"""Isotherm workchain"""
import os
from aiida.plugins import CalculationFactory, DataFactory, WorkflowFactory
from aiida.orm import Dict, Str, List, SinglefileData
from aiida.engine import calcfunction
from aiida.engine import WorkChain, ToContext, append_, while_, if_
from aiida_lsmo.utils import check_resize_unit_cell, aiida_dict_merge
from aiida_lsmo.utils import dict_merge
# import sub-workchains
RaspaBaseWorkChain = WorkflowFactory('raspa.base') # pylint: disable=invalid-name
# import calculations
ZeoppCalculation = CalculationFactory('zeopp.network') # pylint: disable=invalid-name
FFBuilder = CalculationFactory('lsmo.ff_builder') # pylint: disable=invalid-name
# import aiida data
CifData = DataFactory('cif') # pylint: disable=invalid-name
ZeoppParameters = DataFactory('zeopp.parameters') # pylint: disable=invalid-name
# Deafault parameters
ISOTHERMPARAMETERS_DEFAULT = { #TODO: create IsothermParameters instead of Dict # pylint: disable=fixme
"ff_framework": "UFF", # (str) Forcefield of the structure.
"ff_separate_interactions": False, # (bool) Use "separate_interactions" in the FF builder.
"ff_mixing_rule": "Lorentz-Berthelot", # (string) Choose 'Lorentz-Berthelot' or 'Jorgensen'.
"ff_tail_corrections": True, # (bool) Apply tail corrections.
"ff_shifted": False, # (bool) Shift or truncate the potential at cutoff.
"ff_cutoff": 12.0, # (float) CutOff truncation for the VdW interactions (Angstrom).
"temperature": 300, # (float) Temperature of the simulation.
"temperature_list": None, # (list) To be used by IsothermMultiTempWorkChain.
"zeopp_volpo_samples": int(1e5), # (int) Number of samples for VOLPO calculation (per UC volume).
"zeopp_block_samples": int(100), # (int) Number of samples for BLOCK calculation (per A^3).
"raspa_minKh": 1e-10, # (float) If Henry coefficient < raspa_minKh do not run the isotherm (mol/kg/Pa).
"raspa_verbosity": 10, # (int) Print stats every: number of cycles / raspa_verbosity.
"raspa_widom_cycles": int(1e5), # (int) Number of Widom cycles.
"raspa_gcmc_init_cycles": int(1e3), # (int) Number of GCMC initialization cycles.
"raspa_gcmc_prod_cycles": int(1e4), # (int) Number of GCMC production cycles.
"pressure_list": None, # (list) Pressure list for the isotherm (bar): if given it will skip to guess it.
"pressure_precision": 0.1, # (float) Precision in the sampling of the isotherm: 0.1 ok, 0.05 for high resolution.
"pressure_maxstep": 5, # (float) Max distance between pressure points (bar).
"pressure_min": 0.001, # (float) Lower pressure to sample (bar).
"pressure_max": 10 # (float) Upper pressure to sample (bar).
}
# calcfunctions (in order of appearence)
[docs]@calcfunction
def get_molecule_dict(molecule_name):
"""Get a Dict from the isotherm_molecules.yaml"""
import ruamel.yaml as yaml
thisdir = os.path.dirname(os.path.abspath(__file__))
yamlfile = os.path.join(thisdir, "isotherm_data", "isotherm_molecules.yaml")
with open(yamlfile, 'r') as stream:
yaml_dict = yaml.safe_load(stream)
molecule_dict = yaml_dict[molecule_name.value]
return Dict(dict=molecule_dict)
[docs]@calcfunction
def get_atomic_radii(isotparam):
"""Get {ff_framework}.rad as SinglefileData form workchain/isotherm_data. If not existing use DEFAULT.rad."""
thisdir = os.path.dirname(os.path.abspath(__file__))
filename = isotparam['ff_framework'] + ".rad"
filepath = os.path.join(thisdir, "isotherm_data", filename)
if not os.path.isfile(filepath):
filepath = os.path.join(thisdir, "isotherm_data", "DEFAULT.rad")
return SinglefileData(file=filepath)
[docs]@calcfunction
def get_zeopp_parameters(molecule_dict, isotparam):
"""Get the ZeoppParameters from the inputs of the workchain"""
probe_rad = molecule_dict["proberad"]
param_dict = {
'ha': 'DEF',
'volpo': [probe_rad, probe_rad, isotparam['zeopp_volpo_samples']],
'block': [probe_rad, isotparam['zeopp_block_samples']],
}
return ZeoppParameters(dict=param_dict)
[docs]@calcfunction
def get_ff_parameters(molecule_dict, isotparam):
"""Get the parameters for ff_builder."""
