From 8c6825937ded9d5ab1dd05810452b9c9b116d66c Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Fri, 4 Feb 2022 16:30:12 -0800 Subject: [PATCH 01/14] Add caching for get_min_entry_by_formula, fix speed of minimize enumer --- src/rxn_network/entries/entry_set.py | 24 ++++++++-- src/rxn_network/enumerators/basic.py | 23 ++++++++-- src/rxn_network/enumerators/minimize.py | 38 +++++++++++---- src/rxn_network/enumerators/utils.py | 61 ++++++------------------- tests/costs/test_calculators.py | 6 --- 5 files changed, 81 insertions(+), 71 deletions(-) diff --git a/src/rxn_network/entries/entry_set.py b/src/rxn_network/entries/entry_set.py index 7acb88e7..d24f6682 100644 --- a/src/rxn_network/entries/entry_set.py +++ b/src/rxn_network/entries/entry_set.py @@ -6,7 +6,8 @@ import logging import warnings from copy import deepcopy -from typing import Dict, Iterable, List, Optional, Set, Union +from typing import Dict, Iterable, List, Optional, Set, Union, Tuple +from functools import lru_cache from monty.dev import deprecated from monty.json import MontyDecoder, MSONable @@ -162,11 +163,10 @@ def get_min_entry_by_formula(self, formula: str) -> ComputedEntry: Returns: Ground state computed entry object. """ - comp = Composition(formula).reduced_composition - possible_entries = filter( - lambda x: x.composition.reduced_composition == comp, self.entries + return self._get_min_entry_by_formula( + self.entries_tuple, + formula, ) - return sorted(possible_entries, key=lambda x: x.energy_per_atom)[0] def get_stabilized_entry( self, entry: ComputedEntry, tol: float = 1e-6 @@ -268,6 +268,15 @@ def get_interpolated_entry(self, formula: str, tol=1e-6) -> ComputedEntry: comp, energy, energy_adjustments=[adj], entry_id="(Interpolated Entry!)" ) + @staticmethod + @lru_cache(maxsize=None) + def _get_min_entry_by_formula(entries, formula): + formula_clean = Composition(formula).reduced_formula + possible_entries = filter( + lambda x: x.composition.reduced_formula == formula_clean, entries + ) + return sorted(possible_entries, key=lambda x: x.energy_per_atom)[0] + @classmethod def from_pd( cls, @@ -412,6 +421,11 @@ def entries_list(self) -> List[ComputedEntry]: """Returns a list of all entries in the entry set.""" return list(sorted(self.entries, key=lambda e: e.composition.reduced_formula)) + @property + def entries_tuple(self) -> Tuple[ComputedEntry]: + """Returns a tuple of all entries in the entry set.""" + return tuple(self.entries_list) # type: ignore + @property def chemsys(self) -> set: """ diff --git a/src/rxn_network/enumerators/basic.py b/src/rxn_network/enumerators/basic.py index 5cfb0535..0f139fd9 100644 --- a/src/rxn_network/enumerators/basic.py +++ b/src/rxn_network/enumerators/basic.py @@ -248,12 +248,14 @@ def _get_rxns( ): continue - if not (precursor_func(r) or precursor_func(p)): + if not (precursor_func(r) or (p and precursor_func(p))): continue if p and not (target_func(r) or target_func(p)): continue - suggested_rxns = self._react(r, p, calculators, pd, grand_pd) + suggested_rxns = self._react( + r, p, calculators, filtered_entries, pd, grand_pd + ) for rxn in suggested_rxns: if ( @@ -271,12 +273,25 @@ def _get_rxns( return rxns - def _react(self, reactants, products, calculators, pd=None, grand_pd=None): + def _react( + self, + reactants, + products, + calculators, + filtered_entries=None, + pd=None, + grand_pd=None, + ): """ Generates reactions from a list of reactants, products, and optional calculator(s) """ - _ = (pd, grand_pd, self) # unused arguments in BasicEnumerator class + _ = ( + filtered_entries, + pd, + grand_pd, + self, + ) # unused arguments in BasicEnumerator class forward_rxn = ComputedReaction.balance(reactants, products) backward_rxn = forward_rxn.reverse() diff --git a/src/rxn_network/enumerators/minimize.py b/src/rxn_network/enumerators/minimize.py index 361f5703..fb71a0cd 100644 --- a/src/rxn_network/enumerators/minimize.py +++ b/src/rxn_network/enumerators/minimize.py @@ -18,7 +18,6 @@ from rxn_network.enumerators.utils import ( apply_calculators, get_computed_rxn, - get_open_computed_rxn, ) @@ -75,10 +74,19 @@ def estimate_max_num_reactions(self, entries: List[ComputedEntry]) -> int: """ return comb(len(entries), 2) * 2 - def _react(self, reactants, products, calculators, pd=None, grand_pd=None): + def _react( + self, + reactants, + products, + calculators, + filtered_entries=None, + pd=None, + grand_pd=None, + ): """React method for MinimizeGibbsEnumerator, which uses the interfacial reaction approach (see _react_interface())""" r = list(reactants) + print(r) r0 = r[0] if len(r) == 1: @@ -87,7 +95,12 @@ def _react(self, reactants, products, calculators, pd=None, grand_pd=None): r1 = r[1] return self._react_interface( - r0.composition, r1.composition, pd, grand_pd, calculators=calculators + r0.composition, + r1.composition, + filtered_entries, + pd, + grand_pd, + calculators=calculators, ) @staticmethod @@ -98,7 +111,7 @@ def _get_rxn_iterable(combos, open_combos): return product(combos, [None]) @staticmethod - def _react_interface(r1, r2, pd, grand_pd=None, calculators=None): + def _react_interface(r1, r2, filtered_entries, pd, grand_pd=None, calculators=None): """Simple API for InterfacialReactivity module from pymatgen.""" chempots = None @@ -124,11 +137,7 @@ def _react_interface(r1, r2, pd, grand_pd=None, calculators=None): rxns = [] for _, _, _, rxn, _ in interface.get_kinks(): - if grand_pd: - rxn = get_open_computed_rxn(rxn, pd.all_entries, chempots) - else: - rxn = get_computed_rxn(rxn, pd.all_entries) - + rxn = get_computed_rxn(rxn, filtered_entries, chempots) rxn = apply_calculators(rxn, calculators) rxns.append(rxn) @@ -185,7 +194,15 @@ def __init__( self.chempots = {self.open_elem: self.mu} self._build_grand_pd = True - def _react(self, reactants, products, calculators, pd=None, grand_pd=None): + def _react( + self, + reactants, + products, + calculators, + filtered_entries=None, + pd=None, + grand_pd=None, + ): """Same as the MinimizeGibbsEnumerator react function, but with ability to specify open element and grand potential phase diagram""" r = list(reactants) @@ -206,6 +223,7 @@ def _react(self, reactants, products, calculators, pd=None, grand_pd=None): return self._react_interface( r0.composition, r1.composition, + filtered_entries, pd, grand_pd=grand_pd, calculators=calculators, diff --git a/src/rxn_network/enumerators/utils.py b/src/rxn_network/enumerators/utils.py index e2e19cbf..e3f4c228 100644 --- a/src/rxn_network/enumerators/utils.py +++ b/src/rxn_network/enumerators/utils.py @@ -5,7 +5,7 @@ from typing import Dict, Iterable, List, Optional, Set, Tuple, Union from pymatgen.analysis.phase_diagram import PhaseDiagram -from pymatgen.core.composition import Composition, Element +from pymatgen.core.composition import Element from pymatgen.entries.computed_entries import ComputedEntry, Entry import rxn_network.costs.calculators as calcs @@ -157,24 +157,9 @@ def stabilize_entries( return new_entries -def get_min_entry_by_comp(comp: Composition, entries: Iterable[Entry]) -> Entry: - """ - Gets the entry with the lowest energy for a given composition from a set of provided entries. - - Args: - comp: Composition object - entries: Iterable of entries - - Returns: - Entry with the lowest enegy per atom for the given composition - """ - possible_entries = filter( - lambda e: e.composition.reduced_composition == comp.reduced_composition, entries - ) - return sorted(possible_entries, key=lambda e: e.energy_per_atom)[0] - - -def get_computed_rxn(rxn: Reaction, entries: Iterable[Entry]) -> ComputedReaction: +def get_computed_rxn( + rxn: Reaction, entries: GibbsEntrySet, chempots=None +) -> ComputedReaction: """ Provided with a Reaction object and a list of possible entries, this function returns a new ComputedReaction object containing a selection of those entries. @@ -186,32 +171,16 @@ def get_computed_rxn(rxn: Reaction, entries: Iterable[Entry]) -> ComputedReactio Returns: