Source code for pymatgen.analysis.defects.utils

# coding: utf-8
# Copyright (c) Pymatgen Development Team.
# Distributed under the terms of the MIT License.

Utilities for defects module.

import math

from monty.json import MSONable

import itertools
import pandas as pd
import numpy as np
from numpy.linalg import norm
import logging

from collections import defaultdict
from scipy.spatial import Voronoi
from scipy.spatial.distance import squareform
from scipy.cluster.hierarchy import linkage, fcluster
from pymatgen.analysis.local_env import LocalStructOrderParams, \
    MinimumDistanceNN, cn_opt_params
from pymatgen.core.periodic_table import Element, get_el_sp
from pymatgen.core.sites import PeriodicSite
from pymatgen.core.structure import Structure
from import Chgcar
from pymatgen.symmetry.analyzer import SpacegroupAnalyzer
from pymatgen.analysis.phase_diagram import get_facets
from pymatgen.util.coord import pbc_diff
from pymatgen.vis.structure_vtk import StructureVis
from import requires
from copy import deepcopy

    from skimage.feature import peak_local_max

    peak_local_max_found = True
except ImportError:
    peak_local_max_found = False

__author__ = "Danny Broberg, Shyam Dwaraknath, Bharat Medasani, Nils Zimmermann, Geoffroy Hautier"
__copyright__ = "Copyright 2014, The Materials Project"
__version__ = "1.0"
__maintainer__ = "Danny Broberg, Shyam Dwaraknath"
__email__ = ","
__status__ = "Development"
__date__ = "January 11, 2018"

logger = logging.getLogger(__name__)
hart_to_ev = 27.2114
ang_to_bohr = 1.8897
invang_to_ev = 3.80986
kb = 8.6173324e-5  # eV / K
kumagai_to_V = 1.809512739e2  # = Electron charge * 1e10 / VacuumPermittivity Constant

motif_cn_op = {}
for cn, di in cn_opt_params.items():  # type: ignore
    for mot, li in di.items():
        motif_cn_op[mot] = {'cn': int(cn), 'optype': li[0]}
        motif_cn_op[mot]['params'] = deepcopy(li[1]) if len(li) > 1 else None

[docs]class QModel(MSONable): """ Model for the defect charge distribution. A combination of exponential tail and gaussian distribution is used (see Freysoldt (2011), DOI: 10.1002/pssb.201046289 ) q_model(r) = q [x exp(-r/gamma) + (1-x) exp(-r^2/beta^2)] without normalization constants By default, gaussian distribution with 1 Bohr width is assumed. If defect charge is more delocalized, exponential tail is suggested. """ def __init__(self, beta=1.0, expnorm=0.0, gamma=1.0): """ Args: beta: Gaussian decay constant. Default value is 1 Bohr. When delocalized (eg. diamond), 2 Bohr is more appropriate. expnorm: Weight for the exponential tail in the range of [0-1]. Default is 0.0 indicating no tail . For delocalized charges ideal value is around 0.54-0.6. gamma: Exponential decay constant """ self.beta = beta self.expnorm = expnorm self.gamma = gamma self.beta2 = beta * beta self.gamma2 = gamma * gamma if expnorm and not gamma: raise ValueError("Please supply exponential decay constant.")
[docs] def rho_rec(self, g2): """ Reciprocal space model charge value for input squared reciprocal vector. Args: g2: Square of reciprocal vector Returns: Charge density at the reciprocal vector magnitude """ return (self.expnorm / np.sqrt(1 + self.gamma2 * g2) + ( 1 - self.expnorm) * np.exp(-0.25 * self.beta2 * g2))
@property def rho_rec_limit0(self): """ Reciprocal space model charge value close to reciprocal vector 0 . rho_rec(g->0) -> 1 + rho_rec_limit0 * g^2 """ return -2 * self.gamma2 * self.expnorm - 0.25 * self.beta2 * ( 1 - self.expnorm)
[docs]def eV_to_k(energy): """ Convert energy to reciprocal vector magnitude k via hbar*k^2/2m Args: a: Energy in eV. Returns: (double) Reciprocal vector magnitude (units of 1/Bohr). """ return math.sqrt(energy / invang_to_ev) * ang_to_bohr
[docs]def genrecip(a1, a2, a3, encut): """ Args: a1, a2, a3: lattice vectors in bohr encut: energy cut off in eV Returns: reciprocal lattice vectors with energy less than encut """ vol =, np.cross(a2, a3)) # 1/bohr^3 b1 = (2 * np.pi / vol) * np.cross(a2, a3) # units 1/bohr b2 = (2 * np.pi / vol) * np.cross(a3, a1) b3 = (2 * np.pi / vol) * np.cross(a1, a2) # create list of recip space vectors that satisfy |i*b1+j*b2+k*b3|<=encut G_cut = eV_to_k(encut) # Figure out max in all recipricol lattice directions i_max = int(math.ceil(G_cut / norm(b1))) j_max = int(math.ceil(G_cut / norm(b2))) k_max = int(math.ceil(G_cut / norm(b3))) # Build index list i = np.arange(-i_max, i_max) j = np.arange(-j_max, j_max) k = np.arange(-k_max, k_max) # Convert index to vectors using meshgrid indicies = np.array(np.meshgrid(i, j, k)).T.reshape(-1, 3) # Multiply integer vectors to get recipricol space vectors vecs =, [b1, b2, b3]) # Calculate radii of all vectors radii = np.sqrt(np.einsum('ij,ij->i', vecs, vecs)) # Yield based on radii for vec, r in zip(vecs, radii): if r < G_cut and r != 0: yield vec
[docs]def generate_reciprocal_vectors_squared(a1, a2, a3, encut): """ Generate reciprocal vector magnitudes within the cutoff along the specied lattice vectors. Args: a1: Lattice vector a (in Bohrs) a2: Lattice vector b (in Bohrs) a3: Lattice vector c (in Bohrs) encut: Reciprocal vector energy cutoff Returns: [[g1^2], [g2^2], ...] Square of reciprocal vectors (1/Bohr)^2 determined by a1, a2, a3 and whose magntidue is less than gcut^2. """ for vec in genrecip(a1, a2, a3, encut): yield, vec)