ff_params = {}
ff_params['ff_framework'] = isotparam['ff_framework']
ff_params['ff_molecules'] = {molecule_dict['name']: molecule_dict['forcefield']}
ff_params['shifted'] = isotparam['ff_shifted']
ff_params['tail_corrections'] = isotparam['ff_tail_corrections']
ff_params['mixing_rule'] = isotparam['ff_mixing_rule']
ff_params['separate_interactions'] = isotparam['ff_separate_interactions']
return Dict(dict=ff_params)
[docs]@calcfunction
def choose_pressure_points(inp_param, geom, raspa_widom_out):
"""If 'presure_list' is not provide, model the isotherm as single-site langmuir and return the most important
pressure points to evaluate for an isotherm, in a List.
"""
if inp_param["pressure_list"]:
pressure_points = inp_param["pressure_list"]
else:
khenry = list(raspa_widom_out["framework_1"]["components"].values())[0]['henry_coefficient_average'] #mol/kg/Pa
b_value = khenry / geom['Estimated_saturation_loading'] * 1e5 #(1/bar)
pressure_points = [inp_param['pressure_min']]
while True:
pold = pressure_points[-1]
delta_p = min(inp_param['pressure_maxstep'],
inp_param['pressure_precision'] * (b_value * pold**2 + 2 * pold + 1 / b_value))
pnew = pold + delta_p
if pnew <= inp_param['pressure_max']:
pressure_points.append(pnew)
else:
pressure_points.append(inp_param['pressure_max'])
break
return List(list=pressure_points)
[docs]@calcfunction
def get_geometric_dict(zeopp_out, molecule):
"""Return the geometric Dict from Zeopp results, including Qsat and is_porous"""
geometric_dict = zeopp_out.get_dict()
geometric_dict.update({
'Estimated_saturation_loading': zeopp_out['POAV_cm^3/g'] * molecule['molsatdens'],
'Estimated_saturation_loading_unit': 'mol/kg',
'is_porous': geometric_dict["POAV_A^3"] > 0.000
})
return Dict(dict=geometric_dict)
[docs]@calcfunction
def get_output_parameters(geom_out, inp_params, widom_out=None, pressures=None, **gcmc_out_dict):
"""Merge results from all the steps of the work chain."""
out_dict = geom_out.get_dict()
if out_dict['is_porous'] and widom_out:
widom_out_mol = list(widom_out["framework_1"]["components"].values())[0]
out_dict.update({
'temperature': inp_params['temperature'],
'temperature_unit': 'K',
'is_kh_enough': widom_out_mol['henry_coefficient_average'] > inp_params['raspa_minKh']
})
widom_labels = [
'henry_coefficient_average',
'henry_coefficient_dev',
'henry_coefficient_unit',
'adsorption_energy_widom_average',
'adsorption_energy_widom_dev',
'adsorption_energy_widom_unit',
]
for label in widom_labels:
out_dict.update({label: widom_out_mol[label]})
if out_dict['is_kh_enough']:
isotherm = {
'pressure': pressures,
'pressure_unit': 'bar',
'loading_absolute_average': [],
'loading_absolute_dev': [],
'loading_absolute_unit': 'mol/kg',
'enthalpy_of_adsorption_average': [],
'enthalpy_of_adsorption_dev': [],
'enthalpy_of_adsorption_unit': 'kJ/mol'
}
conv_ener = 1.0 / 120.273 # K to kJ/mol
for i in range(len(pressures)):
gcmc_out = gcmc_out_dict['RaspaGCMC_{}'.format(i + 1)]["framework_1"]
gcmc_out_mol = list(gcmc_out["components"].values())[0]
conv_load = gcmc_out_mol["conversion_factor_molec_uc_to_mol_kg"]
for label in ['loading_absolute_average', 'loading_absolute_dev']:
isotherm[label].append(conv_load * gcmc_out_mol[label])
for label in ['enthalpy_of_adsorption_average', 'enthalpy_of_adsorption_dev']:
if gcmc_out['general'][label]:
isotherm[label].append(conv_ener * gcmc_out['general'][label])
else: # when there are no particles and Raspa return Null enthalpy
isotherm[label].append(None)
out_dict.update({
"isotherm": isotherm,
'conversion_factor_molec_uc_to_cm3stp_cm3': gcmc_out_mol['conversion_factor_molec_uc_to_cm3stp_cm3'],
'conversion_factor_molec_uc_to_mg_g': gcmc_out_mol['conversion_factor_molec_uc_to_mg_g'],
'conversion_factor_molec_uc_to_mol_kg': gcmc_out_mol['conversion_factor_molec_uc_to_mol_kg'],
})
return Dict(dict=out_dict)
[docs]class IsothermWorkChain(WorkChain):
"""Workchain that computes volpo and blocking spheres: if accessible volpo>0
it also runs a raspa widom calculation for the Henry coefficient.
