Multi-Halogen Analysis (Advanced)

Note

This is an advanced topic. For standard PFAS / fluorine-only work, use Quickstart which focuses on the PFASGroups import. This page describes how to extend detection to Cl, Br and I groups.

PFASGroups focuses on fluorinated substances (halogens='F' by default). The same codebase can also detect chlorinated, brominated and iodinated structural groups when you pass halogens explicitly, or by importing from HalogenGroups which sets all four halogens as the default.

# Option A — explicit halogens argument with PFASGroups (recommended)
from PFASGroups import parse_smiles
results = parse_smiles(["ClC(Cl)(Cl)Cl", "BrCCBr"], halogens=['F','Cl','Br','I'])

# Option B — import HalogenGroups, all-halogens is the default
from HalogenGroups import parse_smiles
results = parse_smiles(["ClC(Cl)(Cl)Cl", "BrCCBr"])

Import	Default `halogens`	Typical use
`HalogenGroups`	`['F', 'Cl', 'Br', 'I']`	Broad multi-halogen screening
`PFASGroups`	`'F'`	PFAS / fluorine-focused analysis

Either import can be forced to any halogen set by passing the halogens argument explicitly — the results will be identical.

Quick Comparison

from HalogenGroups import parse_smiles as hal_parse
from PFASGroups   import parse_smiles as pfas_parse

smiles = ["ClC(Cl)(Cl)C(Cl)(Cl)Cl",   # perchlorinated
          "BrC(Br)(Br)CBr",             # brominated
          "FC(F)(F)C(F)(F)C(=O)O"]      # PFBA

# HalogenGroups: all halogens included by default
results_all = hal_parse(smiles)

# PFASGroups: fluorine only by default → Cl/Br compounds show 0 matches
results_f   = pfas_parse(smiles)

# Equivalent — pass halogens explicitly to PFASGroups
results_eq  = pfas_parse(smiles, halogens=['F', 'Cl', 'Br', 'I'])

Warning

The default embedding width depends on which module you import from.

parse_smiles from HalogenGroups returns a HalogenGroups.PFASEmbeddingSet subclass. Calling results.to_array() on that object without an explicit halogens argument produces a 464-column array (116 groups × 4 halogens), not the standard 116-column fluorine-only one. To guarantee fluorine-only output, always pass halogens='F' explicitly:

arr = results.to_array(halogens='F')   # always 116 columns

This applies to compute_config, _txp_fingerprint, and any similar helpers in notebooks or scripts that pass **kwargs to to_array() — the halogens key must be present in those kwargs.

Functions with Altered Defaults

The following functions have their halogens default overridden to ['F', 'Cl', 'Br', 'I'] when imported from HalogenGroups:

Function	Default change
`parse_smiles()`	`halogens=['F','Cl','Br','I']`
`parse_mols()`	`halogens=['F','Cl','Br','I']`
`generate_fingerprint()`	`halogens=['F','Cl','Br','I']`
`PFASEmbeddingSet.to_array()`	`halogens=['F','Cl','Br','I']`, `saturation='per'`

All other functions (parse_mol, parse_groups_in_mol, get_HalogenGroups, prioritise_molecules, … ) are re-exported unchanged.

Parsing Multi-Halogen Molecules

from HalogenGroups import parse_smiles

smiles = [
    "FC(F)(F)C(F)(F)C(=O)O",           # PFBA — fluorinated
    "ClC(Cl)(Cl)C(Cl)(Cl)C(=O)O",      # perchlorinated carboxylic acid
    "BrC(Br)(Br)CBr",                   # brominated
]

# All four halogens considered — no extra argument needed
results = parse_smiles(smiles)

for mol in results:
    print(mol.smiles)
    for match in mol.matches:
        comps = match.components
        print(f"  {match.group_name}: {len(comps)} component(s)")

To restrict to a subset of halogens with HalogenGroups:

# Override the default to fluorine + chlorine only
results = parse_smiles(smiles, halogens=['F', 'Cl'])

Multi-Halogen Fingerprints

generate_fingerprint() with multiple halogens stacks per-halogen vectors horizontally. With 116 groups and 4 halogens the resulting fingerprint has 116 × 4 = 464 columns. Group names are suffixed [F], [Cl], [Br], [I].