[docs]def closestsites(struct_blk, struct_def, pos): """ Returns closest site to the input position for both bulk and defect structures Args: struct_blk: Bulk structure struct_def: Defect structure pos: Position Return: (site object, dist, index) """ blk_close_sites = struct_blk.get_sites_in_sphere(pos, 5, include_index=True) blk_close_sites.sort(key=lambda x: x[1]) def_close_sites = struct_def.get_sites_in_sphere(pos, 5, include_index=True) def_close_sites.sort(key=lambda x: x[1]) return blk_close_sites[0], def_close_sites[0]
[docs]class StructureMotifInterstitial: """ Generate interstitial sites at positions where the interstitialcy is coordinated by nearest neighbors in a way that resembles basic structure motifs (e.g., tetrahedra, octahedra). The algorithm is called InFiT (Interstitialcy Finding Tool), it was introducted by Nils E. R. Zimmermann, Matthew K. Horton, Anubhav Jain, and Maciej Haranczyk (Front. Mater., 4, 34, 2017), and it is used by the Python Charged Defect Toolkit (PyCDT: D. Broberg et al., Comput. Phys. Commun., in press, 2018). """ def __init__(self, struct, inter_elem, motif_types=("tetrahedral", "octahedral"), op_threshs=(0.3, 0.5), dl=0.2, doverlap=1, facmaxdl=1.01, verbose=False): """ Generates symmetrically distinct interstitial sites at positions where the interstitial is coordinated by nearest neighbors in a pattern that resembles a supported structure motif (e.g., tetrahedra, octahedra). Args: struct (Structure): input structure for which symmetrically distinct interstitial sites are to be found. inter_elem (string): element symbol of desired interstitial. motif_types ([string]): list of structure motif types that are to be considered. Permissible types are: tet (tetrahedron), oct (octahedron). op_threshs ([float]): threshold values for the underlying order parameters to still recognize a given structural motif (i.e., for an OP value >= threshold the coordination pattern match is positive, for OP < threshold the match is negative. dl (float): grid fineness in Angstrom. The input structure is divided into a grid of dimension a/dl x b/dl x c/dl along the three crystallographic directions, with a, b, and c being the lengths of the three lattice vectors of the input unit cell. doverlap (float): distance that is considered to flag an overlap between any trial interstitial site and a host atom. facmaxdl (float): factor to be multiplied with the maximum grid width that is then used as a cutoff distance for the clustering prune step. verbose (bool): flag indicating whether (True) or not (False; default) to print additional information to screen. """ # Initialize interstitial finding. self._structure = struct.copy() self._motif_types = motif_types[:] if len(self._motif_types) == 0: raise RuntimeError("no motif types provided.") self._op_threshs = op_threshs[:] self.cn_motif_lostop = {} self.target_cns = [] for motif in self._motif_types: if motif not in list(motif_cn_op.keys()): raise RuntimeError("unsupported motif type: {}.".format(motif)) cn = int(motif_cn_op[motif]['cn']) if cn not in self.target_cns: self.target_cns.append(cn) if cn not in list(self.cn_motif_lostop.keys()): self.cn_motif_lostop[cn] = {} tmp_optype = motif_cn_op[motif]['optype'] if tmp_optype == 'tet_max': tmp_optype = 'tet' if tmp_optype == 'oct_max': tmp_optype = 'oct' self.cn_motif_lostop[cn][motif] = LocalStructOrderParams( [tmp_optype], parameters=[motif_cn_op[motif]['params']], cutoff=-10.0) self._dl = dl self._defect_sites = [] self._defect_types = [] self._defect_site_multiplicity = [] self._defect_cns = [] self._defect_opvals = [] rots, trans = SpacegroupAnalyzer(struct)._get_symmetry() nbins = [int(struct.lattice.a / dl), int(struct.lattice.b / dl), int(struct.lattice.c / dl)] dls = [ struct.lattice.a / float(nbins[0]), struct.lattice.b / float(nbins[1]), struct.lattice.c / float(nbins[2]) ] maxdl = max(dls) if verbose: print("Grid size: {} {} {}".format(nbins[0], nbins[1], nbins[2])) print("dls: {} {} {}".format(dls[0], dls[1], dls[2])) struct_w_inter = struct.copy() struct_w_inter.append(inter_elem, [0, 0, 0]) natoms = len(list(struct_w_inter.sites)) trialsites = [] # Build index list i = np.arange(0, nbins[0]) + 0.5 j = np.arange(0, nbins[1]) + 0.5 k = np.arange(0, nbins[2]) + 0.5 # Convert index to vectors using meshgrid indicies = np.array(np.meshgrid(i, j, k)).T.reshape(-1, 3) # Multiply integer vectors to get recipricol space vectors vecs = np.multiply(indicies, np.divide(1, nbins)) # Loop over trial positions that are based on a regular # grid in fractional coordinate space # within the unit cell. for vec in vecs: struct_w_inter.replace(natoms - 1, inter_elem, coords=vec, coords_are_cartesian=False) if len(struct_w_inter.get_sites_in_sphere( struct_w_inter.sites[natoms - 1].coords, doverlap)) == 1: neighs_images_weigths = MinimumDistanceNN(tol=0.8, cutoff=6).get_nn_info( struct_w_inter, natoms - 1) neighs_images_weigths_sorted = sorted(neighs_images_weigths, key=lambda x: x['weight'], reverse=True) for nsite in range(1, len(neighs_images_weigths_sorted) + 1): if nsite not in self.target_cns: continue allsites = [neighs_images_weigths_sorted[i]['site'] for i in range(nsite)] indices_neighs = [i for i in range(len(allsites))] allsites.append(struct_w_inter.sites[natoms - 1]) for mot, ops in self.cn_motif_lostop[nsite].items(): opvals = ops.get_order_parameters( allsites, len(allsites) - 1, indices_neighs=indices_neighs) if opvals[0] > op_threshs[motif_types.index(mot)]: cns = {} for isite in range(nsite): site = neighs_images_weigths_sorted[isite][ 'site'] if isinstance(site.specie, Element): elem = site.specie.symbol else: elem = site.specie.element.symbol if elem in list(cns.keys()): cns[elem] = cns[elem] + 1 else: cns[elem] = 1 trialsites.append({ "mtype": mot, "opval": opvals[0], "coords": struct_w_inter.sites[ natoms - 1].coords[:], "fracs": vec, "cns": dict(cns) }) break # Prune list of trial sites by clustering and find the site # with the largest order parameter value in each cluster. nintersites = len(trialsites) unique_motifs = [] for ts in trialsites: if ts["mtype"] not in unique_motifs: unique_motifs.append(ts["mtype"]) labels = {} connected = [] for i in range(nintersites): connected.append([]) for j in range(nintersites): dist, image = struct_w_inter.lattice.get_distance_and_image( trialsites[i]["fracs"], trialsites[j]["fracs"]) connected[i].append( True if dist < (maxdl * facmaxdl) else False) include = [] for motif in unique_motifs: labels[motif] = [] for i, ts in enumerate(trialsites): labels[motif].append(i if ts["mtype"] == motif else -1) change = True while change: change = False for i in range(nintersites - 1): if change: break if labels[motif][i] == -1: continue for j in range(i + 1, nintersites): if labels[motif][j] == -1: continue if connected[i][j] and labels[motif][i] != \ labels[motif][j]: if labels[motif][i] < labels[motif][j]: labels[motif][j] = labels[motif][i] else: labels[motif][i] = labels[motif][j] change = True break unique_ids = [] for l in labels[motif]: if l != -1 and l not in unique_ids: unique_ids.append(l) if verbose: print("unique_ids {} {}".format(motif, unique_ids)) for uid in unique_ids: maxq = 0.0 imaxq = -1 for i in range(nintersites): if labels[motif][i] == uid: if imaxq < 0 or trialsites[i]["opval"] > maxq: imaxq = i maxq = trialsites[i]["opval"] include.append(imaxq) # Prune by symmetry. multiplicity = {} discard = [] for motif in unique_motifs: discard_motif = [] for indi, i in enumerate(include): if trialsites[i]["mtype"] != motif or \ i in discard_motif: continue multiplicity[i] = 1 symposlist = [ trialsites[i]["fracs"].dot(np.array(m, dtype=float)) for m in rots] for t in trans: symposlist.append(trialsites[i]["fracs"] + np.array(t)) for indj in range(indi + 1, len(include)): j = include[indj] if trialsites[j]["mtype"] != motif or \ j in discard_motif: continue for sympos in symposlist: dist, image = struct.lattice.get_distance_and_image( sympos, trialsites[j]["fracs"]) if dist < maxdl * facmaxdl: discard_motif.append(j) multiplicity[i] += 1 break for i in discard_motif: if i not in discard: discard.append(i) if verbose: print("Initial trial sites: {}\nAfter clustering: {}\n" "After symmetry pruning: {}".format(len(trialsites), len(include), len(include) - len( discard))) for i in include: if i not in discard: self._defect_sites.append( PeriodicSite( Element(inter_elem), trialsites[i]["fracs"], self._structure.lattice, to_unit_cell=False, coords_are_cartesian=False, properties=None)) self._defect_types.append(trialsites[i]["mtype"]) self._defect_cns.append(trialsites[i]["cns"]) self._defect_site_multiplicity.append(multiplicity[i]) self._defect_opvals.append(trialsites[i]["opval"])
[docs] def enumerate_defectsites(self): """ Get all defect sites. Returns: defect_sites ([PeriodicSite]): list of periodic sites representing the interstitials. """ return self._defect_sites
[docs] def get_motif_type(self, i): """ Get the motif type of defect with index i (e.g., "tet"). Returns: motif (string): motif type. """ return self._defect_types[i]
[docs] def get_defectsite_multiplicity(self, n): """ Returns the symmtric multiplicity of the defect site at the index. """ return self._defect_site_multiplicity[n]
[docs] def get_coordinating_elements_cns(self, i): """ Get element-specific coordination numbers of defect with index i. Returns: elem_cn (dict): dictionary storing the coordination numbers (int) with string representation of elements as keys. (i.e., {elem1 (string): cn1 (int), ...}). """ return self._defect_cns[i]
[docs] def get_op_value(self, i): """ Get order-parameter value of defect with index i. Returns: opval (float): OP value. """ return self._defect_opvals[i]
[docs] def make_supercells_with_defects(self, scaling_matrix): """ Generate a sequence of supercells in which each supercell contains a single interstitial, except for the first supercell in the sequence which is a copy of the defect-free input structure. Args: scaling_matrix (3x3 integer array): scaling matrix to transform the lattice vectors. Returns: scs ([Structure]): sequence of supercells. """ scs = [] sc = self._structure.copy() sc.make_supercell(scaling_matrix) scs.append(sc) for ids, defect_site in enumerate(self._defect_sites): sc_with_inter = sc.copy() sc_with_inter.append( defect_site.species_string, defect_site.frac_coords, coords_are_cartesian=False, validate_proximity=False, properties=None) if not sc_with_inter: raise RuntimeError( "could not generate supercell with" " interstitial {}".format( ids + 1)) scs.append(sc_with_inter.copy()) return scs