A ComputedReaction object transformed from a normal Reaction object """ - reactant_entries = [get_min_entry_by_comp(r, entries) for r in rxn.reactants] - product_entries = [get_min_entry_by_comp(p, entries) for p in rxn.products] - - rxn = ComputedReaction.balance(reactant_entries, product_entries) - return rxn - - -def get_open_computed_rxn( - rxn: Reaction, entries: Iterable[Entry], chempots: Dict[Element, float] -) -> OpenComputedReaction: - """ - Provided with a Reaction object and a list of possible entries, as well as a - dictionary of chemical potentials of open elements, this function returns a new - OpenComputedReaction object containing a selection of those entries. - - Args: - rxn: Reaction object - entries: Iterable of entries - chempots: Dictionary of chemical potentials of open elements - ` - Returns: - An OpenComputedReaction object transformed from a normal Reaction object - """ - reactant_entries = [get_min_entry_by_comp(r, entries) for r in rxn.reactants] - product_entries = [get_min_entry_by_comp(p, entries) for p in rxn.products] - - rxn = OpenComputedReaction.balance(reactant_entries, product_entries, chempots) + reactant_entries = [ + entries.get_min_entry_by_formula(r.reduced_formula) for r in rxn.reactants + ] + product_entries = [ + entries.get_min_entry_by_formula(p.reduced_formula) for p in rxn.products + ] + + if chempots: + rxn = OpenComputedReaction.balance(reactant_entries, product_entries, chempots) + else: + rxn = ComputedReaction.balance(reactant_entries, product_entries) return rxn diff --git a/tests/costs/test_calculators.py b/tests/costs/test_calculators.py index 1efbc082..5493c5c3 100644 --- a/tests/costs/test_calculators.py +++ b/tests/costs/test_calculators.py @@ -27,12 +27,6 @@ } -@pytest.fixture(params=["Cl_Mn_Na_O_Y_entries.json.gz"]) -def entries(request): - entries = loadfn(TEST_FILES_PATH / request.param) - return GibbsEntrySet(entries) - - @pytest.fixture( params=[ [["Y2O3", "Mn2O3"], ["YMnO3"]], From d7e91e7f7cb5d57e4afa5ab7948c0861f0c5fd08 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Fri, 4 Feb 2022 16:33:00 -0800 Subject: [PATCH 02/14] remove print statemnet --- src/rxn_network/enumerators/minimize.py | 1 - 1 file changed, 1 deletion(-) diff --git a/src/rxn_network/enumerators/minimize.py b/src/rxn_network/enumerators/minimize.py index fb71a0cd..df3466d6 100644 --- a/src/rxn_network/enumerators/minimize.py +++ b/src/rxn_network/enumerators/minimize.py @@ -86,7 +86,6 @@ def _react( """React method for MinimizeGibbsEnumerator, which uses the interfacial reaction approach (see _react_interface())""" r = list(reactants) - print(r) r0 = r[0] if len(r) == 1: From cc471b60589e58b5aedc96329ced6f4b57c79469 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Mon, 7 Feb 2022 13:08:37 -0800 Subject: [PATCH 03/14] use cached properties for better min entry finding --- src/rxn_network/entries/entry_set.py | 38 +++++++++++++-------------- src/rxn_network/reactions/plotting.py | 4 +-- 2 files changed, 21 insertions(+), 21 deletions(-) diff --git a/src/rxn_network/entries/entry_set.py b/src/rxn_network/entries/entry_set.py index d24f6682..ff45c662 100644 --- a/src/rxn_network/entries/entry_set.py +++ b/src/rxn_network/entries/entry_set.py @@ -7,7 +7,7 @@ import warnings from copy import deepcopy from typing import Dict, Iterable, List, Optional, Set, Union, Tuple -from functools import lru_cache +from functools import cached_property from monty.dev import deprecated from monty.json import MontyDecoder, MSONable @@ -163,10 +163,7 @@ def get_min_entry_by_formula(self, formula: str) -> ComputedEntry: Returns: Ground state computed entry object. """ - return self._get_min_entry_by_formula( - self.entries_tuple, - formula, - ) + return self.min_entries_by_formula[formula] def get_stabilized_entry( self, entry: ComputedEntry, tol: float = 1e-6 @@ -268,15 +265,6 @@ def get_interpolated_entry(self, formula: str, tol=1e-6) -> ComputedEntry: comp, energy, energy_adjustments=[adj], entry_id="(Interpolated Entry!)" ) - @staticmethod - @lru_cache(maxsize=None) - def _get_min_entry_by_formula(entries, formula): - formula_clean = Composition(formula).reduced_formula - possible_entries = filter( - lambda x: x.composition.reduced_formula == formula_clean, entries - ) - return sorted(possible_entries, key=lambda x: x.energy_per_atom)[0] - @classmethod def from_pd( cls, @@ -416,15 +404,27 @@ def from_entries( return cls(list(new_entries)) - @property + @cached_property def entries_list(self) -> List[ComputedEntry]: """Returns a list of all entries in the entry set.""" return list(sorted(self.entries, key=lambda e: e.composition.reduced_formula)) - @property - def entries_tuple(self) -> Tuple[ComputedEntry]: - """Returns a tuple of all entries in the entry set.""" - return tuple(self.entries_list) # type: ignore + @cached_property + def min_entries_by_formula(self) -> Dict[str, ComputedEntry]: + """Returns a dict of minimum energy entries in the entry set, indexed by + formula.""" + min_entries = {} + for e in self.entries: + formula = e.composition.reduced_formula + if formula not in min_entries: + entries = filter( + lambda x: x.composition.reduced_formula == formula, self.entries + ) + min_entries[formula] = sorted(entries, key=lambda x: x.energy_per_atom)[ + 0 + ] + + return min_entries @property def chemsys(self) -> set: diff --git a/src/rxn_network/reactions/plotting.py b/src/rxn_network/reactions/plotting.py index 7e910de9..0fead4d0 100644 --- a/src/rxn_network/reactions/plotting.py +++ b/src/rxn_network/reactions/plotting.py @@ -21,8 +21,8 @@ def plot_energy_distance_scatter(df: DataFrame) -> px.scatter: fig = px.scatter( df, - x="energy", - y="chempot_distance", + x="chempot_distance", + y="c_score", hover_name="rxn", labels={ "energy": r"$\Delta G_{\mathrm{rxn}} ~ \mathrm{\left(" From dee31458abbf29fb1d938a79bdc1bb82dc078ea1 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Mon, 7 Feb 2022 13:26:27 -0800 Subject: [PATCH 04/14] parse formula to prevent bug --- src/rxn_network/entries/entry_set.py | 8 +++++--- 1 file changed, 5 insertions(+), 3 deletions(-) diff --git a/src/rxn_network/entries/entry_set.py b/src/rxn_network/entries/entry_set.py index ff45c662..c381dcfa 100644 --- a/src/rxn_network/entries/entry_set.py +++ b/src/rxn_network/entries/entry_set.py @@ -163,7 +163,7 @@ def get_min_entry_by_formula(self, formula: str) -> ComputedEntry: Returns: Ground state computed entry object. """ - return self.min_entries_by_formula[formula] + return self.min_entries_by_formula[Composition(formula).reduced_formula] def get_stabilized_entry( self, entry: ComputedEntry, tol: float = 1e-6 @@ -411,8 +411,10 @@ def entries_list(self) -> List[ComputedEntry]: @cached_property def min_entries_by_formula(self) -> Dict[str, ComputedEntry]: - """Returns a dict of minimum energy entries in the entry set, indexed by - formula.""" + """ + Returns a dict of minimum energy entries in the entry set, indexed by + formula. + """ min_entries = {} for e in self.entries: formula = e.composition.reduced_formula From e6f0ff9cbee08ea1366d45050cbdebe5809d2258 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Mon, 7 Feb 2022 14:56:39 -0800 Subject: [PATCH 05/14] add metastable_domains to cpd, add energy_adjustments to expt entry --- src/rxn_network/entries/barin.py | 16 +++++++++-- src/rxn_network/entries/entry_set.py | 2 +- src/rxn_network/entries/experimental.py | 12 ++++---- src/rxn_network/entries/nist.py | 16 +++++++++-- src/rxn_network/thermo/__init__.py | 2 -- src/rxn_network/thermo/chempot_diagram.py | 35 ++++++++++++++++++++++- 6 files changed, 67 insertions(+), 16 deletions(-) diff --git a/src/rxn_network/entries/barin.py b/src/rxn_network/entries/barin.py index 1ecf0313..15386801 100644 --- a/src/rxn_network/entries/barin.py +++ b/src/rxn_network/entries/barin.py @@ -1,9 +1,10 @@ """ Implements an Entry that looks up pre-tabulated Gibbs free energies from the Barin tables. """ -from typing import Dict, Optional +from typing import Dict, Optional, List from pymatgen.core.composition import Composition +from pymatgen.entries.computed_entries import EnergyAdjustment from rxn_network.data import PATH_TO_BARIN, load_experimental_data from rxn_network.entries.experimental import ExperimentalReferenceEntry @@ -25,7 +26,11 @@ class BarinReferenceEntry(ExperimentalReferenceEntry): REFERENCES = G_COMPOUNDS def __init__( - self, composition: Composition, temperature: float, data: Optional[Dict] = None + self, + composition: Composition, + temperature: float, + energy_adjustments: Optional[List[EnergyAdjustment]] = None, + data: Optional[Dict] = None, ): """ Args: @@ -34,4 +39,9 @@ def __init__( one of [300, 400, 500, ... 