in system.wfn._cache:
if restricted:
system.wfn.occ_model.assign(system.wfn.exp_alpha)
else:
system.wfn.occ_model.assign(system.wfn.exp_alpha, system.wfn.exp_beta)
system.wfn.clear_dm()
else:
system.wfn.clear()
else:
# if the wfn does not exist yet, create a proper one.
if restricted:
system._wfn = RestrictedWFN(system.lf, system.obasis.nbasis, occ_model)
else:
system._wfn = UnrestrictedWFN(system.lf, system.obasis.nbasis, occ_model)
def setup_mean_field_wfn(system,
charge=0,
mult=None,
restricted=None,
temperature=0):
'''Initialize a mean-field wavefunction and assign it to the given system.
**Arguments:**
system
A System instance.
**Optional Arguments:**
charge
The total charge of the system. Defaults to zero.
mult
The spin multiplicity. Defaults to lowest possible. Use 'free' to
let the SCF algorithm find the spin multiplicity with the lowest
energy. (Beware of local minima.)
temperature
The electronic temperature used for the Fermi smearing.
restricted
Set to True or False to enforce a restricted or unrestricted
wavefunction. Note that restricted open shell is not yet
supported. When not set, restricted is used when mult==1 and
unrestricted otherwise.
If a wavefunction of the correct type is already present, it will be
configured with the requested charge and multiplicity.
'''
if system._obasis is None:
raise RuntimeError(
'A wavefunction can only be initialized when a basis is specified.'
)
# Determine charge, spin, mult and restricted
if charge is None:
charge = 0
nel = system.numbers.sum() - charge
if isinstance(nel, int):
if mult is None:
mult = nel % 2 + 1
elif mult != 'free' and ((nel % 2 == 0) ^ (mult % 2 != 0)):
raise ValueError(
'Not compatible: number of electrons = %i and spin multiplicity = %i'
% (nel, mult))
else:
if mult is None:
if restricted is True:
mult = 1.0
else:
raise ValueError(
'In case of an unrestricted wfn and a fractional number of electrons, mult must be given explicitly or must be set to \'free\'.'
)
if mult != 'free' and mult < 1:
raise ValueError('mult must be strictly positive.')
if restricted is True and mult != 1:
raise ValueError(
'Restricted==True only works when mult==1. Restricted open shell is not supported yet.'
)
if restricted is None:
restricted = mult == 1
# Show some thing on screen.
if log.do_medium:
log('Wavefunction initialization, without initial guess.')
log.deflist([
('Charge', charge),
('Multiplicity', mult),
('Number of e', nel),
('Restricted', restricted),
])
log.blank()
# Create a model for the occupation numbers
if temperature == 0:
if restricted:
occ_model = AufbauOccModel(nel / 2, nel / 2)
elif mult == 'free':
occ_model = AufbauSpinOccModel(nel)
else:
occ_model = AufbauOccModel((nel + (mult - 1)) / 2,
(nel - (mult - 1)) / 2)
else:
if restricted:
occ_model = FermiOccModel(nel / 2, nel / 2, temperature)
elif mult == 'free':
raise NotImplementedError
#occ_model = FermiSpinOccModel(nel)
else:
occ_model = FermiOccModel((nel + (mult - 1)) / 2,
(nel - (mult - 1)) / 2, temperature)
if system._wfn is not None:
# Check if the existing wfn is consistent with the arguments
if not isinstance(system.wfn, MeanFieldWFN):
raise ValueError(
'A wavefunction is already present and it is not a mean-field wavefunction.'
)
elif system.wfn.nbasis != system.obasis.nbasis:
raise ValueError(
'The number of basis functions in the wfn is incorrect.')
elif restricted ^ isinstance(system.wfn, RestrictedWFN):
raise ValueError('The wfn does not match the restricted argument.')
# Assign occ_model
system.wfn.occ_model = occ_model
# If the wfn contains an expansion, update the occupations and remove
# density matrices. Otherwise clean up
if 'exp_alpha' in system.wfn._cache:
if restricted:
system.wfn.occ_model.assign(system.wfn.exp_alpha)
else:
system.wfn.occ_model.assign(system.wfn.exp_alpha,
system.wfn.exp_beta)
system.wfn.clear_dm()
else:
system.wfn.clear()
else:
# if the wfn does not exist yet, create a proper one.
if restricted:
system._wfn = RestrictedWFN(system.lf, system.obasis.nbasis,
occ_model)
else:
system._wfn = UnrestrictedWFN(system.lf, system.obasis.nbasis,
occ_model)
def converge_scf_cs(ham, maxiter=128, threshold=1e-8, skip_energy=False):
'''Minimize the energy of the wavefunction with basic closed-shell SCF
**Arguments:**
ham
A Hamiltonian instance.
**Optional arguments:**
maxiter
The maximum number of iterations. When set to None, the SCF loop
will go one until convergence is reached.
threshold
The convergence threshold for the wavefunction.
skip_energy
When set to True, the final energy is not computed.
**Raises:**
NoSCFConvergence
if the convergence criteria are not met within the specified number
of iterations.
**Returns:** the number of iterations
'''
if log.do_medium:
log('Starting restricted closed-shell SCF')
log.hline()
log('Iter Error(alpha)')
log.hline()
# Get rid of outdated stuff
ham.clear()
lf = ham.system.lf
wfn = ham.system.wfn
overlap = ham.system.get_overlap()
fock = lf.create_one_body()
converged = False
counter = 0
while maxiter is None or counter < maxiter:
# Construct the Fock operator
fock.clear()
ham.compute_fock(fock, None)
# Check for convergence
error = lf.error_eigen(fock, overlap, wfn.exp_alpha)
if log.do_medium:
log('%4i %12.5e' % (counter, error))
if error < threshold:
converged = True
break
# Diagonalize the fock operator
wfn.clear() # discard previous wfn state
wfn.update_exp(fock, overlap)
# Let the hamiltonian know that the wavefunction has changed.
ham.clear()
# Write intermediate results to checkpoint
ham.system.update_chk('wfn')
# counter
counter += 1
if log.do_medium:
log.blank()
if not skip_energy:
ham.compute()
if log.do_medium:
ham.log_energy()
if not converged:
raise NoSCFConvergence
return counter
def __call__(self, ham, lf, overlap, occ_model, *dms):
'''Find a self-consistent set of density matrices.