[docs]class TopographyAnalyzer: """ This is a generalized module to perform topological analyses of a crystal structure using Voronoi tessellations. It can be used for finding potential interstitial sites. Applications including using these sites for inserting additional atoms or for analyzing diffusion pathways. Note that you typically want to do some preliminary postprocessing after the initial construction. The initial construction will create a lot of points, especially for determining potential insertion sites. Some helper methods are available to perform aggregation and elimination of nodes. A typical use is something like:: a = TopographyAnalyzer(structure, ["O"], ["P"]) a.cluster_nodes() a.remove_collisions() """ def __init__(self, structure, framework_ions, cations, tol=0.0001, max_cell_range=1, check_volume=True, constrained_c_frac=0.5, thickness=0.5): """ Init. Args: structure (Structure): An initial structure. framework_ions ([str]): A list of ions to be considered as a framework. Typically, this would be all anion species. E.g., ["O", "S"]. cations ([str]): A list of ions to be considered as non-migrating cations. E.g., if you are looking at Li3PS4 as a Li conductor, Li is a mobile species. Your cations should be [ "P"]. The cations are used to exclude polyhedra from diffusion analysis since those polyhedra are already occupied. tol (float): A tolerance distance for the analysis, used to determine if something are actually periodic boundary images of each other. Default is usually fine. max_cell_range (int): This is the range of periodic images to construct the Voronoi tessellation. A value of 1 means that we include all points from (x +- 1, y +- 1, z+- 1) in the voronoi construction. This is because the Voronoi poly extends beyond the standard unit cell because of PBC. Typically, the default value of 1 works fine for most structures and is fast. But for really small unit cells with high symmetry, you may need to increase this to 2 or higher. check_volume (bool): Set False when ValueError always happen after tuning tolerance. constrained_c_frac (float): Constraint the region where users want to do Topology analysis the default value is 0.5, which is the fractional coordinate of the cell thickness (float): Along with constrained_c_frac, limit the thickness of the regions where we want to explore. Default is 0.5, which is mapping all the site of the unit cell. """ self.structure = structure self.framework_ions = set([get_el_sp(sp) for sp in framework_ions]) self.cations = set([get_el_sp(sp) for sp in cations]) # Let us first map all sites to the standard unit cell, i.e., # 0 ≤ coordinates < 1. # structure = Structure.from_sites(structure, to_unit_cell=True) # lattice = structure.lattice # We could constrain the region where we want to dope/explore by setting # the value of constrained_c_frac and thickness. The default mode is # mapping all sites to the standard unit cell s = structure.copy() constrained_sites = [] for i, site in enumerate(s): if site.frac_coords[2] >= constrained_c_frac - thickness and \ site.frac_coords[ 2] <= constrained_c_frac + thickness: constrained_sites.append(site) structure = Structure.from_sites(sites=constrained_sites) lattice = structure.lattice # Divide the sites into framework and non-framework sites. framework = [] non_framework = [] for site in structure: if self.framework_ions.intersection(site.species.keys()): framework.append(site) else: non_framework.append(site) # We construct a supercell series of coords. This is because the # Voronoi polyhedra can extend beyond the standard unit cell. Using a # range of -2, -1, 0, 1 should be fine. coords = [] cell_range = list(range(-max_cell_range, max_cell_range + 1)) for shift in itertools.product(cell_range, cell_range, cell_range): for site in framework: shifted = site.frac_coords + shift coords.append(lattice.get_cartesian_coords(shifted)) # Perform the voronoi tessellation. voro = Voronoi(coords) # Store a mapping of each voronoi node to a set of points. node_points_map = defaultdict(set) for pts, vs in voro.ridge_dict.items(): for v in vs: node_points_map[v].update(pts) logger.debug("%d total Voronoi vertices" % len(voro.vertices)) # Vnodes store all the valid voronoi polyhedra. Cation vnodes store # the voronoi polyhedra that are already occupied by existing cations. vnodes = [] cation_vnodes = [] def get_mapping(poly): """ Helper function to check if a vornoi poly is a periodic image of one of the existing voronoi polys. """ for v in vnodes: if v.is_image(poly, tol): return v return None # Filter all the voronoi polyhedra so that we only consider those # which are within the unit cell. for i, vertex in enumerate(voro.vertices): if i == 0: continue fcoord = lattice.get_fractional_coords(vertex) poly = VoronoiPolyhedron(lattice, fcoord, node_points_map[i], coords, i) if np.all([-tol <= c < 1 + tol for c in fcoord]): if len(vnodes) == 0: vnodes.append(poly) else: ref = get_mapping(poly) if ref is None: vnodes.append(poly) logger.debug("%d voronoi vertices in cell." % len(vnodes)) # Eliminate all voronoi nodes which are closest to existing cations. if len(cations) > 0: cation_coords = [ site.frac_coords for site in non_framework if self.cations.intersection(site.species.keys()) ] vertex_fcoords = [v.frac_coords for v in vnodes] dist_matrix = lattice.get_all_distances(cation_coords, vertex_fcoords) indices = \ np.where(dist_matrix == np.min(dist_matrix, axis=1)[:, None])[1] cation_vnodes = [v for i, v in enumerate(vnodes) if i in indices] vnodes = [v for i, v in enumerate(vnodes) if i not in indices] logger.debug("%d vertices in cell not with cation." % len(vnodes)) self.coords = coords self.vnodes = vnodes self.cation_vnodes = cation_vnodes self.framework = framework self.non_framework = non_framework if check_volume: self.check_volume()
[docs] def check_volume(self): """ Basic check for volume of all voronoi poly sum to unit cell volume Note that this does not apply after poly combination. """ vol = sum((v.volume for v in self.vnodes)) + sum( (v.volume for v in self.cation_vnodes)) if abs(vol - self.structure.volume) > 1e-8: raise ValueError( "Sum of voronoi volumes is not equal to original volume of " "structure! This may lead to inaccurate results. You need to " "tweak the tolerance and max_cell_range until you get a " "correct mapping.")