2000 K], then free energies will be interpolated. Defaults to 300 K. """ - super().__init__(composition, temperature, data) + super().__init__( + composition=composition, + temperature=temperature, + energy_adjustments=energy_adjustments, + data=data, + ) diff --git a/src/rxn_network/entries/entry_set.py b/src/rxn_network/entries/entry_set.py index c381dcfa..763dcdf1 100644 --- a/src/rxn_network/entries/entry_set.py +++ b/src/rxn_network/entries/entry_set.py @@ -6,7 +6,7 @@ import logging import warnings from copy import deepcopy -from typing import Dict, Iterable, List, Optional, Set, Union, Tuple +from typing import Dict, Iterable, List, Optional, Set, Union from functools import cached_property from monty.dev import deprecated diff --git a/src/rxn_network/entries/experimental.py b/src/rxn_network/entries/experimental.py index 15342013..4ff8bf17 100644 --- a/src/rxn_network/entries/experimental.py +++ b/src/rxn_network/entries/experimental.py @@ -6,6 +6,7 @@ from monty.json import MSONable from pymatgen.core.composition import Composition +from pymatgen.entries.computed_entries import EnergyAdjustment from scipy.interpolate import interp1d @@ -22,6 +23,7 @@ def __init__( self, composition: Composition, temperature: float, + energy_adjustments: Optional[List[EnergyAdjustment]] = None, data: Optional[dict] = None, ): """ @@ -33,7 +35,8 @@ def __init__( data: Optional dictionary containing entry data """ self._composition = Composition(composition) - self.temperature = temperature + self._temperature = temperature + self.energy_adjustments = energy_adjustments if energy_adjustments else [] self.data = data if data else {} # type: Dict[Any, Any] formula = self._composition.reduced_formula @@ -123,11 +126,8 @@ def correction_uncertainty_per_atom(self) -> float: return 0 @property - def energy_adjustments(self) -> List: - """ - Returns a list of energy adjustments. Not implemented for experimental data. - """ - return [] + def temperature(self) -> float: + return self._temperature @property def is_experimental(self) -> bool: diff --git a/src/rxn_network/entries/nist.py b/src/rxn_network/entries/nist.py index 25abf6f7..a007f6ca 100644 --- a/src/rxn_network/entries/nist.py +++ b/src/rxn_network/entries/nist.py @@ -2,9 +2,10 @@ Implements an Entry that looks up pre-tabulated Gibbs free energies from the NIST-JANAF tables. """ -from typing import Dict, Optional +from typing import Dict, Optional, List from pymatgen.core.composition import Composition +from pymatgen.entries.computed_entries import EnergyAdjustment from rxn_network.data import PATH_TO_NIST, load_experimental_data from rxn_network.entries.experimental import ExperimentalReferenceEntry @@ -27,7 +28,11 @@ class NISTReferenceEntry(ExperimentalReferenceEntry): REFERENCES = G_COMPOUNDS def __init__( - self, composition: Composition, temperature: float, data: Optional[Dict] = None + self, + composition: Composition, + temperature: float, + energy_adjustments: Optional[List[EnergyAdjustment]] = None, + data: Optional[Dict] = None, ): """ Args: @@ -37,4 +42,9 @@ def __init__( interpolated. Defaults to 300 K. data: Optional dictionary containing entry data """ - super().__init__(composition, temperature, data) + super().__init__( + composition=composition, + temperature=temperature, + energy_adjustments=energy_adjustments, + data=data, + ) diff --git a/src/rxn_network/thermo/__init__.py b/src/rxn_network/thermo/__init__.py index f39e099b..fa366d50 100644 --- a/src/rxn_network/thermo/__init__.py +++ b/src/rxn_network/thermo/__init__.py @@ -2,5 +2,3 @@ Thermodynamic functions for the reaction network package, including chemical potential diagrams. """ - -from rxn_network.thermo.chempot_diagram import ChemicalPotentialDiagram diff --git a/src/rxn_network/thermo/chempot_diagram.py b/src/rxn_network/thermo/chempot_diagram.py index 17efe9e0..3ac97750 100644 --- a/src/rxn_network/thermo/chempot_diagram.py +++ b/src/rxn_network/thermo/chempot_diagram.py @@ -5,6 +5,7 @@ import warnings from functools import cached_property from typing import Dict, List, Optional +from copy import deepcopy import numpy as np from pymatgen.analysis.chempot_diagram import ChemicalPotentialDiagram as ChempotDiagram @@ -12,9 +13,12 @@ from pymatgen.core.composition import Element from scipy.spatial import KDTree +from rxn_network.entries.entry_set import GibbsEntrySet + class ChemicalPotentialDiagram(ChempotDiagram): - """This class is an extension of the ChemicalPotentialDiagram class from pymatgen. + """ + This class is an extension of the ChemicalPotentialDiagram class from pymatgen. Several features have been added to the original class for the purpose of calculating the shortest distance between two chemical potential domains. """ @@ -24,6 +28,7 @@ def __init__( entries: List[PDEntry], limits: Optional[Dict[Element, float]] = None, default_min_limit: Optional[float] = -20.0, + calculate_metastable_domains=False, ): """ Initialize a ChemicalPotentialDiagram object. @@ -46,6 +51,7 @@ def __init__( super().__init__( entries=entries, limits=limits, default_min_limit=default_min_limit ) + self.calculate_metastable_domains = calculate_metastable_domains @cached_property def domains(self) -> Dict[str, np.ndarray]: @@ -54,6 +60,13 @@ def domains(self) -> Dict[str, np.ndarray]: """ return self._get_domains() + @property + def metastable_domains(self) -> Dict[str, np.ndarray]: + """Gets a dictionary of the chemical potential domains for metastable chemical + formulas. This corresponds to the domains of the relevant phases if they were + just barely stable""" + return self._get_metastable_domains() + def shortest_domain_distance(self, f1: str, f2: str) -> float: """ Args: @@ -95,3 +108,23 @@ def shortest_elemental_domain_distances(self, f1: str, f2: str) -> float: diff = diff.reshape(-1, num_elems) return diff.min(axis=0) + + def _get_metastable_domains(self): + e_set = GibbsEntrySet(self.entries) + e_dict = e_set.min_entries_by_formula + stable_formulas = list(self.domains.keys()) + + metastable_entries = [e for f, e in e_dict.items() if f not in stable_formulas] + + metastable_domains = {} + for e in metastable_entries: + print(e.as_dict()) + e_set_copy = deepcopy(e_set) + e_set_copy.add(e_set_copy.get_stabilized_entry(e)) + + formula = e.composition.reduced_formula + + domain = self.