**Arguments:**
ham
An effective Hamiltonian.
lf
The linalg factory to be used.
overlap
The overlap operator.
occ_model
Model for the orbital occupations.
dm1, dm2, ...
The initial density matrices. The number of dms must match
ham.ndm.
'''
# Some type checking
if ham.ndm != len(dms):
raise TypeError('The number of initial density matrices does not match the Hamiltonian.')
# Check input density matrices.
for i in xrange(ham.ndm):
check_dm(dms[i], overlap, lf)
occ_model.check_dms(overlap, *dms)
# keep local variables as attributes for inspection/debugging by caller
self._history = self.DIISHistoryClass(lf, self.nvector, ham.ndm, ham.deriv_scale, overlap)
self._focks = [lf.create_two_index() for i in xrange(ham.ndm)]
self._exps = [lf.create_expansion() for i in xrange(ham.ndm)]
if log.do_medium:
log('Starting restricted closed-shell %s-SCF' % self._history.name)
log.hline()
log('Iter Error CN Last nv Method Energy Change')
log.hline()
converged = False
counter = 0
while self.maxiter is None or counter < self.maxiter:
# Construct the Fock operator from scratch if the history is empty:
if self._history.nused == 0:
# feed the latest density matrices in the hamiltonian
ham.reset(*dms)
# Construct the Fock operators
ham.compute_fock(*self._focks)
# Compute the energy if needed by the history
energy = ham.compute_energy() if self._history.need_energy \
else None
# Add the current fock+dm pair to the history
error = self._history.add(energy, dms, self._focks)
# Screen logging
if log.do_high:
log(' DIIS add')
if error < self.threshold:
converged = True
break
if log.do_high:
log.blank()
if log.do_medium:
energy_str = ' '*20 if energy is None else '% 20.13f' % energy
log('%4i %12.5e %2i %20s' % (
counter, error, self._history.nused, energy_str
))
if log.do_high:
log.blank()
fock_interpolated = False
else:
energy = None
fock_interpolated = True
# Take a regular SCF step using the current fock matrix. Then
# construct a new density matrix and fock matrix.
for i in xrange(ham.ndm):
self._exps[i].from_fock(self._focks[i], overlap)
occ_model.assign(*self._exps)
for i in xrange(ham.ndm):
self._exps[i].to_dm(dms[i])
ham.reset(*dms)
energy = ham.compute_energy() if self._history.need_energy else None
ham.compute_fock(*self._focks)
# Add the current (dm, fock) pair to the history
if log.do_high:
log(' DIIS add')
error = self._history.add(energy, dms, self._focks)
# break when converged
if error < self.threshold:
converged = True
break
# Screen logging
if log.do_high:
log.blank()
if log.do_medium:
energy_str = ' '*20 if energy is None else '% 20.13f' % energy
log('%4i %12.5e %2i %20s' % (
counter, error, self._history.nused, energy_str
))
if log.do_high:
log.blank()
# get extra/intra-polated Fock matrix
while True:
# The following method writes the interpolated dms and focks
# in-place.
energy_approx, coeffs, cn, method, error = self._history.solve(dms, self._focks)
# if the error is small on the interpolated state, we have
# converged to a solution that may have fractional occupation
# numbers.
if error < self.threshold:
converged = True
break
#if coeffs[coeffs<0].sum() < -1:
# if log.do_high:
# log(' DIIS (coeffs too negative) -> drop %i and retry' % self._history.stack[0].identity)
# self._history.shrink()
if self._history.nused <= 2:
break
if coeffs[-1] == 0.0:
if log.do_high:
log(' DIIS (last coeff zero) -> drop %i and retry' % self._history.stack[0].identity)
self._history.shrink()
else:
break
if False and len(coeffs) == 2:
dms_tmp = [dm.copy() for dm in dms]
import matplotlib.pyplot as pt
xs = np.linspace(0.0, 1.0, 25)
a, b = self._history._setup_equations()
energies1 = []
energies2 = []
for x in xs:
x_coeffs = np.array([1-x, x])
energies1.append(np.dot(x_coeffs, 0.5*np.dot(a, x_coeffs) - b))
self._history._build_combinations(x_coeffs, dms_tmp, None)
ham.reset(*dms_tmp)
energies2.append(ham.compute_energy())
print x, energies1[-1], energies2[-1]
pt.clf()
pt.plot(xs, energies1, label='est')
pt.plot(xs, energies2, label='ref')
pt.axvline(coeffs[1], color='k')
pt.legend(loc=0)
pt.savefig('diis_test_%05i.png' % counter)
if energy_approx is not None:
energy_change = energy_approx - min(state.energy for state in self._history.stack)
else:
energy_change = None
# log
if log.do_high:
self._history.log(coeffs)
if log.do_medium:
change_str = ' '*10 if energy_change is None else '% 12.7f' % energy_change
log('%4i %10.3e %12.7f %2i %s %12s' % (
counter, cn, coeffs[-1], self._history.nused, method,
change_str
))
if log.do_high:
log.blank()
if self.prune_old_states:
# get rid of old states with zero coeff
for i in xrange(self._history.nused):
if coeffs[i] == 0.0:
if log.do_high:
log(' DIIS insignificant -> drop %i' % self._history.stack[0].identity)
self._history.shrink()
else:
break
# counter
counter += 1
if log.do_medium:
if converged:
log('%4i %12.5e (converged)' % (counter, error))
log.blank()
if not self.skip_energy or self._history.need_energy:
if not self._history.need_energy:
ham.compute_energy()
if log.do_medium:
ham.log()
if not converged:
raise NoSCFConvergence
return counter
def __call__(self, ham, lf, overlap, occ_model, *exps):
'''Find a self-consistent set of orbitals.