[docs] def cluster_nodes(self, tol=0.2): """ Cluster nodes that are too close together using a tol. Args: tol (float): A distance tolerance. PBC is taken into account. """ lattice = self.structure.lattice vfcoords = [v.frac_coords for v in self.vnodes] # Manually generate the distance matrix (which needs to take into # account PBC. dist_matrix = np.array(lattice.get_all_distances(vfcoords, vfcoords)) dist_matrix = (dist_matrix + dist_matrix.T) / 2 for i in range(len(dist_matrix)): dist_matrix[i, i] = 0 condensed_m = squareform(dist_matrix) z = linkage(condensed_m) cn = fcluster(z, tol, criterion="distance") merged_vnodes = [] for n in set(cn): poly_indices = set() frac_coords = [] for i, j in enumerate(np.where(cn == n)[0]): poly_indices.update(self.vnodes[j].polyhedron_indices) if i == 0: frac_coords.append(self.vnodes[j].frac_coords) else: fcoords = self.vnodes[j].frac_coords # We need the image to combine the frac_coords properly. d, image = lattice.get_distance_and_image(frac_coords[0], fcoords) frac_coords.append(fcoords + image) merged_vnodes.append( VoronoiPolyhedron(lattice, np.average(frac_coords, axis=0), poly_indices, self.coords)) self.vnodes = merged_vnodes logger.debug("%d vertices after combination." % len(self.vnodes))
[docs] def remove_collisions(self, min_dist=0.5): """ Remove vnodes that are too close to existing atoms in the structure Args: min_dist(float): The minimum distance that a vertex needs to be from existing atoms. """ vfcoords = [v.frac_coords for v in self.vnodes] sfcoords = self.structure.frac_coords dist_matrix = self.structure.lattice.get_all_distances(vfcoords, sfcoords) all_dist = np.min(dist_matrix, axis=1) new_vnodes = [] for i, v in enumerate(self.vnodes): if all_dist[i] > min_dist: new_vnodes.append(v) self.vnodes = new_vnodes
[docs] def get_structure_with_nodes(self): """ Get the modified structure with the voronoi nodes inserted. The species is set as a DummySpecie X. """ new_s = Structure.from_sites(self.structure) for v in self.vnodes: new_s.append("X", v.frac_coords) return new_s
[docs] def print_stats(self): """ Print stats such as the MSE dist. """ latt = self.structure.lattice def get_min_dist(fcoords): n = len(fcoords) dist = latt.get_all_distances(fcoords, fcoords) all_dist = [dist[i, j] for i in range(n) for j in range(i + 1, n)] return min(all_dist) voro = [s[1] for s in self.vertices] print("Min dist between voronoi vertices centers = %.4f" % get_min_dist( voro)) def get_non_framework_dist(fcoords): cations = [site.frac_coords for site in self.non_framework] dist_matrix = latt.get_all_distances(cations, fcoords) min_dist = np.min(dist_matrix, axis=1) if len(cations) != len(min_dist): raise Exception("Could not calculate distance to all cations") return np.linalg.norm(min_dist), min(min_dist), max(min_dist) print(len(self.non_framework)) print("MSE dist voro = %s" % str(get_non_framework_dist(voro)))
[docs] def write_topology(self, fname="Topo.cif"): """ Write topology to a file. :param fname: Filename """ new_s = Structure.from_sites(self.structure) for v in self.vnodes: new_s.append("Mg", v.frac_coords)
[docs] def analyze_symmetry(self, tol): """ :param tol: Tolerance for SpaceGroupAnalyzer :return: List """ s = Structure.from_sites(self.framework) site_to_vindex = {} for i, v in enumerate(self.vnodes): s.append("Li", v.frac_coords) site_to_vindex[s[-1]] = i print(len(s)) finder = SpacegroupAnalyzer(s, tol) print(finder.get_space_group_operations()) symm_structure = finder.get_symmetrized_structure() print(len(symm_structure.equivalent_sites)) return [[site_to_vindex[site] for site in sites] for sites in symm_structure.equivalent_sites if sites[0].specie.symbol == "Li"]
[docs] def vtk(self): """ Show VTK visualization. """ if StructureVis is None: raise NotImplementedError("vtk must be present to view.") lattice = self.structure.lattice vis = StructureVis() vis.set_structure(Structure.from_sites(self.structure)) for v in self.vnodes: vis.add_site(PeriodicSite("K", v.frac_coords, lattice)) vis.add_polyhedron( [PeriodicSite("S", c, lattice, coords_are_cartesian=True) for c in v.polyhedron_coords], PeriodicSite("Na", v.frac_coords, lattice), color="element", draw_edges=True, edges_color=(0, 0, 0))
[docs]class VoronoiPolyhedron: """ Convenience container for a voronoi point in PBC and its associated polyhedron. """ def __init__(self, lattice, frac_coords, polyhedron_indices, all_coords, name=None): """ :param lattice: :param frac_coords: :param polyhedron_indices: :param all_coords: :param name: """ self.lattice = lattice self.frac_coords = frac_coords self.polyhedron_indices = polyhedron_indices self.polyhedron_coords = np.array(all_coords)[list(polyhedron_indices), :] = name
[docs] def is_image(self, poly, tol): """ :param poly: VoronoiPolyhedron :param tol: Coordinate tolerance. :return: Whether a poly is an image of the current one. """ frac_diff = pbc_diff(poly.frac_coords, self.frac_coords) if not np.allclose(frac_diff, [0, 0, 0], atol=tol): return False to_frac = self.lattice.get_fractional_coords for c1 in self.polyhedron_coords: found = False for c2 in poly.polyhedron_coords: d = pbc_diff(to_frac(c1), to_frac(c2)) if not np.allclose(d, [0, 0, 0], atol=tol): found = True break if not found: return False return True