__class__(e_set_copy).domains[formula] + metastable_domains[formula] = domain + + return metastable_domains From a03af788e309b871287ef1a76a78956351cd1c9b Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Tue, 8 Feb 2022 14:19:48 -0800 Subject: [PATCH 06/14] Add FREEDReferenceEntry, compress existing data, --- scripts/generate_free_data.py | 57 + scripts/generate_janaf_data.py | 8 +- src/rxn_network/data/__init__.py | 1 + src/rxn_network/data/barin/compounds.json | 29803 ----------------- src/rxn_network/data/barin/compounds.json.gz | Bin 0 -> 313516 bytes src/rxn_network/data/freed/compounds.json.gz | Bin 0 -> 261382 bytes src/rxn_network/data/nist/compounds.json | 13241 -------- src/rxn_network/data/nist/compounds.json.gz | Bin 0 -> 137084 bytes src/rxn_network/entries/barin.py | 2 +- src/rxn_network/entries/entry_set.py | 15 + src/rxn_network/entries/experimental.py | 91 +- src/rxn_network/entries/freed.py | 48 + src/rxn_network/entries/nist.py | 2 +- src/rxn_network/thermo/chempot_diagram.py | 4 +- 14 files changed, 178 insertions(+), 43094 deletions(-) create mode 100644 scripts/generate_free_data.py delete mode 100644 src/rxn_network/data/barin/compounds.json create mode 100644 src/rxn_network/data/barin/compounds.json.gz create mode 100644 src/rxn_network/data/freed/compounds.json.gz delete mode 100644 src/rxn_network/data/nist/compounds.json create mode 100644 src/rxn_network/data/nist/compounds.json.gz create mode 100644 src/rxn_network/entries/freed.py diff --git a/scripts/generate_free_data.py b/scripts/generate_free_data.py new file mode 100644 index 00000000..326d9d29 --- /dev/null +++ b/scripts/generate_free_data.py @@ -0,0 +1,57 @@ +""" +This script generates the data/freed/compounds.json file by using the s4 package as an interface. +""" + +import numpy as np +from pymatgen.core.composition import Composition +from collections import OrderedDict +import json +import gzip + +from s4.thermo.exp.freed import ExpThermoDatabase + + +if __name__ == "__main__": + xp = ExpThermoDatabase() + temps = np.arange(300, 2100, 100) + data = {} + + # Acquire data + for c in xp.compositions: + if c.is_element: + continue + + formula, factor = c.get_integer_formula_and_factor() + + if not data.get(formula): + data[formula] = dict() + + phases = xp.compositions[c] + + for t in temps: + energies = [] + for p in phases: + if t > p.tmax: + continue + energies.append(p.dgf(t)) + + if not energies: + continue + + final_energy = min(energies) + g = final_energy / factor + + if data[formula].get(t): + data[formula][t].append(g) + else: + data[formula][t] = [g] + + # Clean the data + cleaned_data = {} + for f, energy_dict in data.items(): + cleaned_data[f] = {str(t): min(e) for t, e in energy_dict.items()} + + # Write to file + cleaned_data = OrderedDict(sorted(cleaned_data.items())) + with gzip.open("compounds.json.gz", "wt", encoding="ascii") as zipfile: + json.dump(cleaned_data, zipfile) diff --git a/scripts/generate_janaf_data.py b/scripts/generate_janaf_data.py index 17832be3..30246854 100644 --- a/scripts/generate_janaf_data.py +++ b/scripts/generate_janaf_data.py @@ -4,6 +4,7 @@ """ import os +import gzip import json from collections import OrderedDict import pandas @@ -74,6 +75,7 @@ formula, factor = Composition(f).get_integer_formula_and_factor() all_data[formula] = {temp: g / factor for temp, g in zip(temps, dGf)} -all_data = OrderedDict(sorted(all_data.items())) -with open("compounds.json", "w") as f: - json.dump(all_data, f) + all_data = OrderedDict(sorted(all_data.items())) + + with gzip.open("compounds.json.gz", "wt", encoding="ascii") as zipfile: + json.dump(all_data, zipfile) diff --git a/src/rxn_network/data/__init__.py b/src/rxn_network/data/__init__.py index 20a921fc..febd8d41 100644 --- a/src/rxn_network/data/__init__.py +++ b/src/rxn_network/data/__init__.py @@ -10,6 +10,7 @@ cwd = Path(__file__).parent.resolve() PATH_TO_BARIN = cwd / "barin" +PATH_TO_FREED = cwd / "freed" PATH_TO_NIST = cwd / "nist" G_ELEMS = loadfn(cwd / "elements.json") diff --git a/src/rxn_network/data/barin/compounds.json b/src/rxn_network/data/barin/compounds.json deleted file mode 100644 index af830072..00000000 --- a/src/rxn_network/data/barin/compounds.json +++ /dev/null @@ -1,29803 +0,0 @@ -{ - "Ag2CO3": { - "298.15": -4.5271555983107525, - "300.0": -4.522719689765783, - "400.0": -4.284507255191983, - "500.0": -4.049891223106744 - }, - "Ag2O": { - "298.15": -0.334807452422209, - "300.0": -0.33409231763341707, - "400.0": -0.2917231724655744, - "500.0": -0.24767501518491603, - "600.0": -0.20325374410140973, - "700.0": -0.1587910159286981, - "800.0": -0.11455630174661577, - "900.0": -0.07073615845658668 - }, - "Ag2S": { - "298.15": -0.4200017707391529, - "300.0": -0.42050962008191817, - "400.0": -0.44777802050672105, - "450.0": -0.45913726294898016, - "500.0": -0.4744971144995533, - "600.0": -0.5040041977414438, - "700.0": -0.5326095892931184, - "800.0": -0.5604065676052892, - "860.0": -0.5765851966676674, - "900.0": -0.5756109550713423, - "1000.0": -0.5409942855848955, - "1100.0": -0.5068647368966113, - "1110.0": -0.5034756198540759, - "1200.0": -0.47994872173005365, - "1300.0": -0.4421398563747967, - "1400.0": -0.39849590571389026 - }, - "Ag2SO4": { - "298.15": -6.408229563913193, - "300.0": -6.4019591791708885, - "400.0": -6.062114690410231, - "500.0": -5.717523364935566, - "600.0": -5.37316005345153, - "700.0": -5.03126343877521, - "800.0": -4.720542555181296, - "900.0": -4.402007010272176, - "933.0": -4.281439430590789, - "1000.0": -4.052129905923832, - "1100.0": -3.7147521139708926, - "1200.0": -3.3825357296240166 - }, - "Ag2Te": { - "298.15": -8.593142536301464, - "300.0": -8.586944701465269, - "400.0": -8.254593581578476, - "500.0": -7.927611154743771 - }, - "Ag2WO4": { - "298.15": -0.4307184282987296, - "300.0": -0.4310811778292762, - "400.0": -0.45218283623478683, - "421.0": -0.45708513703331655, - "500.0": -0.48903818853832126, - "600.0": -0.5299148784947721, - "700.0": -0.5704495474652792, - "800.0": -0.5906495141805741 - }, - "Ag3AsO4": { - "298.15": -1.0063190190977704, - "300.0": -1.0061013693794425, - "400.0": -0.9629030824274935, - "500.0": -0.907848067962821, - "600.0": -0.8563894559867108, - "700.0": -0.8102995370626901, - "800.0": -0.7822330876706848, - "900.0": -0.7558560146637964, - "1000.0": -0.730826297056081, - "1100.0": -0.7068744637677042, - "1200.0": -0.6837621365357353, - "1300.0": -0.655011645171842, - "1400.0": -0.623452436014288, - "1500.0": -0.5922352478426779, - "1600.0": -0.5612875307509023, - "1633.91": -0.5508507085434616 - }, - "AgBr": { - "298.15": 0.5729991584514068, - "300.0": 0.570345904742266, - "400.0": 0.4611893888646438, - "500.0": 0.3691339222842185, - "600.0": 0.2785812751874862, - "700.0": 0.18937598348992699, - "800.0": 0.10141440446852758, - "900.0": 0.01462398821717858, - "1000.0": -0.0710367223533253, - "1100.0": -0.15559882005988804, - "1200.0": -0.23908303344711232, - "1300.0": -0.3152086135003913, - "1400.0": -0.38698119918711116, - "1500.0": -0.45769662909909514, - "1600.0": -0.5274274531424528, - "1700.0": -0.5962151284063891, - "1800.0": -0.6641425690693149, - "1900.0": -0.731230503675833, - "2000.0": -0.7975411178597511 - }, - "AgBrO3": { - "298.15": 0.740205963488786, - "300.0": 0.7454710138178624, - "400.0": 1.0597468428111338 - }, - "AgCN": { - "298.15": 1.6275742293841762, - "300.0": 1.6282789999006666, - "400.0": 1.6638388181665347, - "500.0": 1.695118191971953 - }, - "AgCl": { - "298.15": 0.6752530689763422, - "300.0": 0.6734911426851159, - "400.0": 0.5793524573721229, - "500.0": 0.48706897680106825, - "600.0": 0.39638159416441865, - "700.0": 0.30715557392225684, - "800.0": 0.2192872733515694, - "900.0": 0.13268341400164435, - "1000.0": 0.04731290305557776, - "1100.0": -0.03687608084813705, - "1200.0": -0.11989390198180142, - "1300.0": -0.1954805398754112, - "1400.0": -0.2666312692240511, - "1500.0": -0.3366626571641472, - "1600.0": -0.4056368893295076, - "1700.0": -0.4736161513539402, - "1800.0": -0.5406626288712528, - "1900.0": -0.6068281432429524, - "2000.0": -0.6721437872859428, - "2100.0": -0.736671746634032, - "2200.0": -0.8004327498318227 - }, - "AgF": { - "298.15": -0.20957595020522188, - "300.0": -0.2113275122241469, - "400.0": -0.3051863621850039, - "500.0": -0.39705527186400524, - "600.0": -0.48716225525178025, - "700.0": -0.5756524121605476, - "800.0": -0.6626190210410192, - "900.0": -0.7481553603439072, - "1000.0": -0.8323132514307179, - "1100.0": -0.915134151390657, - "1200.0": -0.9966595173129297, - "1300.0": -1.0706086001829291, - "1400.0": -1.140007767512644, - "1500.0": -1.208163222166199, - "1600.0": -1.275147514049704, - "1700.0": -1.3410331930692674, - "1800.0": -1.405882444858698, - "1900.0": -1.4697470907795018, - "2000.0": -1.5326893164654876 - }, - "AgI": { - "298.15": 0.8197828462184082, - "300.0": 