**Arguments:**
ham
An effective Hamiltonian.
lf
The linalg factory to be used.
overlap
The overlap operator.
occ_model
Model for the orbital occupations.
exp1, exp2, ...
The initial orbitals. The number of dms must match ham.ndm.
'''
# Some type checking
if ham.ndm != len(exps):
raise TypeError('The number of initial orbital expansions does not match the Hamiltonian.')
# Impose the requested occupation numbers
occ_model.assign(*exps)
# Check the orthogonality of the orbitals
for exp in exps:
exp.check_normalization(overlap)
if log.do_medium:
log('Starting plain SCF solver. ndm=%i' % ham.ndm)
log.hline()
log('Iter Error')
log.hline()
focks = [lf.create_two_index() for i in xrange(ham.ndm)]
dms = [lf.create_two_index() for i in xrange(ham.ndm)]
converged = False
counter = 0
while self.maxiter is None or counter < self.maxiter:
# convert the orbital expansions to density matrices
for i in xrange(ham.ndm):
exps[i].to_dm(dms[i])
# feed the latest density matrices in the hamiltonian
ham.reset(*dms)
# Construct the Fock operator
ham.compute_fock(*focks)
# Check for convergence
error = 0.0
for i in xrange(ham.ndm):
error += exps[i].error_eigen(focks[i], overlap)
if log.do_medium:
log('%4i %12.5e' % (counter, error))
if error < self.threshold:
converged = True
break
# Diagonalize the fock operators to obtain new orbitals and
for i in xrange(ham.ndm):
exps[i].from_fock(focks[i], overlap)
# Assign new occupation numbers.
occ_model.assign(*exps)
# counter
counter += 1
if log.do_medium:
log.blank()
if not self.skip_energy:
ham.compute_energy()
if log.do_medium:
ham.log()
if not converged:
raise NoSCFConvergence
return counter
def converge_scf_diis_cs(ham, DIISHistoryClass, maxiter=128, threshold=1e-6, nvector=6, prune_old_states=False, skip_energy=False, scf_step='regular'):
'''Minimize the energy of the closed-shell wavefunction with EDIIS
**Arguments:**
ham
A Hamiltonian instance.
DIISHistoryClass
A DIIS history class.
**Optional arguments:**
maxiter
The maximum number of iterations. When set to None, the SCF loop
will go one until convergence is reached.
threshold
The convergence threshold for the wavefunction
prune_old_states
When set to True, old states are pruned from the history when their
coefficient is zero. Pruning starts at the oldest state and stops
as soon as a state is encountered with a non-zero coefficient. Even
if some newer states have a zero coefficient.
skip_energy
When set to True, the final energy is not computed. Note that some
DIIS variants need to compute the energy anyway. for these methods
this option is irrelevant.
scf_step
The type of SCF step to take after the interpolated states was
create from the DIIS history. This can be 'regular', 'oda2' or
'oda3'.
**Raises:**
NoSCFConvergence
if the convergence criteria are not met within the specified number
of iterations.
**Returns:** the number of iterations
'''
# allocated and define some one body operators
lf = ham.system.lf
wfn = ham.system.wfn
overlap = ham.system.get_overlap()
history = DIISHistoryClass(lf, nvector, overlap)
fock = lf.create_one_body()
dm = lf.create_one_body()
# The scf step
if scf_step == 'regular':
cs_scf_step = CSSCFStep(ham)
elif scf_step == 'oda2':
cs_scf_step = CSQuadraticODAStep(ham)
elif scf_step == 'oda3':
cs_scf_step = CSCubicODAStep(ham)
else:
raise ValueError('scf_step argument not recognized: %s' % scf_step)
# Get rid of outdated stuff
ham.clear()
if log.do_medium:
log('Starting restricted closed-shell %s-SCF' % history.name)
log.hline()
log('Iter Error(alpha) CN(alpha) Last(alpha) nv Method Energy Change')
log.hline()
converged = False
counter = 0
while maxiter is None or counter < maxiter:
# Construct the Fock operator from scratch:
if history.nused == 0:
# Update the Fock matrix
fock.clear()
ham.compute_fock(fock, None)
# Put this state also in the history
energy = ham.compute() if history.need_energy else None
# Add the current fock+dm pair to the history
error = history.add(energy, wfn.dm_alpha, fock)
if log.do_high:
log(' DIIS add')
if error < threshold:
converged = True
break
if log.do_high:
log.blank()
if log.do_medium:
energy_str = ' '*20 if energy is None else '% 20.13f' % energy
log('%4i %12.5e %2i %20s' % (
counter, error, history.nused, energy_str
))
if log.do_high:
log.blank()
fock_interpolated = False
else:
energy = None
fock_interpolated = True
# Construct a new density matrix and fock matrix (based on the current
# density matrix or fock matrix). The fock matrix is modified in-place
# while the density matrix is stored in ham.system.wfn
mixing = cs_scf_step(energy, fock, fock_interpolated)
if mixing == 0.0:
converged = True
break
energy = ham.compute() if history.need_energy else None
# Write intermediate results to checkpoint
ham.system.update_chk('wfn')
# Add the current (dm, fock) pair to the history
if log.do_high:
log(' DIIS add')
error = history.add(energy, wfn.dm_alpha, fock)
# break when converged
if error < threshold:
converged = True
break
if log.do_high:
log.blank()
if log.do_medium:
energy_str = ' '*20 if energy is None else '% 20.13f' % energy
log('%4i %12.5e %2i %20s' % (
counter, error, history.nused, energy_str
))
if log.do_high:
log.blank()
# get extra/intra-polated Fock matrix
while True:
energy_approx, coeffs, cn, method = history.solve(dm, fock)
#if coeffs[coeffs<0].sum() < -1:
# if log.do_high:
# log(' DIIS (coeffs too negative) -> drop %i and retry' % history.stack[0].identity)
# history.shrink()
if history.nused <= 2:
break
if coeffs[-1] == 0.0:
if log.do_high:
log(' DIIS (last coeff zero) -> drop %i and retry' % history.stack[0].identity)
history.shrink()
else:
break
if False and len(coeffs) == 2:
tmp = dm.copy()
import matplotlib.pyplot as pt
xs = np.linspace(0.0, 1.0, 25)
a, b = history._setup_equations()
energies1 = []
energies2 = []
for x in xs:
x_coeffs = np.array([1-x, x])
energies1.append(np.dot(x_coeffs, 0.5*np.dot(a, x_coeffs) - b))
history._build_combinations(x_coeffs, tmp, None)
wfn.clear()
wfn.update_dm('alpha', tmp)
ham.clear()
energies2.append(ham.compute())
print(x, energies1[-1], energies2[-1])
pt.clf()
pt.plot(xs, energies1, label='est')
pt.plot(xs, energies2, label='ref')
pt.axvline(coeffs[1], color='k')
pt.legend(loc=0)
pt.savefig('ediis2_test_%05i.png' % counter)
wfn.clear()
wfn.update_dm('alpha', dm)
ham.clear()
if energy_approx is not None:
energy_change = energy_approx - min(state.energy for state in history.stack)
else:
energy_change = None
# log
if log.do_high:
history.log(coeffs)
if log.do_medium:
change_str = ' '*10 if energy_change is None else '% 12.7f' % energy_change
log('%4i %10.3e %12.7f %2i %s %12s' % (
counter, cn, coeffs[-1], history.nused, method,
change_str
))
if log.do_high:
log.blank()
if prune_old_states:
# get rid of old states with zero coeff
for i in xrange(history.nused):
if coeffs[i] == 0.0:
if log.do_high:
log(' DIIS insignificant -> drop %i' % history.stack[0].identity)
history.shrink()
else:
break
# counter
counter += 1
if log.do_medium:
if converged:
log('%4i %12.5e (converged)' % (counter, error))
log.blank()
if not skip_energy or history.need_energy:
if not history.need_energy:
ham.compute()
if log.do_medium:
ham.log_energy()
if not converged:
raise NoSCFConvergence
return counter
def __init__(self, coordinates, numbers, pseudo_numbers, grid, moldens, spindens, local, lmax):
'''
**Arguments:**
coordinates
An array (N, 3) with centers for the atom-centered grids.
numbers
An array (N,) with atomic numbers.
pseudo_numbers
An array (N,) with effective charges. When set to None, this
defaults to``numbers.astype(float)``.
grid
The integration grid
moldens
The spin-summed electron density on the grid.
spindens
The spin difference density on the grid. (Can be None)
local
Whether or not to use local (non-periodic) subgrids for atomic
integrals.
lmax
The maximum angular momentum in multipole expansions.
'''
# Init base class
JustOnceClass.__init__(self)
# Some type checking for first three arguments
natom, coordinates, numbers, pseudo_numbers = typecheck_geo(coordinates, numbers, pseudo_numbers)
self._natom = natom
self._coordinates = coordinates
self._numbers = numbers
self._pseudo_numbers = pseudo_numbers
# Assign remaining arguments as attributes
self._grid = grid
self._moldens = moldens
self._spindens = spindens
self._local = local
self._lmax = lmax
# Caching stuff, to avoid recomputation of earlier results
self._cache = Cache()
# Initialize the subgrids
if local:
self._init_subgrids()
# Some screen logging
self._init_log_base()
self._init_log_scheme()
self._init_log_memory()
if log.do_medium:
log.blank()
def __call__(self, ham, overlap, occ_model, *orbs):
"""Find a self-consistent set of orbitals.
Parameters
----------
ham : EffHam
An effective Hamiltonian.
overlap : np.ndarray, shape=(nbasis, nbasis)
The overlap operator.
occ_model : OccModel
Model for the orbital occupations.
orb1, orb2, ... : Orbitals
The initial orbitals. The number of dms must match ham.ndm.
"""
# Some type checking
if ham.ndm != len(orbs):
raise TypeError('The number of initial orbital expansions does not match the Hamiltonian.')
# Impose the requested occupation numbers
occ_model.assign(*orbs)
# Check the orthogonality of the orbitals
for orb in orbs:
orb.check_normalization(overlap)
if log.do_medium:
log('Starting plain SCF solver. ndm=%i' % ham.ndm)
log.hline()
log('Iter Error')
log.hline()
focks = [np.zeros(overlap.shape) for i in xrange(ham.ndm)]
dms = [None] * ham.ndm
converged = False
counter = 0
while self.maxiter is None or counter < self.maxiter:
# convert the orbital expansions to density matrices
for i in xrange(ham.ndm):
dms[i] = orbs[i].to_dm()
# feed the latest density matrices in the hamiltonian
ham.reset(*dms)
# Construct the Fock operator
ham.compute_fock(*focks)
# Check for convergence
error = 0.0
for i in xrange(ham.ndm):
error += orbs[i].error_eigen(focks[i], overlap)
if log.do_medium:
log('%4i %12.5e' % (counter, error))
if error < self.threshold:
converged = True
break
# If requested, add the level shift to the Fock operator
if self.level_shift > 0:
for i in xrange(ham.ndm):
# The normal behavior is to shift down the occupied levels.
focks[i] += -self.level_shift*get_level_shift(dms[i], overlap)
# Diagonalize the fock operators to obtain new orbitals and
for i in xrange(ham.ndm):
orbs[i].from_fock(focks[i], overlap)
# If requested, compensate for level-shift. This compensation
# is only correct when the SCF has converged.
if self.level_shift > 0:
orbs[i].energies[:] += self.level_shift*orbs[i].occupations
# Assign new occupation numbers.
occ_model.assign(*orbs)
# counter
counter += 1
if log.do_medium:
log.blank()
if not self.skip_energy:
ham.compute_energy()
if log.do_medium:
ham.log()
if not converged:
raise NoSCFConvergence
return counter
def converge_scf_diis_cs(ham,
DIISHistoryClass,
maxiter=128,
threshold=1e-6,
nvector=6,
prune_old_states=False,
skip_energy=False,
scf_step='regular'):
'''Minimize the energy of the closed-shell wavefunction with EDIIS
**Arguments:**
ham
A Hamiltonian instance.