from HalogenGroups import generate_fingerprint

smiles = ["FC(F)(F)C(F)(F)C(=O)O",
          "ClC(Cl)(Cl)C(Cl)(Cl)C(=O)O"]

# Default: all 4 halogens, per-saturation → shape (2, 464)
fps, info = generate_fingerprint(smiles)
print(fps.shape)           # (2, 464)
print(info['halogens'])    # ['F', 'Cl', 'Br', 'I']
print(info['group_names'][:3])  # ['... [F]', '... [F]', '... [F]']

Via PFASEmbeddingSet

from HalogenGroups import parse_smiles

results = parse_smiles(smiles)

# to_array() defaults to all halogens in HalogenGroups
arr_all  = results.to_array()                                   # shape (n, 464)
arr_f    = results.to_array(halogens='F')                      # shape (n, 116)
arr_fc   = results.to_array(halogens=['F', 'Cl'])              # shape (n, 232)
arr_oecd = results.to_array(
    group_selection='oecd', halogens=['F', 'Cl', 'Br', 'I'])   # shape (n, 112)

# Best preset (binary + effective_graph_resistance) with F only
arr_best = results.to_array(preset='best', halogens='F')       # shape (n, 232)

# Explicit component_metrics — count mode + graph metric with all halogens
arr_cm = results.to_array(
    component_metrics=['binary', 'effective_graph_resistance'],
    halogens=['F', 'Cl', 'Br', 'I'])  # shape (n, 928)  — 2 × 116 × 4

Each entry in component_metrics adds one block of n_groups × n_halogens columns. The column naming follows the pattern "GroupName [halogen] [metric]" (e.g. "Perfluoroalkyl [F] [binary]", "Perfluoroalkyl [F] [effective_graph_resistance]").

Combining with Saturation Filters

The saturation parameter ('per', 'poly', or None) applies to all halogens simultaneously and controls which component SMARTS are used for groups that have halogenated-chain components (OECD groups 1–28).

from HalogenGroups import parse_smiles

# Perhalogenated components only (default when using HalogenGroups fingerprinting)
r_per  = parse_smiles(smiles, saturation='per')

# Polyhalogenated components only
r_poly = parse_smiles(smiles, saturation='poly')

# All components (per + poly)
r_all  = parse_smiles(smiles, saturation=None)

CLI with Multiple Halogens

The CLI always requires an explicit --halogens flag:

# All four halogens
halogengroups parse --halogens F Cl Br I "ClC(Cl)(Cl)C(Cl)(Cl)C(=O)O"

# Per-saturation, F + Cl, OECD groups
halogengroups parse --halogens F Cl --saturation per "FC(F)(F)C(F)(F)C(=O)O"

# Stacked fingerprint with F + Cl
halogengroups fingerprint --halogens F Cl "FC(F)(F)C(F)(F)C(=O)O"

See Command-Line Interface for the full CLI reference.

Implementation Details

HalogenGroups/__init__.py uses functools.wraps()-compatible wrappers that inject halogens=['F', 'Cl', 'Br', 'I'] as a default keyword argument. Because Python keyword defaults can always be overridden at call time, every explicit halogens=... argument takes precedence.

The PFASEmbeddingSet subclass in HalogenGroups overrides only to_array(); all other methods (show(), summary(), to_sql(), etc.) are inherited unchanged from PFASGroups.PFASEmbeddings.PFASEmbeddingSet.

When to Use Which Import

Use HalogenGroups when:

Your compounds include Cl-, Br- or I-containing structures
You want to compare fluorination vs. chlorination patterns side by side
You are building a generic halogenated-substance screening workflow

Use PFASGroups (halogens='F') when:

You are working exclusively with PFAS (fluorine-only)
You need strict compatibility with published PFAS fingerprint benchmarks
You want smaller fingerprints (116-column vs. 464-column)
You mix fluorine-only and multi-halogen calls in the same script