0.8168083000679263, - "400.0": 0.6614685868155715, - "500.0": 0.5494308032381792, - "600.0": 0.4665269890998295, - "700.0": 0.3844626810178876, - "800.0": 0.30318605763084694, - "900.0": 0.2226971189387074, - "1000.0": 0.14299586494146907, - "1100.0": 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z9zH&`xzoO@)!3ok-9FLmgeOP?7h#I);L!Ju#V#yCTu+x(r4VAV`dhWayZ8n9fFyk| zb>u~Rm@aSR!yvR2{WCET#aS8RxS)ND&XkK@vS?JWMzkyv0q;m$Tv z|J**hiIV0ztqWkYT|Y>?mx3y~s!50K-I&MGOyFTE>q}RZaA8R=2uX4M@AZOILL3R&EZhEGZ+A=+_VhF& z+-*_X01JsK+9GS1n~XXEMkmE_Tc-4UCGZL4NymYi+!3D "GibbsEntrySet": """ Constructor method for building a GibbsEntrySet from an existing phase diagram. @@ -336,6 +338,17 @@ def from_pd( logging.warning( f"Compound {formula} is in Barin tables but not at this temperature! {error}" ) + if include_freed_data and formula in FREEDReferenceEntry.REFERENCES: + try: + e = FREEDReferenceEntry( + composition=Composition(formula), temperature=temperature + ) + experimental = True + new_entries.append(e) + except ValueError as error: + logging.warning( + f"Compound {formula} is in FREED tables but not at this temperature! {error}" + ) if experimental: experimental_formulas.append(formula) @@ -366,6 +379,7 @@ def from_entries( temperature: float, include_nist_data=True, include_barin_data=False, + include_freed_data=False, ) -> "GibbsEntrySet": """ Constructor method for initializing GibbsEntrySet from T = 0 K @@ -393,6 +407,7 @@ def from_entries( temperature, include_nist_data=include_nist_data, include_barin_data=include_barin_data, + include_freed_data=include_freed_data, ) pd_dict = expand_pd(list(e_set)) diff --git a/src/rxn_network/entries/experimental.py b/src/rxn_network/entries/experimental.py index 4ff8bf17..a7fd3f7c 100644 --- a/src/rxn_network/entries/experimental.py +++ b/src/rxn_network/entries/experimental.py @@ -2,15 +2,15 @@ Implements an Entry that looks up NIST pre-tabulated Gibbs free energies """ import hashlib -from typing import Any, Dict, List, Optional -from monty.json import MSONable +from typing import Dict, List, Optional from pymatgen.core.composition import Composition -from pymatgen.entries.computed_entries import EnergyAdjustment +from pymatgen.entries.computed_entries import ComputedEntry, EnergyAdjustment +from monty.json import MontyDecoder from scipy.interpolate import interp1d -class ExperimentalReferenceEntry(MSONable): +class ExperimentalReferenceEntry(ComputedEntry): """ An Entry class for experimental reference data, to be sub-classed for specific data sources. Given a composition, automatically finds the Gibbs free energy of formation, dGf(T) from tabulated @@ -34,19 +34,23 @@ def __init__( interpolated. Defaults to 300 K. data: Optional dictionary containing entry data """ - self._composition = Composition(composition) - self._temperature = temperature - self.energy_adjustments = energy_adjustments if energy_adjustments else [] - self.data = data if data else {} # type: Dict[Any, Any] + formula = Composition(composition).reduced_formula + entry_id = self.__class__.__name__ - formula = self._composition.reduced_formula + self._temperature = temperature self._validate_temperature(formula, temperature) - self._energy = self._get_energy(formula, temperature) + energy = self._get_energy(formula, temperature) + + super().__init__( + composition, + energy, + energy_adjustments=energy_adjustments, + data=data, + entry_id=entry_id, + ) - self._formula = formula self.name = formula - self.entry_id = self.__class__.__name__ def get_new_temperature( self, new_temperature: float @@ -98,35 +102,9 @@ def _get_energy(cls, formula: str, temperature: float) -> float: return data[temperature] - @property - def composition(self) -> Composition: - """ - :return: the composition of the entry. - """ - return self._composition - - @property - def energy(self) -> float: - """The energy of the entry, as supplied by the reference tables.""" - return self._energy - - @property - def energy_per_atom(self) -> float: - """The energy of the entry, as supplied by the reference tables.""" - return self.energy / self.composition.num_atoms - - @property - def correction_uncertainty(self) -> float: - """Uncertainty of experimental data is not supplied.""" - return 0 - - @property - def correction_uncertainty_per_atom(self) -> float: - """Uncertainty of experimental data is not supplied.""" - return 0 - @property def temperature(self) -> float: + """Returns temperature used to calculate entry's energy""" return self._temperature @property @@ -139,18 +117,45 @@ def is_element(self) -> bool: """Returns True if the entry is an element.""" return self.composition.is_element + def as_dict(self): + """ + Returns: + A dict representation of the Entry. + """ + d = super().as_dict() + + d["temperature"] = self.temperature + + del d["energy"] + del d["entry_id"] + del d["parameters"] + del d["correction"] + + return d + + @classmethod + def from_dict(cls, d): + dec = MontyDecoder() + entry = cls( + composition=d["composition"], + temperature=d["temperature"], + energy_adjustments=dec.process_decoded(d["energy_adjustments"]), + data=d["data"], + ) + return entry + def __repr__(self): output = [ - f"{self.__class__.__name__} | {self._formula}", + f"{self.__class__.__name__} | {self.composition.reduced_formula}", f"Gibbs Energy ({self.temperature} K) = {self.energy:.4f}", ] return "\n".join(output) def __eq__(self, other): if isinstance(other, self.__class__): - return (self._formula == other._formula) and ( - self.temperature == other.temperature - ) + return ( + self.composition.reduced_formula == other.composition.reduced_formula + ) and (self.temperature == other.temperature) return False def __hash__(self): diff --git a/src/rxn_network/entries/freed.py b/src/rxn_network/entries/freed.py new file mode 100644 index 00000000..ea69aae9 --- /dev/null +++ b/src/rxn_network/entries/freed.py @@ -0,0 +1,48 @@ +""" +Implements an Entry that looks up pre-tabulated Gibbs free energies from the NIST-JANAF +tables. +""" +from typing import Dict, Optional, List + +from pymatgen.core.composition import Composition +from pymatgen.entries.computed_entries import EnergyAdjustment + +from rxn_network.data import PATH_TO_FREED, load_experimental_data +from rxn_network.entries.experimental import ExperimentalReferenceEntry + +G_COMPOUNDS = load_experimental_data(PATH_TO_FREED / "compounds.json.gz") + + +class FREEDReferenceEntry(ExperimentalReferenceEntry): + """ + An Entry class for FREED experimental reference data. Given a composition, + automatically finds the Gibbs free energy of formation, dGf(T) from tabulated + reference values. + + Reference: + https://www.thermart.net/freed-thermodynamic-database/ + """ + + REFERENCES = G_COMPOUNDS + + def __init__( + self, + composition: Composition, + temperature: float, + energy_adjustments: Optional[List[EnergyAdjustment]] = None, + data: Optional[Dict] = None, + ): + """ + Args: + composition: Composition object (within pymatgen). + temperature: Temperature in Kelvin. If temperature is not selected from + one of [300, 400, 500, ... 2000 K], then free energies will be + interpolated. Defaults to 300 K. + data: Optional dictionary containing entry data + """ + super().