DIISHistoryClass
A DIIS history class.
**Optional arguments:**
maxiter
The maximum number of iterations. When set to None, the SCF loop
will go one until convergence is reached.
threshold
The convergence threshold for the wavefunction
prune_old_states
When set to True, old states are pruned from the history when their
coefficient is zero. Pruning starts at the oldest state and stops
as soon as a state is encountered with a non-zero coefficient. Even
if some newer states have a zero coefficient.
skip_energy
When set to True, the final energy is not computed. Note that some
DIIS variants need to compute the energy anyway. for these methods
this option is irrelevant.
scf_step
The type of SCF step to take after the interpolated states was
create from the DIIS history. This can be 'regular', 'oda2' or
'oda3'.
**Raises:**
NoSCFConvergence
if the convergence criteria are not met within the specified number
of iterations.
**Returns:** the number of iterations
'''
# allocated and define some one body operators
lf = ham.system.lf
wfn = ham.system.wfn
overlap = ham.system.get_overlap()
history = DIISHistoryClass(lf, nvector, overlap)
fock = lf.create_one_body()
dm = lf.create_one_body()
# The scf step
if scf_step == 'regular':
cs_scf_step = CSSCFStep(ham)
elif scf_step == 'oda2':
cs_scf_step = CSQuadraticODAStep(ham)
elif scf_step == 'oda3':
cs_scf_step = CSCubicODAStep(ham)
else:
raise ValueError('scf_step argument not recognized: %s' % scf_step)
# Get rid of outdated stuff
ham.clear()
if log.do_medium:
log('Starting restricted closed-shell %s-SCF' % history.name)
log.hline()
log('Iter Error(alpha) CN(alpha) Last(alpha) nv Method Energy Change'
)
log.hline()
converged = False
counter = 0
while maxiter is None or counter < maxiter:
# Construct the Fock operator from scratch:
if history.nused == 0:
# Update the Fock matrix
fock.clear()
ham.compute_fock(fock, None)
# Put this state also in the history
energy = ham.compute() if history.need_energy else None
# Add the current fock+dm pair to the history
error = history.add(energy, wfn.dm_alpha, fock)
if log.do_high:
log(' DIIS add')
if error < threshold:
converged = True
break
if log.do_high:
log.blank()
if log.do_medium:
energy_str = ' ' * 20 if energy is None else '% 20.13f' % energy
log('%4i %12.5e %2i %20s' %
(counter, error, history.nused, energy_str))
if log.do_high:
log.blank()
fock_interpolated = False
else:
energy = None
fock_interpolated = True
# Construct a new density matrix and fock matrix (based on the current
# density matrix or fock matrix). The fock matrix is modified in-place
# while the density matrix is stored in ham.system.wfn
mixing = cs_scf_step(energy, fock, fock_interpolated)
if mixing == 0.0:
converged = True
break
energy = ham.compute() if history.need_energy else None
# Write intermediate results to checkpoint
ham.system.update_chk('wfn')
# Add the current (dm, fock) pair to the history
if log.do_high:
log(' DIIS add')
error = history.add(energy, wfn.dm_alpha, fock)
# break when converged
if error < threshold:
converged = True
break
if log.do_high:
log.blank()
if log.do_medium:
energy_str = ' ' * 20 if energy is None else '% 20.13f' % energy
log('%4i %12.5e %2i %20s' %
(counter, error, history.nused, energy_str))
if log.do_high:
log.blank()
# get extra/intra-polated Fock matrix
while True:
energy_approx, coeffs, cn, method = history.solve(dm, fock)
#if coeffs[coeffs<0].sum() < -1:
# if log.do_high:
# log(' DIIS (coeffs too negative) -> drop %i and retry' % history.stack[0].identity)
# history.shrink()
if history.nused <= 2:
break
if coeffs[-1] == 0.0:
if log.do_high:
log(' DIIS (last coeff zero) -> drop %i and retry'
% history.stack[0].identity)
history.shrink()
else:
break
if False and len(coeffs) == 2:
tmp = dm.copy()
import matplotlib.pyplot as pt
xs = np.linspace(0.0, 1.0, 25)
a, b = history._setup_equations()
energies1 = []
energies2 = []
for x in xs:
x_coeffs = np.array([1 - x, x])
energies1.append(
np.dot(x_coeffs, 0.5 * np.dot(a, x_coeffs) - b))
history._build_combinations(x_coeffs, tmp, None)
wfn.clear()
wfn.update_dm('alpha', tmp)
ham.clear()
energies2.append(ham.compute())
print x, energies1[-1], energies2[-1]
pt.clf()
pt.plot(xs, energies1, label='est')
pt.plot(xs, energies2, label='ref')
pt.axvline(coeffs[1], color='k')
pt.legend(loc=0)
pt.savefig('ediis2_test_%05i.png' % counter)
wfn.clear()
wfn.update_dm('alpha', dm)
ham.clear()
if energy_approx is not None:
energy_change = energy_approx - min(state.energy
for state in history.stack)
else:
energy_change = None
# log
if log.do_high:
history.log(coeffs)
if log.do_medium:
change_str = ' ' * 10 if energy_change is None else '% 12.7f' % energy_change
log('%4i %10.3e %12.7f %2i %s %12s'
% (counter, cn, coeffs[-1], history.nused, method, change_str))
if log.do_high:
log.blank()
if prune_old_states:
# get rid of old states with zero coeff
for i in xrange(history.nused):
if coeffs[i] == 0.0:
if log.do_high:
log(' DIIS insignificant -> drop %i' %
history.stack[0].identity)
history.shrink()
else:
break
# counter
counter += 1
if log.do_medium:
if converged:
log('%4i %12.5e (converged)' % (counter, error))
log.blank()
if not skip_energy or history.need_energy:
if not history.need_energy:
ham.compute()
if log.do_medium:
ham.log_energy()
if not converged:
raise NoSCFConvergence
return counter
def __init__(self, coordinates, numbers, pseudo_numbers, grid, moldens, spindens, local, lmax):
'''
**Arguments:**
coordinates
An array (N, 3) with centers for the atom-centered grids.