@property def coordination(self): """ :return: Coordination number """ return len(self.polyhedron_indices) @property def volume(self): """ :return: Volume """ return calculate_vol(self.polyhedron_coords) def __str__(self): return "Voronoi polyhedron %s" %
[docs]class ChargeDensityAnalyzer: """ Analyzer to find potential interstitial sites based on charge density. The `total` charge density is used. """ def __init__(self, chgcar): """ Initialization. Args: chgcar (pmg.Chgcar): input Chgcar object. """ self.chgcar = chgcar self.structure = chgcar.structure self.extrema_coords = [] # list of frac_coords of local extrema self.extrema_type = None # "local maxima" or "local minima" self._extrema_df = None # extrema frac_coords - chg density table self._charge_distribution_df = None # frac_coords - chg density table
[docs] @classmethod def from_file(cls, chgcar_filename): """ Init from a CHGCAR. :param chgcar_filename: :return: """ chgcar = Chgcar.from_file(chgcar_filename) return cls(chgcar=chgcar)
@property def charge_distribution_df(self): """ :return: Charge distribution. """ if self._charge_distribution_df is None: return self._get_charge_distribution_df() else: return self._charge_distribution_df @property def extrema_df(self): """ :return: The extrema in charge density. """ if self.extrema_type is None: logger.warning( "Please run ChargeDensityAnalyzer.get_local_extrema first!") return self._extrema_df def _get_charge_distribution_df(self): """ Return a complete table of fractional coordinates - charge density. """ # Fraction coordinates and corresponding indices axis_grid = np.array([np.array(self.chgcar.get_axis_grid(i)) /[i] for i in range(3)]) axis_index = np.array([range(len(axis_grid[i])) for i in range(3)]) data = {} for index in itertools.product(*axis_index): a, b, c = index f_coords = (axis_grid[0][a], axis_grid[1][b], axis_grid[2][c]) data[f_coords] =["total"][a][b][c] # Fraction coordinates - charge density table df = pd.Series(data).reset_index() df.columns = ['a', 'b', 'c', 'Charge Density'] self._charge_distribution_df = df return df def _update_extrema(self, f_coords, extrema_type, threshold_frac=None, threshold_abs=None): """Update _extrema_df, extrema_type and extrema_coords""" if threshold_frac is not None: if threshold_abs is not None: logger.warning( # Exit if both filter are set "Filter can be either threshold_frac or threshold_abs!") return if threshold_frac > 1 or threshold_frac < 0: raise Exception("threshold_frac range is [0, 1]!") # Return empty result if coords list is empty if len(f_coords) == 0: df = pd.DataFrame({}, columns=['A', 'B', 'C', "Chgcar"]) self._extrema_df = df self.extrema_coords = []"Find {} {}.".format(len(df), extrema_type)) return data = {} unit = 1 / np.array(self.chgcar.dim) # pixel along a, b, c for fc in f_coords: a, b, c = tuple(map(int, fc / unit)) data[tuple(fc)] =["total"][a][b][c] df = pd.Series(data).reset_index() df.columns = ['a', 'b', 'c', 'Charge Density'] ascending = (extrema_type == "local minima") if threshold_abs is None: threshold_frac = threshold_frac \ if threshold_frac is not None else 1.0 num_extrema = int(threshold_frac * len(f_coords)) df = df.sort_values(by="Charge Density", ascending=ascending)[ 0:num_extrema] df.reset_index(drop=True, inplace=True) # reset major index else: # threshold_abs is set df = df.sort_values(by="Charge Density", ascending=ascending) df = df[df["Charge Density"] <= threshold_abs] if ascending \ else df[df["Charge Density"] >= threshold_abs] extrema_coords = [] for row in df.iterrows(): fc = np.array(row[1]["a":"c"]) extrema_coords.append(fc) self._extrema_df = df self.extrema_type = extrema_type self.extrema_coords = extrema_coords"Find {} {}.".format(len(df), extrema_type))
[docs] @requires(peak_local_max_found, "get_local_extrema requires skimage.feature.peak_local_max module" " to be installed. Please confirm your skimage installation.") def get_local_extrema(self, find_min=True, threshold_frac=None, threshold_abs=None): """ Get all local extrema fractional coordinates in charge density, searching for local minimum by default. Note that sites are NOT grouped symmetrically. Args: find_min (bool): True to find local minimum else maximum, otherwise find local maximum. threshold_frac (float): optional fraction of extrema shown, which returns `threshold_frac * tot_num_extrema` extrema fractional coordinates based on highest/lowest intensity. E.g. set 0.2 to show the extrema with 20% highest or lowest intensity. Value range: 0 <= threshold_frac <= 1 Note that threshold_abs and threshold_frac should not set in the same time. threshold_abs (float): optional filter. When searching for local minima, intensity <= threshold_abs returns; when searching for local maxima, intensity >= threshold_abs returns. Note that threshold_abs and threshold_frac should not set in the same time. Returns: extrema_coords (list): list of fractional coordinates corresponding to local extrema. """ sign, extrema_type = 1, "local maxima" if find_min: sign, extrema_type = -1, "local minima" # Make 3x3x3 supercell # This is a trick to resolve the periodical boundary issue. total_chg = sign *["total"] total_chg = np.tile(total_chg, reps=(3, 3, 3)) coordinates = peak_local_max(total_chg, min_distance=1) # Remove duplicated sites introduced by supercell. f_coords = [coord / total_chg.shape * 3 for coord in coordinates] f_coords = [f - 1 for f in f_coords if all(np.array(f) < 2) and all(np.array(f) >= 1)] # Update information self._update_extrema(f_coords, extrema_type, threshold_frac=threshold_frac, threshold_abs=threshold_abs) return self.extrema_coords