"""
[docs] @classmethod
def define(cls, spec):
super().define(spec)
spec.expose_inputs(ZeoppCalculation, namespace='zeopp', include=['code', 'metadata'])
spec.expose_inputs(RaspaBaseWorkChain, namespace='raspa_base', exclude=['raspa.structure', 'raspa.parameters'])
spec.input('structure', valid_type=CifData, help='Adsorbent framework CIF.')
spec.input("molecule",
valid_type=(Str, Dict),
help='Adsorbate molecule: settings to be read from the yaml.' +
'Advanced: input a Dict for non-standard settings.')
spec.input("parameters",
valid_type=Dict,
help='Parameters for the Isotherm workchain: will be merged with IsothermParameters_defaults.')
spec.input("geometric",
valid_type=Dict,
required=False,
help='[Only used by IsothermMultiTempWorkChain] Already computed geometric properties')
spec.outline(
cls.setup,
cls.run_zeopp, # computes volpo and blocks
if_(cls.should_run_widom)( # run Widom only if porous
cls.run_raspa_widom, # run raspa widom calculation
if_(cls.should_run_gcmc)( # Kh is high enough
cls.init_raspa_gcmc, # initializate setting for GCMC
while_(cls.should_run_another_gcmc)( # new pressure
cls.run_raspa_gcmc, # run raspa GCMC calculation
),
),
),
cls.return_output_parameters,
)
spec.expose_outputs(ZeoppCalculation, include=['block']) #only if porous
spec.output(
'output_parameters',
valid_type=Dict,
required=True,
help='Results of the single temperature wc: keys can vay depending on is_porous and is_kh_enough booleans.')
[docs] def setup(self):
"""Initialize the parameters"""
# Get the molecule Dict from the yaml or directly as an input
if isinstance(self.inputs.molecule, Str):
self.ctx.molecule = get_molecule_dict(self.inputs.molecule)
elif isinstance(self.inputs.molecule, Dict):
self.ctx.molecule = self.inputs.molecule
# Get the parameters Dict, merging defaults with user settings
self.ctx.parameters = aiida_dict_merge(Dict(dict=ISOTHERMPARAMETERS_DEFAULT), self.inputs.parameters)
# Get integer temperature in context for easy reports
self.ctx.temperature = int(round(self.ctx.parameters['temperature']))
# Understand if IsothermMultiTempWorkChain is calling this work chain
if "geometric" in self.inputs:
self.ctx.multitemp_mode = 'run_single_temp'
elif self.ctx.parameters['temperature_list']:
self.ctx.multitemp_mode = 'run_geom_only'
else:
self.ctx.multitemp_mode = None
[docs] def run_zeopp(self):
"""Perform Zeo++ block and VOLPO calculations."""
# Skip zeopp calculation if the geometric properties are already provided by IsothermMultiTemp
if self.ctx.multitemp_mode == 'run_single_temp':
return None
# create inputs: exposed are code and metadata
inputs = self.exposed_inputs(ZeoppCalculation, 'zeopp')
# Set inputs for zeopp
dict_merge(
inputs, {
'metadata': {
'label': "ZeoppVolpoBlock",
'call_link_label': 'run_zeopp_block_and_volpo',
},
'structure': self.inputs.structure,
'atomic_radii': get_atomic_radii(self.ctx.parameters),
'parameters': get_zeopp_parameters(self.ctx.molecule, self.ctx.parameters)
})
running = self.submit(ZeoppCalculation, **inputs)
self.report("Running zeo++ block and volpo for {} Calculation<{}>".format(self.ctx.molecule['name'],
running.id))
return ToContext(zeopp=running)
[docs] def should_run_widom(self):
"""Submit widom calculation only if there is some accessible volume,
also check the number of blocking spheres and estimate the saturation loading.
Also, stop if called by IsothermMultiTemp for geometric results only."""