numbers
An array (N,) with atomic numbers.
pseudo_numbers
An array (N,) with effective charges. When set to None, this
defaults to``numbers.astype(float)``.
grid
The integration grid
moldens
The spin-summed electron density on the grid.
spindens
The spin difference density on the grid. (Can be None)
local
Whether or not to use local (non-periodic) subgrids for atomic
integrals.
lmax
The maximum angular momentum in multipole expansions.
'''
# Init base class
JustOnceClass.__init__(self)
# Some type checking for first three arguments
natom, coordinates, numbers, pseudo_numbers = typecheck_geo(coordinates, numbers, pseudo_numbers)
self._natom = natom
self._coordinates = coordinates
self._numbers = numbers
self._pseudo_numbers = pseudo_numbers
# Assign remaining arguments as attributes
self._grid = grid
self._moldens = moldens
self._spindens = spindens
self._local = local
self._lmax = lmax
# Caching stuff, to avoid recomputation of earlier results
self._cache = Cache()
# Initialize the subgrids
if local:
self._init_subgrids()
# Some screen logging
self._init_log_base()
self._init_log_scheme()
self._init_log_memory()
if log.do_medium:
log.blank()
def __call__(self, ham, lf, overlap, occ_model, *exps):
'''Find a self-consistent set of orbitals.
**Arguments:**
ham
An effective Hamiltonian.
lf
The linalg factory to be used.
overlap
The overlap operator.
occ_model
Model for the orbital occupations.
exp1, exp2, ...
The initial orbitals. The number of dms must match ham.ndm.
'''
# Some type checking
if ham.ndm != len(exps):
raise TypeError(
'The number of initial orbital expansions does not match the Hamiltonian.'
)
# Impose the requested occupation numbers
occ_model.assign(*exps)
# Check the orthogonality of the orbitals
for exp in exps:
exp.check_normalization(overlap)
if log.do_medium:
log('Starting plain SCF solver. ndm=%i' % ham.ndm)
log.hline()
log('Iter Error')
log.hline()
focks = [lf.create_two_index() for i in xrange(ham.ndm)]
dms = [lf.create_two_index() for i in xrange(ham.ndm)]
converged = False
counter = 0
while self.maxiter is None or counter < self.maxiter:
# convert the orbital expansions to density matrices
for i in xrange(ham.ndm):
exps[i].to_dm(dms[i])
# feed the latest density matrices in the hamiltonian
ham.reset(*dms)
# Construct the Fock operator
ham.compute_fock(*focks)
# Check for convergence
error = 0.0
for i in xrange(ham.ndm):
error += exps[i].error_eigen(focks[i], overlap)
if log.do_medium:
log('%4i %12.5e' % (counter, error))
if error < self.threshold:
converged = True
break
# Diagonalize the fock operators to obtain new orbitals and
for i in xrange(ham.ndm):
exps[i].from_fock(focks[i], overlap)
# Assign new occupation numbers.
occ_model.assign(*exps)
# counter
counter += 1
if log.do_medium:
log.blank()
if not self.skip_energy:
ham.compute_energy()
if log.do_medium:
ham.log()
if not converged:
raise NoSCFConvergence
return counter
def converge_scf_oda_os(ham, maxiter=128, threshold=1e-6, debug=False):
'''Minimize the energy of the open-shell wavefunction with optimal damping
**Arguments:**
ham
A Hamiltonian instance.
**Optional arguments:**
maxiter
The maximum number of iterations. When set to None, the SCF loop
will go one until convergence is reached.
threshold
The convergence threshold for the wavefunction.
debug
Make debug plots with matplotlib of the linear interpolation
**Raises:**
NoSCFConvergence
if the convergence criteria are not met within the specified number
of iterations.
**Returns:** the number of iterations
'''
if log.do_medium:
log('Starting restricted closed-shell SCF with optimal damping')
log.hline()
log(' Iter Energy Error(alpha) Error(beta) Mixing')
log.hline()
# initialization of variables and datastructures
lf = ham.system.lf
wfn = ham.system.wfn
overlap = ham.system.get_overlap()
# suffixes
# 0 = current or initial state
# 1 = state after conventional SCF step
# 2 = state after optimal damping
# a = alpha
# b = beta
fock0a = lf.create_one_body()
fock1a = lf.create_one_body()
fock0b = lf.create_one_body()
fock1b = lf.create_one_body()
dm0a = lf.create_one_body()
dm2a = lf.create_one_body()
dm0b = lf.create_one_body()
dm2b = lf.create_one_body()
converged = False
mixing = None
errora = None
errorb = None
# Get rid of outdated stuff
ham.clear()
# If an input density matrix is present, check if it sensible. This avoids
# redundant testing of a density matrix that is derived here from the
# orbitals.
if 'dm_alpha' in wfn._cache:
check_dm(wfn.dm_alpha, overlap, lf, 'alpha')
if 'dm_beta' in wfn._cache:
check_dm(wfn.dm_beta, overlap, lf, 'beta')
counter = 0
while maxiter is None or counter < maxiter:
# A) Construct Fock operator, compute energy and keep dm at current/initial point
fock0a.clear()
fock0b.clear()
ham.compute_fock(fock0a, fock0b)
energy0 = ham.compute()
dm0a.assign(wfn.dm_alpha)
dm0b.assign(wfn.dm_beta)
if log.do_medium:
if mixing is None:
log('%5i %20.13f' % (counter, energy0))
else:
log('%5i %20.13f %12.5e %12.5e %10.5f' % (counter, energy0, errora, errorb, mixing))
# B) Diagonalize fock operator and go to state 1
wfn.clear()
wfn.update_exp(fock0a, fock0b, overlap)