[docs] def cluster_nodes(self, tol=0.2): """ Cluster nodes that are too close together using a tol. Args: tol (float): A distance tolerance. PBC is taken into account. """ lattice = self.structure.lattice vf_coords = self.extrema_coords if len(vf_coords) == 0: if self.extrema_type is None: logger.warning( "Please run ChargeDensityAnalyzer.get_local_extrema first!") return new_f_coords = [] self._update_extrema(new_f_coords, self.extrema_type) return new_f_coords # Manually generate the distance matrix (which needs to take into # account PBC. dist_matrix = np.array(lattice.get_all_distances(vf_coords, vf_coords)) dist_matrix = (dist_matrix + dist_matrix.T) / 2 for i in range(len(dist_matrix)): dist_matrix[i, i] = 0 condensed_m = squareform(dist_matrix) z = linkage(condensed_m) cn = fcluster(z, tol, criterion="distance") merged_fcoords = [] for n in set(cn): frac_coords = [] for i, j in enumerate(np.where(cn == n)[0]): if i == 0: frac_coords.append(self.extrema_coords[j]) else: f_coords = self.extrema_coords[j] # We need the image to combine the frac_coords properly. d, image = lattice.get_distance_and_image(frac_coords[0], f_coords) frac_coords.append(f_coords + image) merged_fcoords.append(np.average(frac_coords, axis=0)) merged_fcoords = [f - np.floor(f) for f in merged_fcoords] merged_fcoords = [f * (np.abs(f - 1) > 1E-15) for f in merged_fcoords] # the second line for fringe cases like # np.array([ 5.0000000e-01 -4.4408921e-17 5.0000000e-01]) # where the shift to [0,1) does not work due to float precision self._update_extrema(merged_fcoords, extrema_type=self.extrema_type) logger.debug( "{} vertices after combination.".format(len(self.extrema_coords)))
[docs] def remove_collisions(self, min_dist=0.5): """ Remove predicted sites that are too close to existing atoms in the structure. Args: min_dist (float): The minimum distance (in Angstrom) that a predicted site needs to be from existing atoms. A min_dist with value <= 0 returns all sites without distance checking. """ s_f_coords = self.structure.frac_coords f_coords = self.extrema_coords if len(f_coords) == 0: if self.extrema_type is None: logger.warning( "Please run ChargeDensityAnalyzer.get_local_extrema first!") return new_f_coords = [] self._update_extrema(new_f_coords, self.extrema_type) return new_f_coords dist_matrix = self.structure.lattice.get_all_distances(f_coords, s_f_coords) all_dist = np.min(dist_matrix, axis=1) new_f_coords = [] for i, f in enumerate(f_coords): if all_dist[i] > min_dist: new_f_coords.append(f) self._update_extrema(new_f_coords, self.extrema_type) return new_f_coords
[docs] def get_structure_with_nodes(self, find_min=True, min_dist=0.5, tol=0.2, threshold_frac=None, threshold_abs=None): """ Get the modified structure with the possible interstitial sites added. The species is set as a DummySpecie X. Args: find_min (bool): True to find local minimum else maximum, otherwise find local maximum. min_dist (float): The minimum distance (in Angstrom) that a predicted site needs to be from existing atoms. A min_dist with value <= 0 returns all sites without distance checking. tol (float): A distance tolerance of nodes clustering that sites too closed to other predicted sites will be merged. PBC is taken into account. threshold_frac (float): optional fraction of extrema, which returns `threshold_frac * tot_num_extrema` extrema fractional coordinates based on highest/lowest intensity. E.g. set 0.2 to insert DummySpecie atom at the extrema with 20% highest or lowest intensity. Value range: 0 <= threshold_frac <= 1 Note that threshold_abs and threshold_frac should not set in the same time. threshold_abs (float): optional filter. When searching for local minima, intensity <= threshold_abs returns; when searching for local maxima, intensity >= threshold_abs returns. Note that threshold_abs and threshold_frac should not set in the same time. Returns: structure (Structure) """ structure = self.structure.copy() self.get_local_extrema(find_min=find_min, threshold_frac=threshold_frac, threshold_abs=threshold_abs) self.remove_collisions(min_dist) self.cluster_nodes(tol=tol) for fc in self.extrema_coords: structure.append("X", fc) return structure
[docs] def sort_sites_by_integrated_chg(self, r=0.4): """ Get the average charge density around each local minima in the charge density and store the result in _extrema_df Args: r (float): radius of sphere around each site to evaluate the average """ if self.extrema_type is None: self.get_local_extrema() int_den = [] for isite in self.extrema_coords: mask = self._dist_mat(isite) < r vol_sphere = self.chgcar.structure.volume * (mask.sum() / self.chgcar.ngridpts) chg_in_sphere = np.sum(['total'] * mask) / mask.size / vol_sphere int_den.append(chg_in_sphere) self._extrema_df['avg_charge_den'] = int_den self._extrema_df.sort_values(by=['avg_charge_den'], inplace=True) self._extrema_df.reset_index(drop=True, inplace=True)