# Get geometric properties and consider if IsothermMultiTempWorkChain is calling this workchain
if self.ctx.multitemp_mode == 'run_single_temp':
self.ctx.geom = self.inputs.geometric
return True
self.ctx.geom = get_geometric_dict(self.ctx.zeopp.outputs.output_parameters, self.ctx.molecule)
if self.ctx.geom['is_porous']:
self.report("Found accessible pore volume for {}: continue".format(self.ctx.molecule['name']))
self.report("Found {} blocking spheres".format(self.ctx.geom['Number_of_blocking_spheres']))
# Return block file only if blocking spheres are present
if self.ctx.geom['Number_of_blocking_spheres'] > 0:
self.out_many(self.exposed_outputs(self.ctx.zeopp, ZeoppCalculation))
else:
self.report("No accessible pore volume to {}: stop".format(self.ctx.molecule['name']))
return self.ctx.geom['is_porous'] and not self.ctx.multitemp_mode == 'run_geom_only'
[docs] def _get_widom_param(self):
"""Write Raspa input parameters from scratch, for a Widom calculation"""
param = {
"GeneralSettings": {
"SimulationType":
"MonteCarlo",
"NumberOfInitializationCycles":
0,
"NumberOfCycles":
self.ctx.parameters['raspa_widom_cycles'],
"PrintPropertiesEvery":
self.ctx.parameters['raspa_widom_cycles'] / self.ctx.parameters['raspa_verbosity'],
"PrintEvery":
int(1e10),
"RemoveAtomNumberCodeFromLabel":
True, # BE CAREFULL: needed in AiiDA-1.0.0 because of github.com/aiidateam/aiida-core/issues/3304
"Forcefield":
"Local",
"UseChargesFromCIFFile":
"yes",
"CutOff":
self.ctx.parameters['ff_cutoff'],
},
"System": {
"framework_1": {
"type": "Framework",
"HeliumVoidFraction": self.ctx.geom["POAV_Volume_fraction"],
"ExternalTemperature": self.ctx.parameters['temperature'],
}
},
"Component": {
self.ctx.molecule['name']: {
"MoleculeDefinition": "Local",
"WidomProbability": 1.0,
},
},
}
# Check particular conditions and settings
mult = check_resize_unit_cell(self.inputs.structure, 2 * self.ctx.parameters['ff_cutoff'])
param["System"]["framework_1"]["UnitCells"] = "{} {} {}".format(mult[0], mult[1], mult[2])
if self.ctx.geom['Number_of_blocking_spheres'] > 0:
param["Component"][self.ctx.molecule['name']]["BlockPocketsFileName"] = "block_file"
if self.ctx.molecule['charged']: # NOTE: `Chargemethod Ewald` is the default in Raspa!
param["GeneralSettings"].update({"ChargeMethod": "Ewald", "EwaldPrecision": 1e-6})
else:
param["GeneralSettings"].update({"ChargeMethod": "None"})
return param
[docs] def run_raspa_widom(self):
"""Run a Widom calculation in Raspa."""
# Initialize the input for raspa_base, which later will need only minor updates for GCMC
self.ctx.inp = self.exposed_inputs(RaspaBaseWorkChain, 'raspa_base')
self.ctx.inp['metadata']['label'] = "RaspaWidom"
self.ctx.inp['metadata']['call_link_label'] = "run_raspa_widom"
self.ctx.inp['raspa']['framework'] = {"framework_1": self.inputs.structure}
if self.ctx.geom['Number_of_blocking_spheres'] > 0 and self.ctx.multitemp_mode != 'run_single_temp':
self.ctx.inp["raspa"]["block_pocket"] = {"block_file": self.ctx.zeopp.outputs.block}
self.ctx.raspa_param = self._get_widom_param()
self.ctx.inp['raspa']['parameters'] = Dict(dict=self.ctx.raspa_param)
# Generate the force field with the ff_builder
ff_params = get_ff_parameters(self.ctx.molecule, self.ctx.parameters)
files_dict = FFBuilder(ff_params)
self.ctx.inp['raspa']['file'] = files_dict
running = self.submit(RaspaBaseWorkChain, **self.ctx.inp)
self.report("Running Raspa Widom {} @ {}K for the Henry coefficient".format(self.ctx.molecule['name'],
self.ctx.temperature))
return ToContext(raspa_widom=running)
[docs] def should_run_gcmc(self):
"""Output the widom results and decide to compute the isotherm if kH > kHmin, as defined by the user"""
self.ctx.is_kh_enough = list(self.ctx.raspa_widom.outputs['output_parameters']["framework_1"]["components"].