# Let the hamiltonian know that the wavefunction has changed.
ham.clear()
# C) Compute Fock matrix at state 1
fock1a.clear()
fock1b.clear()
ham.compute_fock(fock1a, fock1b)
# Compute energy at new point
energy1 = ham.compute()
# take the density matrix
dm1a = wfn.dm_alpha
dm1b = wfn.dm_beta
# D) Find the optimal damping
# Compute the derivatives of the energy towards lambda at edges 0 and 1
ev_00 = fock0a.expectation_value(dm0a) + fock0b.expectation_value(dm0b)
ev_01 = fock0a.expectation_value(dm1a) + fock0b.expectation_value(dm1b)
ev_10 = fock1a.expectation_value(dm0a) + fock1b.expectation_value(dm0b)
ev_11 = fock1a.expectation_value(dm1a) + fock1b.expectation_value(dm1b)
energy0_deriv = (ev_01-ev_00)
energy1_deriv = (ev_11-ev_10)
# find the lambda that minimizes the cubic polynomial in the range [0,1]
if log.do_high:
log(' E0: % 10.5e D0: % 10.5e' % (energy0, energy0_deriv))
log(' E1-E0: % 10.5e D1: % 10.5e' % (energy1-energy0, energy1_deriv))
mixing = find_min_cubic(energy0, energy1, energy0_deriv, energy1_deriv)
if log.do_high:
log(' mixing: % 10.5f' % mixing)
if debug:
check_cubic_os(ham, dm0a, dm0b, dm1a, dm1b, energy0, energy1, energy0_deriv, energy1_deriv)
# E) Construct the new dm
# Put the mixed dm in dm_old, which is local in this routine.
dm2a.clear()
dm2a.iadd(dm1a, factor=mixing)
dm2a.iadd(dm0a, factor=1-mixing)
dm2b.clear()
dm2b.iadd(dm1b, factor=mixing)
dm2b.iadd(dm0b, factor=1-mixing)
# Wipe the caches and use the interpolated density matrix
wfn.clear()
wfn.update_dm('alpha', dm2a)
wfn.update_dm('beta', dm2b)
ham.clear()
errora = dm2a.distance(dm0a)
errorb = dm2b.distance(dm0b)
if errora < threshold and errorb < threshold:
if abs(energy0_deriv) > threshold:
raise RuntimeError('The ODA algorithm stopped a point with non-zero gradient.')
converged = True
break
# Write intermediate wfn to checkpoint.
ham.system.update_chk('wfn')
# counter
counter += 1
# compute orbitals, energies and occupation numbers
# Note: suffix 0 is used for final state here
dm0a.assign(wfn.dm_alpha)
dm0b.assign(wfn.dm_beta)
fock0a.clear()
fock0b.clear()
ham.compute_fock(fock0a, fock0b)
wfn.clear()
wfn.update_exp(fock0a, fock0b, overlap, dm0a, dm0b)
energy0 = ham.compute()
# Write final wfn to checkpoint.
ham.system.update_chk('wfn')
if log.do_medium:
log('%5i %20.13f %12.5e %12.5e %10.5f' % (counter+1, energy0, errora, errorb, mixing))
log.blank()
if log.do_medium:
ham.log_energy()
if not converged:
raise NoSCFConvergence
return counter
def __call__(self, ham, overlap, occ_model, *orbs):
"""Find a self-consistent set of orbitals.
Parameters
----------
ham : EffHam
An effective Hamiltonian.
overlap : np.ndarray, shape=(nbasis, nbasis)
The overlap operator.
occ_model : OccModel
Model for the orbital occupations.
orb1, orb2, ... : Orbitals
The initial orbitals. The number of dms must match ham.ndm.
"""
# Some type checking
if ham.ndm != len(orbs):
raise TypeError(
'The number of initial orbital expansions does not match the Hamiltonian.'
)
# Impose the requested occupation numbers
occ_model.assign(*orbs)
# Check the orthogonality of the orbitals
for orb in orbs:
orb.check_normalization(overlap)
if log.do_medium:
log('Starting plain SCF solver. ndm=%i' % ham.ndm)
log.hline()
log('Iter Error')
log.hline()
focks = [np.zeros(overlap.shape) for i in xrange(ham.ndm)]
dms = [None] * ham.ndm
converged = False
counter = 0
while self.maxiter is None or counter < self.maxiter:
# convert the orbital expansions to density matrices
for i in xrange(ham.ndm):
dms[i] = orbs[i].to_dm()
# feed the latest density matrices in the hamiltonian
ham.reset(*dms)
# Construct the Fock operator
ham.compute_fock(*focks)
# Check for convergence
error = 0.0
for i in xrange(ham.ndm):
error += orbs[i].error_eigen(focks[i], overlap)
if log.do_medium:
log('%4i %12.5e' % (counter, error))
if error < self.threshold:
converged = True
break
# If requested, add the level shift to the Fock operator
if self.level_shift > 0:
for i in xrange(ham.ndm):
# The normal behavior is to shift down the occupied levels.
focks[i] += -self.level_shift * get_level_shift(
dms[i], overlap)
# Diagonalize the fock operators to obtain new orbitals and
for i in xrange(ham.ndm):
orbs[i].from_fock(focks[i], overlap)
# If requested, compensate for level-shift. This compensation
# is only correct when the SCF has converged.
if self.level_shift > 0:
orbs[i].energies[:] += self.level_shift * orbs[
i].occupations
# Assign new occupation numbers.
occ_model.assign(*orbs)
# counter
counter += 1
if log.do_medium:
log.blank()
if not self.skip_energy:
ham.compute_energy()
if log.do_medium:
ham.log()
if not converged:
raise NoSCFConvergence
return counter
def converge_scf_oda_os(ham, maxiter=128, threshold=1e-6, debug=False):
'''Minimize the energy of the open-shell wavefunction with optimal damping
**Arguments:**
ham
A Hamiltonian instance.