def _dist_mat(self, pos_frac): # return a matrix that contains the distances aa = np.linspace(0, 1, len(self.chgcar.get_axis_grid(0)), endpoint=False) bb = np.linspace(0, 1, len(self.chgcar.get_axis_grid(1)), endpoint=False) cc = np.linspace(0, 1, len(self.chgcar.get_axis_grid(2)), endpoint=False) AA, BB, CC = np.meshgrid(aa, bb, cc, indexing='ij') dist_from_pos = self.chgcar.structure.lattice.get_all_distances( fcoords1=np.vstack([AA.flatten(), BB.flatten(), CC.flatten()]).T, fcoords2=pos_frac) return dist_from_pos.reshape(AA.shape)
[docs]def calculate_vol(coords): """ Calculate volume given a set of coords. :param coords: List of coords. :return: Volume """ if len(coords) == 4: coords_affine = np.ones((4, 4)) coords_affine[:, 0:3] = np.array(coords) return abs(np.linalg.det(coords_affine)) / 6 else: simplices = get_facets(coords, joggle=True) center = np.average(coords, axis=0) vol = 0 for s in simplices: c = list(coords[i] for i in s) c.append(center) vol += calculate_vol(c) return vol
[docs]def converge(f, step, tol, max_h): """ simple newton iteration based convergence function """ g = f(0) dx = 10000 h = step while (dx > tol): g2 = f(h) dx = abs(g - g2) g = g2 h += step if h > max_h: raise Exception("Did not converge before {}".format(h)) return g
[docs]def tune_for_gamma(lattice, epsilon): """ This tunes the gamma parameter for Kumagai anisotropic Ewald calculation. Method is to find a gamma parameter which generates a similar number of reciprocal and real lattice vectors, given the suggested cut off radii by Kumagai and Oba """ logger.debug("Converging for ewald parameter...") prec = 25 # a reasonable precision to tune gamma for gamma = (2 * np.average( ** (-1 / 2.) recip_set, _, real_set, _ = generate_R_and_G_vecs(gamma, prec, lattice, epsilon) recip_set = recip_set[0] real_set = real_set[0] logger.debug("First approach with gamma ={}\nProduced {} real vecs and {} recip " "vecs.".format(gamma, len(real_set), len(recip_set))) while float(len(real_set)) / len(recip_set) > 1.05 or \ float(len(recip_set)) / len(real_set) > 1.05: gamma *= (float(len(real_set)) / float(len(recip_set))) ** 0.17 logger.debug("\tNot converged...Try modifying gamma to {}.".format(gamma)) recip_set, _, real_set, _ = generate_R_and_G_vecs(gamma, prec, lattice, epsilon) recip_set = recip_set[0] real_set = real_set[0] logger.debug("Now have {} real vecs and {} recip vecs.".format(len(real_set), len(recip_set))) logger.debug("Converged with gamma = {}".format(gamma)) return gamma
[docs]def generate_R_and_G_vecs(gamma, prec_set, lattice, epsilon): """ This returns a set of real and reciprocal lattice vectors (and real/recip summation values) based on a list of precision values (prec_set) gamma (float): Ewald parameter prec_set (list or number): for prec values to consider (20, 25, 30 are sensible numbers) lattice: Lattice object of supercell in question """ if type(prec_set) != list: prec_set = [prec_set] [a1, a2, a3] = lattice.matrix # Angstrom volume = lattice.volume [b1, b2, b3] = lattice.reciprocal_lattice.matrix # 1/ Angstrom invepsilon = np.linalg.inv(epsilon) rd_epsilon = np.sqrt(np.linalg.det(epsilon)) # generate reciprocal vector set (for each prec_set) recip_set = [[] for prec in prec_set] recip_summation_values = [0. for prec in prec_set] recip_cut_set = [(2 * gamma * prec) for prec in prec_set] i_max = int(math.ceil(max(recip_cut_set) / np.linalg.norm(b1))) j_max = int(math.ceil(max(recip_cut_set) / np.linalg.norm(b2))) k_max = int(math.ceil(max(recip_cut_set) / np.linalg.norm(b3))) for i in np.arange(-i_max, i_max + 1): for j in np.arange(-j_max, j_max + 1): for k in np.arange(-k_max, k_max + 1): if not i and not j and not k: continue gvec = i * b1 + j * b2 + k * b3 normgvec = np.linalg.norm(gvec) for recip_cut_ind, recip_cut in enumerate(recip_cut_set): if normgvec <= recip_cut: recip_set[recip_cut_ind].append(gvec) Gdotdiel =,, gvec)) summand = math.exp(-Gdotdiel / (4 * (gamma ** 2))) / Gdotdiel recip_summation_values[recip_cut_ind] += summand recip_summation_values = np.array(recip_summation_values) recip_summation_values /= volume # generate real vector set (for each prec_set) real_set = [[] for prec in prec_set] real_summation_values = [0. for prec in prec_set] real_cut_set = [(prec / gamma) for prec in prec_set] i_max = int(math.ceil(max(real_cut_set) / np.linalg.norm(a1))) j_max = int(math.ceil(max(real_cut_set) / np.linalg.norm(a2))) k_max = int(math.ceil(max(real_cut_set) / np.linalg.norm(a3))) for i in np.arange(-i_max, i_max + 1): for j in np.arange(-j_max, j_max + 1): for k in np.arange(-k_max, k_max + 1): rvec = i * a1 + j * a2 + k * a3 normrvec = np.linalg.norm(rvec) for real_cut_ind, real_cut in enumerate(real_cut_set): if normrvec <= real_cut: real_set[real_cut_ind].append(rvec) if normrvec > 1e-8: sqrt_loc_res = np.sqrt(,, rvec))) nmr = math.erfc(gamma * sqrt_loc_res) real_summation_values[real_cut_ind] += nmr / sqrt_loc_res real_summation_values = np.array(real_summation_values) real_summation_values /= (4 * np.pi * rd_epsilon) return recip_set, recip_summation_values, real_set, real_summation_values