values())[0]['henry_coefficient_average'] > self.ctx.parameters['raspa_minKh']
if self.ctx.is_kh_enough:
self.report("kH larger than the threshold for {}: continue".format(self.ctx.molecule['name']))
return True
self.report("kHh lower than the threshold for {}: stop".format(self.ctx.molecule['name']))
return False
[docs] def _update_param_for_gcmc(self):
"""Update Raspa input parameter, from Widom to GCMC"""
param = self.ctx.raspa_param
param["GeneralSettings"].update({
"NumberOfInitializationCycles": self.ctx.parameters['raspa_gcmc_init_cycles'],
"NumberOfCycles": self.ctx.parameters['raspa_gcmc_prod_cycles'],
"PrintPropertiesEvery": int(1e6),
"PrintEvery": self.ctx.parameters['raspa_gcmc_prod_cycles'] / self.ctx.parameters['raspa_verbosity']
})
param["Component"][self.ctx.molecule['name']].update({
"WidomProbability": 0.0,
"TranslationProbability": 1.0,
"ReinsertionProbability": 1.0,
"SwapProbability": 2.0,
})
# Check particular conditions
if not self.ctx.molecule['singlebead']:
param["Component"][self.ctx.molecule['name']].update({"RotationProbability": 1.0})
return param
[docs] def init_raspa_gcmc(self):
"""Choose the pressures we want to sample, report some details, and update settings for GCMC"""
self.ctx.current_p_index = 0
self.ctx.pressures = choose_pressure_points(self.ctx.parameters, self.ctx.geom,
self.ctx.raspa_widom.outputs.output_parameters)
self.report("{}: Kh(mol/kg/Pa)={:.2e} POAV(cm3/g)={:.3f} Qsat(mol/kg)={:.2f}".format(
self.ctx.molecule['name'],
list(self.ctx.raspa_widom.outputs['output_parameters']["framework_1"]["components"].values())[0]
['henry_coefficient_average'], self.ctx.geom['POAV_cm^3/g'], self.ctx.geom['Estimated_saturation_loading']))
self.report("Now evaluating the isotherm {} @ {}K for {} pressure points".format(
self.ctx.molecule['name'], self.ctx.temperature, len(self.ctx.pressures)))
self.ctx.raspa_param = self._update_param_for_gcmc()
[docs] def should_run_another_gcmc(self):
"""We run another raspa calculation only if the current iteration is
smaller than the total number of pressures we want to compute.
"""
return self.ctx.current_p_index < len(self.ctx.pressures)
[docs] def run_raspa_gcmc(self):
"""Run a GCMC calculation in Raspa @ T,P. """
# Update labels
self.ctx.inp['metadata']['label'] = "RaspaGCMC_{}".format(self.ctx.current_p_index + 1)
self.ctx.inp['metadata']['call_link_label'] = "run_raspa_gcmc_{}".format(self.ctx.current_p_index + 1)
# Update pressure (NOTE: need to convert from bar to Pa)
self.ctx.raspa_param["System"]["framework_1"]['ExternalPressure'] = \
self.ctx.pressures[self.ctx.current_p_index] * 1e5
# Update parameters Dict
self.ctx.inp['raspa']['parameters'] = Dict(dict=self.ctx.raspa_param)
# Update restart (if present, i.e., if current_p_index>0)
if self.ctx.current_p_index > 0:
self.ctx.inp['raspa']['retrieved_parent_folder'] = self.ctx.raspa_gcmc[self.ctx.current_p_index -
1].outputs.retrieved
# Create the calculation process, launch it and update pressure index
running = self.submit(RaspaBaseWorkChain, **self.ctx.inp)
self.report("Running Raspa GCMC {} @ {}K/{:.3f}bar (pressure {} of {})".format(
self.ctx.molecule['name'], self.ctx.temperature, self.ctx.pressures[self.ctx.current_p_index],
self.ctx.current_p_index + 1, len(self.ctx.pressures)))
self.ctx.current_p_index += 1
return ToContext(raspa_gcmc=append_(running))
[docs] def return_output_parameters(self):
"""Merge all the parameters into output_parameters, depending on is_porous and is_kh_ehough."""
gcmc_out_dict = {}
if self.ctx.geom['is_porous'] and not self.ctx.multitemp_mode == 'run_geom_only':
widom_out = self.ctx.raspa_widom.outputs.output_parameters
if self.ctx.is_kh_enough:
for calc in self.ctx.raspa_gcmc:
gcmc_out_dict[calc.label] = calc.outputs.output_parameters
else:
self.ctx.pressures = None
else:
widom_out = None
self.ctx.pressures = None
self.out(
"output_parameters",
get_output_parameters(geom_out=self.ctx.geom,
inp_params=self.ctx.parameters,
widom_out=widom_out,
pressures=self.ctx.pressures,
**gcmc_out_dict))
if not self.ctx.multitemp_mode == 'run_geom_only':
self.report("Isotherm {} @ {}K computed: ouput Dict<{}>".format(self.ctx.molecule['name'],
self.ctx.temperature,
self.outputs['output_parameters'].pk))