def test_temp_energy_adjustment():
ea = TemperatureEnergyAdjustment(-0.1, 298, 5, uncertainty_per_deg=0, name="entropy")
assert ea.name == "entropy"
assert ea.value == -0.1 * 298 * 5
assert ea.n_atoms == 5
assert ea.temp == 298
assert ea.explain == "Temperature-based energy adjustment (-0.1000 eV/K/atom x 298 K x 5 atoms)"
ead = ea.as_dict()
ea2 = TemperatureEnergyAdjustment.from_dict(ead)
assert str(ead) == str(ea2.as_dict())
def test_temp_energy_adjustment():
ea = TemperatureEnergyAdjustment(-0.1, 298, 5, "entropy")
assert ea.name == "entropy"
assert ea.value == -0.1 * 298 * 5
assert ea.n_atoms == 5
assert ea.temp == 298
assert ea.description == "Temperature-based energy adjustment (-0.1000 eV/K/atom x 298 K x 5 atoms)"
def test_normalize_energy_adjustments(self):
ealist = [ManualEnergyAdjustment(5),
ConstantEnergyAdjustment(5),
CompositionEnergyAdjustment(1, 5, uncertainty_per_atom=0, name="Na"),
TemperatureEnergyAdjustment(0.005, 100, 10, uncertainty_per_degK=0)
]
entry = ComputedEntry("Na5Cl5", 6.9, energy_adjustments=ealist)
assert entry.correction == 20
entry.normalize()
assert entry.correction == 4
for ea in entry.energy_adjustments:
assert ea.value == 1
def test_normalize_not_in_place(self):
ealist = [
ManualEnergyAdjustment(5),
ConstantEnergyAdjustment(5),
CompositionEnergyAdjustment(1, 5, uncertainty_per_atom=0, name="Na"),
TemperatureEnergyAdjustment(0.005, 100, 10, uncertainty_per_deg=0),
]
entry = ComputedEntry("Na5Cl5", 6.9, energy_adjustments=ealist)
normed_entry = entry.normalize(inplace=False)
entry.normalize()
self.assertEqual(normed_entry.as_dict(), entry.as_dict())
def get_adjustments(self, entry: ComputedEntry):
"""
Returns the corrections applied to a particular entry.
Args:
entry: A ComputedEntry object.
Returns:
[EnergyAdjustment]: Energy adjustments to be applied to entry.
Raises:
CompatibilityError if the required O2 and H2O energies have not been provided to
MaterialsProjectAqueousCompatibility during init or in the list of entries passed to process_entries.
"""
adjustments = []
if self.o2_energy is None or self.h2o_energy is None or self.h2o_adjustments is None:
raise CompatibilityError(
"You did not provide the required O2 and H2O energies. "
"{} needs these energies in order to compute "
"the appropriate energy adjustments. Either specify the energies as arguments "
"to {}.__init__ or run process_entries on a list that includes ComputedEntry for "
"the ground state of O2 and H2O.".format(
type(self).__name__,
type(self).__name__))
# compute the free energies of H2 and H2O (eV/atom) to guarantee that the
# formationfree energy of H2O is equal to -2.4583 eV/H2O from experiments
# (MU_H2O from pourbaix module)
# Free energy of H2 in eV/atom, fitted using Eq. 40 of Persson et al. PRB 2012 85(23)
# for this calculation ONLY, we need the (corrected) DFT energy of water
self.h2_energy = round(
0.5 * (3 * (self.h2o_energy - self.cpd_entropies["H2O"]) -
(self.o2_energy - self.cpd_entropies["O2"]) - MU_H2O), 6)
# Free energy of H2O, fitted for consistency with the O2 and H2 energies.
self.fit_h2o_energy = round(
(2 * self.h2_energy +
(self.o2_energy - self.cpd_entropies["O2"]) + MU_H2O) / 3, 6)
comp = entry.composition
rform = comp.reduced_formula
# pin the energy of all H2 entries to h2_energy
if rform == "H2":
adjustments.append(
ConstantEnergyAdjustment(
self.h2_energy * comp.num_atoms - entry.energy,
name="MP Aqueous H2 / H2O referencing",
cls=self.as_dict(),
description=
"Adjusts the H2 and H2O energy to reproduce the experimental "
"Gibbs formation free energy of H2O, based on the DFT energy "
"of Oxygen"))
# pin the energy of all H2O entries to fit_h2o_energy
elif rform == "H2O":
adjustments.append(
ConstantEnergyAdjustment(
self.fit_h2o_energy * comp.num_atoms - entry.energy,
name="MP Aqueous H2 / H2O referencing",
cls=self.as_dict(),
description=
"Adjusts the H2 and H2O energy to reproduce the experimental "
"Gibbs formation free energy of H2O, based on the DFT energy "
"of Oxygen"))
# add minus T delta S to the DFT energy (enthalpy) of compounds that are
# molecular-like at room temperature
elif rform in self.cpd_entropies and rform != "H2O":
adjustments.append(
TemperatureEnergyAdjustment(
-1 * self.cpd_entropies[rform] / 298,
298,
comp.num_atoms,
name="Compound entropy at room temperature",
cls=self.as_dict(),
description=
"Adds the entropy (T delta S) to energies of compounds that "
"are gaseous or liquid at standard state"))
# TODO - detection of embedded water molecules is not very sophisticated
# Should be replaced with some kind of actual structure detection
# For any compound except water, check to see if it is a hydrate (contains)
# H2O in its structure. If so, adjust the energy to remove MU_H2O ev per
# embedded water molecule.
# in other words, we assume that the DFT energy of such a compound is really
# a superposition of the "real" solid DFT energy (FeO in this case) and the free
# energy of some water molecules
# e.g. that E_FeO.nH2O = E_FeO + n * g_H2O
# so, to get the most accurate gibbs free energy, we want to replace
# g_FeO.nH2O = E_FeO.nH2O + dE_Fe + (n+1) * dE_O + 2n dE_H
# with
# g_FeO = E_FeO.nH2O + dE_Fe + dE_O + n g_H2O
# where E is DFT energy, dE is an energy correction, and g is gibbs free energy
# This means we have to 1) remove energy corrections associated with H and O in water
# and then 2) remove the free energy of the water molecules
if not rform == "H2O":
# count the number of whole water molecules in the composition
nH2O = int(min(comp["H"] / 2.0, comp["O"]))
if nH2O > 0:
# first, remove any H or O corrections already applied to H2O in the
# formation energy so that we don't double count them
# next, remove MU_H2O for each water molecule present
hydrate_adjustment = -1 * (self.h2o_adjustments * 3 + MU_H2O)
adjustments.append(
CompositionEnergyAdjustment(
hydrate_adjustment,
nH2O,
name="MP Aqueous hydrate",
cls=self.as_dict(),
description=
"Adjust the energy of solid hydrate compounds (compounds "
"containing H2O molecules in their structure) so that the "
"free energies of embedded H2O molecules match the experimental"
" value enforced by the MP Aqueous energy referencing scheme."
))
return adjustments