__init__( + composition=composition, + temperature=temperature, + energy_adjustments=energy_adjustments, + data=data, + ) diff --git a/src/rxn_network/entries/nist.py b/src/rxn_network/entries/nist.py index a007f6ca..db093f1d 100644 --- a/src/rxn_network/entries/nist.py +++ b/src/rxn_network/entries/nist.py @@ -10,7 +10,7 @@ from rxn_network.data import PATH_TO_NIST, load_experimental_data from rxn_network.entries.experimental import ExperimentalReferenceEntry -G_COMPOUNDS = load_experimental_data(PATH_TO_NIST / "compounds.json") +G_COMPOUNDS = load_experimental_data(PATH_TO_NIST / "compounds.json.gz") class NISTReferenceEntry(ExperimentalReferenceEntry): diff --git a/src/rxn_network/thermo/chempot_diagram.py b/src/rxn_network/thermo/chempot_diagram.py index 3ac97750..2242e666 100644 --- a/src/rxn_network/thermo/chempot_diagram.py +++ b/src/rxn_network/thermo/chempot_diagram.py @@ -118,9 +118,9 @@ def _get_metastable_domains(self): metastable_domains = {} for e in metastable_entries: - print(e.as_dict()) e_set_copy = deepcopy(e_set) - e_set_copy.add(e_set_copy.get_stabilized_entry(e)) + new_entry = e_set_copy.get_stabilized_entry(e) + e_set_copy.add(new_entry) formula = e.composition.reduced_formula From b1b448b357e2e9a458f6d714d434e0e34fa46785 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Tue, 8 Feb 2022 14:33:56 -0800 Subject: [PATCH 07/14] fix bug in __eq__ for experimental entries --- src/rxn_network/entries/experimental.py | 6 ++++-- 1 file changed, 4 insertions(+), 2 deletions(-) diff --git a/src/rxn_network/entries/experimental.py b/src/rxn_network/entries/experimental.py index a7fd3f7c..24f5dda1 100644 --- a/src/rxn_network/entries/experimental.py +++ b/src/rxn_network/entries/experimental.py @@ -154,8 +154,10 @@ def __repr__(self): def __eq__(self, other): if isinstance(other, self.__class__): return ( - self.composition.reduced_formula == other.composition.reduced_formula - ) and (self.temperature == other.temperature) + (self.composition.reduced_formula == other.composition.reduced_formula) + and (self.temperature == other.temperature) + and (set(self.energy_adjustments) == set(other.energy_adjustments)) + ) return False def __hash__(self): From 871900bee47eca4baf7ae1c4729de41d0f228bdd Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Tue, 8 Feb 2022 17:01:24 -0800 Subject: [PATCH 08/14] Add support for adding entry to existing cpd. Some bugs for domain assgn --- src/rxn_network/thermo/chempot_diagram.py | 129 ++++++++++++++-------- 1 file changed, 85 insertions(+), 44 deletions(-) diff --git a/src/rxn_network/thermo/chempot_diagram.py b/src/rxn_network/thermo/chempot_diagram.py index 2242e666..dbaf97f6 100644 --- a/src/rxn_network/thermo/chempot_diagram.py +++ b/src/rxn_network/thermo/chempot_diagram.py @@ -3,15 +3,16 @@ pymatgen. """ import warnings -from functools import cached_property -from typing import Dict, List, Optional +from functools import cached_property, lru_cache +from typing import Dict, List, Optional, Tuple from copy import deepcopy import numpy as np from pymatgen.analysis.chempot_diagram import ChemicalPotentialDiagram as ChempotDiagram -from pymatgen.analysis.phase_diagram import PDEntry +from pymatgen.analysis.phase_diagram import PDEntry, PhaseDiagram from pymatgen.core.composition import Element -from scipy.spatial import KDTree + +from scipy.spatial import KDTree, HalfspaceIntersection from rxn_network.entries.entry_set import GibbsEntrySet @@ -19,7 +20,7 @@ class ChemicalPotentialDiagram(ChempotDiagram): """ This class is an extension of the ChemicalPotentialDiagram class from pymatgen. - Several features have been added to the original class for the purpose of + Several features have been added to the original class for the purpose of efficiently calculating the shortest distance between two chemical potential domains. """ @@ -28,7 +29,6 @@ def __init__( entries: List[PDEntry], limits: Optional[Dict[Element, float]] = None, default_min_limit: Optional[float] = -20.0, - calculate_metastable_domains=False, ): """ Initialize a ChemicalPotentialDiagram object. @@ -51,21 +51,7 @@ def __init__( super().__init__( entries=entries, limits=limits, default_min_limit=default_min_limit ) - self.calculate_metastable_domains = calculate_metastable_domains - - @cached_property - def domains(self) -> Dict[str, np.ndarray]: - """ - Mapping of formulas to array of domain boundary points. Cached for speed. - """ - return self._get_domains() - - @property - def metastable_domains(self) -> Dict[str, np.ndarray]: - """Gets a dictionary of the chemical potential domains for metastable chemical - formulas. This corresponds to the domains of the relevant phases if they were - just barely stable""" - return self._get_metastable_domains() + self._hs_int = self._get_halfspace_intersection() def shortest_domain_distance(self, f1: str, f2: str) -> float: """ @@ -84,30 +70,84 @@ def shortest_domain_distance(self, f1: str, f2: str) -> float: return min(tree.query(pts2)[0]) - def shortest_elemental_domain_distances(self, f1: str, f2: str) -> float: - """ - Args: - f1: chemical formula (1) - f2: chemical formula (2) + def add_entry(self, entry): + hyperplane = self._get_hyperplane(entry) + idx = len(self._hyperplanes) - self.dim + self._hyperplanes = np.vstack( + [self._hyperplanes[:idx], hyperplane, self._hyperplanes[idx:]] + ) + self._hyperplane_entries.insert(idx, entry) + self._hs_int.add_halfspaces([hyperplane], restart=True) + self._entry_dict[entry.composition.reduced_formula] = entry + del self.domains # clear cache - Returns: - Shortest distance between domain boundaries along one elemental axis. - """ - warnings.warn( - "Use with caution; this function may not result in anything meaningful!" + def remove_entry(self, entry): + pass + + def _get_halfspace_intersection(self): + hs_hyperplanes = np.vstack([self._hyperplanes, self._border_hyperplanes]) + interior_point = np.min(self.lims, axis=1) + + return HalfspaceIntersection( + hs_hyperplanes, interior_point + 1e-6, incremental=True ) - pts1 = self.domains[f1] - pts2 = self.domains[f2] - pts1 = pts1[~np.isclose(pts1, self.default_min_limit).any(axis=1)] - pts2 = pts2[~np.isclose(pts2, self.default_min_limit).any(axis=1)] - num_elems = pts1.shape[1] + def _get_domains(self) -> Dict[str, np.ndarray]: + """Returns a dictionary of domains as {formula: np.ndarray}""" + entries = self._hyperplane_entries + domains = {entry.composition.reduced_formula: [] for entry in entries} # type: ignore + + for intersection, facet in zip( + self.hs_int.intersections, self.hs_int.dual_facets + ): + for v in facet: + if v < len(entries): + this_entry = entries[v] + formula = this_entry.composition.reduced_formula + domains[formula].append(intersection) + + return {k: np.array(v) for k, v in domains.items() if v} + + def _get_hyperplanes_and_entries(self) -> Tuple[np.ndarray, List[PDEntry]]: + """Returns both the array of hyperplanes, as well as a list of the minimum + entries""" + data = np.array([self._get_hyperplane(e) for e in self._min_entries]) + vec = [self.el_refs[el].energy_per_atom for el in self.elements] + [1] + form_e = -np.dot(data, vec) - mesh = np.meshgrid(pts1, pts2) - diff = abs(mesh[0] - mesh[1]) - diff = diff.reshape(-1, num_elems) + inds = np.where(form_e < -PhaseDiagram.formation_energy_tol)[0].tolist() - return diff.min(axis=0) + inds.extend([self._min_entries.index(el) for el in self.el_refs.values()]) + + hyperplanes = data[inds] + hyperplane_entries = [self._min_entries[i] for i in inds] + + return hyperplanes, hyperplane_entries + + def _get_hyperplane(self, entry): + data = np.array( + [entry.composition.get_atomic_fraction(el) for el in self.elements] + + [-entry.energy_per_atom] + ) + return data + + @property + def hs_int(self): + return self._hs_int + + @cached_property + def domains(self) -> Dict[str, np.ndarray]: + """ + Mapping of formulas to array of domain boundary points. Cached for speed. + """ + return self._get_domains() + + @cached_property + def metastable_domains(self) -> Dict[str, np.ndarray]: + """Gets a dictionary of the chemical potential domains for metastable chemical + formulas. This corresponds to the domains of the relevant phases if they were + just barely stable""" + return self._get_metastable_domains() def _get_metastable_domains(self): e_set = GibbsEntrySet(self.entries) @@ -118,13 +158,14 @@ def _get_metastable_domains(self): metastable_domains = {} for e in metastable_entries: - e_set_copy = deepcopy(e_set) - new_entry = e_set_copy.get_stabilized_entry(e) - e_set_copy.add(new_entry) + new_entry = e_set.get_stabilized_entry(e) + e_set.add(new_entry) formula = e.composition.reduced_formula - domain = self.