**Optional arguments:**
maxiter
The maximum number of iterations. When set to None, the SCF loop
will go one until convergence is reached.
threshold
The convergence threshold for the wavefunction.
debug
Make debug plots with matplotlib of the linear interpolation
**Raises:**
NoSCFConvergence
if the convergence criteria are not met within the specified number
of iterations.
**Returns:** the number of iterations
'''
if log.do_medium:
log('Starting restricted closed-shell SCF with optimal damping')
log.hline()
log(' Iter Energy Error(alpha) Error(beta) Mixing')
log.hline()
# initialization of variables and datastructures
lf = ham.system.lf
wfn = ham.system.wfn
overlap = ham.system.get_overlap()
# suffixes
# 0 = current or initial state
# 1 = state after conventional SCF step
# 2 = state after optimal damping
# a = alpha
# b = beta
fock0a = lf.create_one_body()
fock1a = lf.create_one_body()
fock0b = lf.create_one_body()
fock1b = lf.create_one_body()
dm0a = lf.create_one_body()
dm2a = lf.create_one_body()
dm0b = lf.create_one_body()
dm2b = lf.create_one_body()
converged = False
mixing = None
errora = None
errorb = None
# Get rid of outdated stuff
ham.clear()
# If an input density matrix is present, check if it sensible. This avoids
# redundant testing of a density matrix that is derived here from the
# orbitals.
if 'dm_alpha' in wfn._cache:
check_dm(wfn.dm_alpha, overlap, lf, 'alpha')
if 'dm_beta' in wfn._cache:
check_dm(wfn.dm_beta, overlap, lf, 'beta')
counter = 0
while maxiter is None or counter < maxiter:
# A) Construct Fock operator, compute energy and keep dm at current/initial point
fock0a.clear()
fock0b.clear()
ham.compute_fock(fock0a, fock0b)
energy0 = ham.compute()
dm0a.assign(wfn.dm_alpha)
dm0b.assign(wfn.dm_beta)
if log.do_medium:
if mixing is None:
log('%5i %20.13f' % (counter, energy0))
else:
log('%5i %20.13f %12.5e %12.5e %10.5f' % (counter, energy0, errora, errorb, mixing))
# B) Diagonalize fock operator and go to state 1
wfn.clear()
wfn.update_exp(fock0a, fock0b, overlap)
# Let the hamiltonian know that the wavefunction has changed.
ham.clear()
# C) Compute Fock matrix at state 1
fock1a.clear()
fock1b.clear()
ham.compute_fock(fock1a, fock1b)
# Compute energy at new point
energy1 = ham.compute()
# take the density matrix
dm1a = wfn.dm_alpha
dm1b = wfn.dm_beta
# D) Find the optimal damping
# Compute the derivatives of the energy towards lambda at edges 0 and 1
ev_00 = fock0a.expectation_value(dm0a) + fock0b.expectation_value(dm0b)
ev_01 = fock0a.expectation_value(dm1a) + fock0b.expectation_value(dm1b)
ev_10 = fock1a.expectation_value(dm0a) + fock1b.expectation_value(dm0b)
ev_11 = fock1a.expectation_value(dm1a) + fock1b.expectation_value(dm1b)
energy0_deriv = (ev_01-ev_00)
energy1_deriv = (ev_11-ev_10)
# find the lambda that minimizes the cubic polynomial in the range [0,1]
if log.do_high:
log(' E0: % 10.5e D0: % 10.5e' % (energy0, energy0_deriv))
log(' E1-E0: % 10.5e D1: % 10.5e' % (energy1-energy0, energy1_deriv))
mixing = find_min_cubic(energy0, energy1, energy0_deriv, energy1_deriv)
if log.do_high:
log(' mixing: % 10.5f' % mixing)
if debug:
check_cubic_os(ham, dm0a, dm0b, dm1a, dm1b, energy0, energy1, energy0_deriv, energy1_deriv)
# E) Construct the new dm
# Put the mixed dm in dm_old, which is local in this routine.
dm2a.clear()
dm2a.iadd(dm1a, factor=mixing)
dm2a.iadd(dm0a, factor=1-mixing)
dm2b.clear()
dm2b.iadd(dm1b, factor=mixing)
dm2b.iadd(dm0b, factor=1-mixing)
# Wipe the caches and use the interpolated density matrix
wfn.clear()
wfn.update_dm('alpha', dm2a)
wfn.update_dm('beta', dm2b)
ham.clear()
errora = dm2a.distance(dm0a)
errorb = dm2b.distance(dm0b)
if errora < threshold and errorb < threshold:
if abs(energy0_deriv) > threshold:
raise RuntimeError('The ODA algorithm stopped a point with non-zero gradient.')
converged = True
break
# Write intermediate wfn to checkpoint.
ham.system.update_chk('wfn')
# counter
counter += 1
# compute orbitals, energies and occupation numbers
# Note: suffix 0 is used for final state here
dm0a.assign(wfn.dm_alpha)
dm0b.assign(wfn.dm_beta)
fock0a.clear()
fock0b.clear()
ham.compute_fock(fock0a, fock0b)
wfn.clear()
wfn.update_exp(fock0a, fock0b, overlap, dm0a, dm0b)
energy0 = ham.compute()
# Write final wfn to checkpoint.
ham.system.update_chk('wfn')
if log.do_medium:
log('%5i %20.13f %12.5e %12.5e %10.5f' % (counter+1, energy0, errora, errorb, mixing))
log.blank()
if log.do_medium:
ham.log_energy()
if not converged:
raise NoSCFConvergence
return counter