__class__(e_set_copy).domains[formula] + domain = self.__class__(e_set).domains[formula] metastable_domains[formula] = domain + e_set.remove(new_entry) + return metastable_domains From 8988340d7a19ea1c70eac39384b9681aec63d048 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Thu, 10 Feb 2022 13:05:50 -0800 Subject: [PATCH 09/14] adding entries to CPDs does not work --- src/rxn_network/thermo/chempot_diagram.py | 65 ++++++++++++++++------- 1 file changed, 45 insertions(+), 20 deletions(-) diff --git a/src/rxn_network/thermo/chempot_diagram.py b/src/rxn_network/thermo/chempot_diagram.py index dbaf97f6..36fd88b1 100644 --- a/src/rxn_network/thermo/chempot_diagram.py +++ b/src/rxn_network/thermo/chempot_diagram.py @@ -5,7 +5,7 @@ import warnings from functools import cached_property, lru_cache from typing import Dict, List, Optional, Tuple -from copy import deepcopy +from copy import copy import numpy as np from pymatgen.analysis.chempot_diagram import ChemicalPotentialDiagram as ChempotDiagram @@ -53,6 +53,13 @@ def __init__( ) self._hs_int = self._get_halfspace_intersection() + num_hyperplanes = len(self._hyperplanes) + num_border_hyperplanes = len(self._border_hyperplanes) + + self._border_hyperplane_indices = list( + range(num_hyperplanes, num_hyperplanes + num_border_hyperplanes) + ) + def shortest_domain_distance(self, f1: str, f2: str) -> float: """ Args: @@ -71,18 +78,33 @@ def shortest_domain_distance(self, f1: str, f2: str) -> float: return min(tree.query(pts2)[0]) def add_entry(self, entry): + """ + Adds an entry to existing chemical potential diagram. Uses scipy's + add_halfspaces() method to save some time/memory. + + Args: + entry: + + Returns: + None + + """ + if entry in self.entries: + return + elif not set(entry.composition.elements).issubset(self.elements): + raise ValueError("New entry is not within the same chemical system!") + hyperplane = self._get_hyperplane(entry) - idx = len(self._hyperplanes) - self.dim - self._hyperplanes = np.vstack( - [self._hyperplanes[:idx], hyperplane, self._hyperplanes[idx:]] - ) - self._hyperplane_entries.insert(idx, entry) + self._hyperplanes = np.vstack([self._hyperplanes, hyperplane]) + self._hyperplane_entries.append(entry) self._hs_int.add_halfspaces([hyperplane], restart=True) self._entry_dict[entry.composition.reduced_formula] = entry - del self.domains # clear cache + self.entries.append(entry) - def remove_entry(self, entry): - pass + try: + del self.domains # clear cache + except AttributeError: + pass def _get_halfspace_intersection(self): hs_hyperplanes = np.vstack([self._hyperplanes, self._border_hyperplanes]) @@ -94,14 +116,16 @@ def _get_halfspace_intersection(self): def _get_domains(self) -> Dict[str, np.ndarray]: """Returns a dictionary of domains as {formula: np.ndarray}""" + domains = {entry.composition.reduced_formula: [] for entry in self._hyperplane_entries} # type: ignore entries = self._hyperplane_entries - domains = {entry.composition.reduced_formula: [] for entry in entries} # type: ignore for intersection, facet in zip( self.hs_int.intersections, self.hs_int.dual_facets ): for v in facet: - if v < len(entries): + if v not in self._border_hyperplane_indices: + if v > max(self._border_hyperplane_indices): + v = v - len(self._border_hyperplane_indices) this_entry = entries[v] formula = this_entry.composition.reduced_formula domains[formula].append(intersection) @@ -133,6 +157,7 @@ def _get_hyperplane(self, entry): @property def hs_int(self): + """Returns the scipy HalfSpaceIntersection object""" return self._hs_int @cached_property @@ -155,17 +180,17 @@ def _get_metastable_domains(self): stable_formulas = list(self.domains.keys()) metastable_entries = [e for f, e in e_dict.items() if f not in stable_formulas] - metastable_domains = {} - for e in metastable_entries: - new_entry = e_set.get_stabilized_entry(e) - e_set.add(new_entry) + for e in metastable_entries: formula = e.composition.reduced_formula - - domain = self.__class__(e_set).domains[formula] - metastable_domains[formula] = domain - - e_set.remove(new_entry) + new_entry = e_set.get_stabilized_entry(e) + cpd = ChemicalPotentialDiagram.from_dict(self.as_dict()) + print(cpd) + print(cpd.domains) + cpd.add_entry(new_entry) + print(cpd) + print(cpd.domains) + metastable_domains[formula] = cpd.domains[formula] return metastable_domains From db6db8f6b2b3d0bf6753b45ce34a4409fb335408 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Thu, 10 Feb 2022 13:30:01 -0800 Subject: [PATCH 10/14] fix metastable domain bug (interior point was wrong) --- src/rxn_network/thermo/chempot_diagram.py | 20 +++++--------------- 1 file changed, 5 insertions(+), 15 deletions(-) diff --git a/src/rxn_network/thermo/chempot_diagram.py b/src/rxn_network/thermo/chempot_diagram.py index 36fd88b1..cb4f4f88 100644 --- a/src/rxn_network/thermo/chempot_diagram.py +++ b/src/rxn_network/thermo/chempot_diagram.py @@ -2,10 +2,9 @@ This module implements added features to the ChemicalPotentialDiagram class from pymatgen. """ -import warnings -from functools import cached_property, lru_cache + +from functools import cached_property from typing import Dict, List, Optional, Tuple -from copy import copy import numpy as np from pymatgen.analysis.chempot_diagram import ChemicalPotentialDiagram as ChempotDiagram @@ -55,7 +54,6 @@ def __init__( num_hyperplanes = len(self._hyperplanes) num_border_hyperplanes = len(self._border_hyperplanes) - self._border_hyperplane_indices = list( range(num_hyperplanes, num_hyperplanes + num_border_hyperplanes) ) @@ -108,11 +106,8 @@ def add_entry(self, entry): def _get_halfspace_intersection(self): hs_hyperplanes = np.vstack([self._hyperplanes, self._border_hyperplanes]) - interior_point = np.min(self.lims, axis=1) - - return HalfspaceIntersection( - hs_hyperplanes, interior_point + 1e-6, incremental=True - ) + interior_point = np.min(self.lims, axis=1) + 1e-1 + return HalfspaceIntersection(hs_hyperplanes, interior_point, incremental=True) def _get_domains(self) -> Dict[str, np.ndarray]: """Returns a dictionary of domains as {formula: np.ndarray}""" @@ -185,12 +180,7 @@ def _get_metastable_domains(self): for e in metastable_entries: formula = e.composition.reduced_formula new_entry = e_set.get_stabilized_entry(e) - cpd = ChemicalPotentialDiagram.from_dict(self.as_dict()) - print(cpd) - print(cpd.domains) - cpd.add_entry(new_entry) - print(cpd) - print(cpd.domains) + cpd = ChemicalPotentialDiagram(list(e_dict.values()) + [new_entry]) metastable_domains[formula] = cpd.domains[formula] return metastable_domains From e719fdc53a60526fae07e27f973bc2a9c4e42d6b Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Thu, 10 Feb 2022 14:10:28 -0800 Subject: [PATCH 11/14] add support for chemical potential distance to metastable phases --- src/rxn_network/enumerators/basic.py | 2 -- src/rxn_network/thermo/chempot_diagram.py | 19 +++++++++++++++---- 2 files changed, 15 insertions(+), 6 deletions(-) diff --git a/src/rxn_network/enumerators/basic.py b/src/rxn_network/enumerators/basic.py index 0f139fd9..9e9b01a5 100644 --- a/src/rxn_network/enumerators/basic.py +++ b/src/rxn_network/enumerators/basic.py @@ -84,8 +84,6 @@ def __init__( self.quiet = quiet self._stabilize = False - if "ChempotDistanceCalculator" in self.calculators: - self._stabilize = True # ChempotDistanceCalculator requires stable entries self.open_phases: Optional[List] = None self._build_pd = False diff --git a/src/rxn_network/thermo/chempot_diagram.py b/src/rxn_network/thermo/chempot_diagram.py index cb4f4f88..d4201e1f 100644 --- a/src/rxn_network/thermo/chempot_diagram.py +++ b/src/rxn_network/thermo/chempot_diagram.py @@ -10,8 +10,7 @@ from pymatgen.analysis.chempot_diagram import ChemicalPotentialDiagram as ChempotDiagram from pymatgen.analysis.phase_diagram import PDEntry, PhaseDiagram from pymatgen.core.composition import Element - -from scipy.spatial import KDTree, HalfspaceIntersection +from scipy.spatial import HalfspaceIntersection, KDTree from rxn_network.entries.entry_set import GibbsEntrySet @@ -68,8 +67,20 @@ def shortest_domain_distance(self, f1: str, f2: str) -> float: Shortest distance between domain boundaries in the full (hyper)dimensional space, calculated using KDTree. """ - pts1 = self.domains[f1] - pts2 = self.domains[f2] + + if f1 in self.domains: + pts1 = self.domains[f1] + elif f1 in self.metastable_domains: + pts1 = self.metastable_domains[f1] + else: + raise ValueError(f"Formula {f1} not in domains!") + + if f2 in self.domains: + pts2 = self.domains[f2] + elif f2 in self.metastable_domains: + pts2 = self.metastable_domains[f2] + else: + raise ValueError(f"Formula {f2} not in domains!") tree = KDTree(pts1) From a61866bb3aeaebeb13466b9efcb62584052f4628 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Thu, 10 Feb 2022 16:21:01 -0800 Subject: [PATCH 12/14] improve competitiveness score calculator by better filtering --- src/rxn_network/costs/competitiveness.py | 12 +++++++++++- src/rxn_network/entries/entry_set.py | 14 +++++++++++++- src/rxn_network/enumerators/utils.py | 6 +++--- 3 files changed, 27 insertions(+), 5 deletions(-) diff --git a/src/rxn_network/costs/competitiveness.py b/src/rxn_network/costs/competitiveness.py index 6edda756..07713b85 100644 --- a/src/rxn_network/costs/competitiveness.py +++ b/src/rxn_network/costs/competitiveness.py @@ -40,6 +40,7 @@ def __init__( use_minimize=False, basic_enumerator_kwargs: Optional[Dict] = None, minimize_enumerator_kwargs: Optional[Dict] = None, + quiet=True, name: str = "c_score", ): """ @@ -70,6 +71,10 @@ def __init__( if not self.minimize_enumerator_kwargs.get("calculators"): self.minimize_enumerator_kwargs["calculators"] = calcs + if quiet: + self.basic_enumerator_kwargs["quiet"] = True + self.minimize_enumerator_kwargs["quiet"] = True + def calculate(self, rxn: ComputedReaction) -> float: """ Calculates the competitiveness score for a given reaction by enumerating @@ -105,6 +110,8 @@ def get_competing_rxns(self, rxn: ComputedReaction) -> List[ComputedReaction]: A list of competing reactions """ + chemsys = rxn.chemical_system.split("-") + precursors = [r.reduced_formula for r in rxn.reactants] open_elem = self.open_elem @@ -116,6 +123,9 @@ def get_competing_rxns(self, rxn: ComputedReaction) -> List[ComputedReaction]: if open_phases: precursors = list(set(precursors) - set(open_phases)) + entries = self.entries.filter_by_stability(0.0).get_subset_in_chemsys(chemsys) + entries.update(rxn.entries) # add back entries which may have been filtered out + enumerators = [] if self.use_basic: kwargs = self.basic_enumerator_kwargs.copy() @@ -143,7 +153,7 @@ def get_competing_rxns(self, rxn: ComputedReaction) -> List[ComputedReaction]: rxns = set() for e in enumerators: - rxns.update(e.enumerate(self.entries)) + rxns.update(e.enumerate(entries)) if rxn in rxns: rxns.remove(rxn) diff --git a/src/rxn_network/entries/entry_set.py b/src/rxn_network/entries/entry_set.py index 00700d91..6a190e9e 100644 --- a/src/rxn_network/entries/entry_set.py +++ b/src/rxn_network/entries/entry_set.py @@ -63,10 +63,22 @@ def add(self, entry: Union[GibbsComputedEntry, ExperimentalReferenceEntry]): """ Add an entry to the set. - :param element: Entry + Args: + entry: An entry object. """ self.entries.add(entry) + def update( + self, entries: Iterable[Union[GibbsComputedEntry, ExperimentalReferenceEntry]] + ): + """ + Add an iterable of entries to the set. + + Args: + entry: An iterable of entry objects. + """ + self.entries.update(entries) + def discard(self, entry: Union[GibbsComputedEntry, ExperimentalReferenceEntry]): """ Discard an entry. diff --git a/src/rxn_network/enumerators/utils.py b/src/rxn_network/enumerators/utils.py index e3f4c228..28710d10 100644 --- a/src/rxn_network/enumerators/utils.py +++ b/src/rxn_network/enumerators/utils.py @@ -15,7 +15,7 @@ from rxn_network.reactions.open import OpenComputedReaction -def initialize_entry(formula: str, entry_set: GibbsEntrySet, stabilize: bool = True): +def initialize_entry(formula: str, entry_set: GibbsEntrySet, stabilize: bool = False): """ Acquire a (stabilized) entry by user-specified formula. @@ -28,14 +28,14 @@ def initialize_entry(formula: str, entry_set: GibbsEntrySet, stabilize: bool = T """ try: entry = entry_set.get_min_entry_by_formula(formula) - except IndexError: + except KeyError: entry = entry_set.get_interpolated_entry(formula) warnings.warn( f"Using interpolated entry for {entry.composition.reduced_formula}" ) if stabilize: - entry = entry_set.get_stabilized_entry(entry, tol=1e-1) + entry = entry_set.get_stabilized_entry(entry, tol=1e-3) return entry From 19c0de09af90d2241c5d3d3e7fe917951bec81ac Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Thu, 10 Feb 2022 18:33:31 -0800 Subject: [PATCH 13/14] linting --- requirements-testing.txt | 4 ++-- setup.cfg | 2 ++ src/rxn_network/pathways/pathway_set.py | 2 +- src/rxn_network/thermo/chempot_diagram.py | 4 ++-- 4 files changed, 7 insertions(+), 5 deletions(-) diff --git a/requirements-testing.txt b/requirements-testing.txt index 5cbd9a10..5370c1e0 100644 --- a/requirements-testing.txt +++ b/requirements-testing.txt @@ -4,7 +4,7 @@ pytest-cov==3.0.0 pycodestyle==2.8.0 pydocstyle==6.1.1 flake8==4.0.1 -mypy==0.910 +mypy==0.931 mypy-extensions==0.4.3 pylint==2.12.2 -black==21.12b0 +black==22.1.0 \ No newline at end of file diff --git a/setup.cfg b/setup.cfg index 97fac142..2a76d2e8 100644 --- a/setup.cfg +++ b/setup.cfg @@ -24,6 +24,8 @@ ignore = D105,D2,D4 ignore_missing_imports = True [pylint.MASTER] +ignored-modules=scipy +extension-pkg-whitelist=scipy ignore-patterns=test_ disable=unsubscriptable-object, invalid-name, diff --git a/src/rxn_network/pathways/pathway_set.py b/src/rxn_network/pathways/pathway_set.py index 7acc8e0a..99426931 100644 --- a/src/rxn_network/pathways/pathway_set.py +++ b/src/rxn_network/pathways/pathway_set.py @@ -98,7 +98,7 @@ def from_paths( return cls( reaction_set=reaction_set, indices=indices, - coefficients=coefficients, + coefficients=coefficients, # type: ignore costs=costs, ) diff --git a/src/rxn_network/thermo/chempot_diagram.py b/src/rxn_network/thermo/chempot_diagram.py index d4201e1f..f0df0ea2 100644 --- a/src/rxn_network/thermo/chempot_diagram.py +++ b/src/rxn_network/thermo/chempot_diagram.py @@ -38,7 +38,7 @@ def __init__( of with 2+ elements limits: Bounds of elemental chemical potentials (min, max), which are used to construct the border hyperplanes used in the - HalfSpaceIntersection algorithm; these constrain the space over which the + HalfspaceIntersection algorithm; these constrain the space over which the domains are calculated and also determine the size of the plotted diagram. Any elemental limits not specified are covered in the default_min_limit argument @@ -100,7 +100,7 @@ def add_entry(self, entry): """ if entry in self.entries: return - elif not set(entry.composition.elements).issubset(self.elements): + if not set(entry.composition.elements).issubset(self.elements): raise ValueError("New entry is not within the same chemical system!") hyperplane = self._get_hyperplane(entry) From cf343f8391bd6324a88b1f2012679cc26e388e53 Mon Sep 17 00:00:00 2001 From: Matthew McDermott Date: Thu, 10 Feb 2022 18:40:10 -0800 Subject: [PATCH 14/14] run black --- src/rxn_network/enumerators/basic.py | 2 +- 1 file changed, 1 insertion(+), 1 deletion(-) diff --git a/src/rxn_network/enumerators/basic.py b/src/rxn_network/enumerators/basic.py index 9e9b01a5..c838f980 100644 --- a/src/rxn_network/enumerators/basic.py +++ b/src/rxn_network/enumerators/basic.py @@ -487,7 +487,7 @@ def estimate_max_num_reactions(self, entries: List[ComputedEntry]) -> int: num_combos = comb(len(entries), i) num_total_combos += num_combos_with_open * num_combos - return num_total_combos ** 2 + return num_total_combos**2 def _get_open_combos(self, open_entries): """Get all possible combinations of open entries. For a single entry,

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