def resonance_dominant_bond_orders(rgr):
""" resonance-dominant bond orders, by bond
"""
bnd_keys = list(_bond_keys(rgr))
bnd_ords_by_res = [
dict_.values_by_key(_bond_orders(dom_rgr), bnd_keys)
for dom_rgr in dominant_resonances(rgr)]
bnd_ords_lst = list(map(frozenset, zip(*bnd_ords_by_res)))
bnd_dom_res_ords_dct = dict(zip(bnd_keys, bnd_ords_lst))
return bnd_dom_res_ords_dct
def _bond_capacities(rgr):
""" the number of electron pairs available for further pi-bonding, by bond
"""
atm_unsat_vlc_dct = _atom_unsaturated_valences(rgr)
def _pi_capacities(bnd_key):
return min(map(atm_unsat_vlc_dct.__getitem__, bnd_key))
bnd_keys = list(_bond_keys(rgr))
bnd_caps = tuple(map(_pi_capacities, bnd_keys))
bnd_cap_dct = dict(zip(bnd_keys, bnd_caps))
return bnd_cap_dct
def resonance_avg_bond_orders(rgr):
""" resonance-dominant bond orders, by bond
"""
bnd_keys = list(_bond_keys(rgr))
bnd_ords_by_res = [
dict_.values_by_key(_bond_orders(dom_rgr), bnd_keys)
for dom_rgr in dominant_resonances(rgr)]
nres = len(bnd_ords_by_res)
bnd_ords_lst = zip(*bnd_ords_by_res)
avg_bnd_ord_lst = [sum(bnd_ords)/nres for bnd_ords in bnd_ords_lst]
avg_bnd_ord_dct = dict(zip(bnd_keys, avg_bnd_ord_lst))
return avg_bnd_ord_dct
def _add_pi_bonds(rgr, bnd_ord_inc_dct):
""" add pi bonds to this graph
"""
bnd_keys = _bond_keys(rgr)
assert set(bnd_ord_inc_dct.keys()) <= bnd_keys
bnd_keys = list(bnd_keys)
bnd_ords = dict_.values_by_key(_bond_orders(rgr), bnd_keys)
bnd_ord_incs = dict_.values_by_key(bnd_ord_inc_dct, bnd_keys, fill_val=0)
new_bnd_ords = numpy.add(bnd_ords, bnd_ord_incs)
bnd_ord_dct = dict(zip(bnd_keys, new_bnd_ords))
rgr = _set_bond_orders(rgr, bnd_ord_dct)
return rgr
def subresonances(rgr):
""" this connected graph and its lower-spin (more pi-bonded) resonances
"""
def _inc_range(bnd_cap):
return tuple(range(0, bnd_cap+1))
add_pi_bonds_ = functools.partial(_add_pi_bonds, rgr)
atm_keys = list(_atom_keys(rgr))
bnd_keys = list(_bond_keys(rgr))
atm_unsat_vlcs = dict_.values_by_key(
_atom_unsaturated_valences(rgr), atm_keys)
atm_bnd_keys_lst = dict_.values_by_key(_atom_bond_keys(rgr), atm_keys)
bnd_caps = dict_.values_by_key(_bond_capacities(rgr), bnd_keys)
bnd_ord_dct = _bond_orders(rgr)
def _is_valid(bnd_ord_inc_dct):
# check if pi bonds exceed unsaturated valences
def __tally(atm_bnd_keys):
return sum(dict_.values_by_key(bnd_ord_inc_dct, atm_bnd_keys))
atm_unsat_vlc_decs = tuple(map(__tally, atm_bnd_keys_lst))
enough_elecs = numpy.all(
numpy.less_equal(atm_unsat_vlc_decs, atm_unsat_vlcs))
# check if all bond orders are less than 4 (should only affect C2)
bnd_inc_keys = bnd_ord_inc_dct.keys()
bnd_incs = dict_.values_by_key(bnd_ord_inc_dct, bnd_inc_keys)
bnd_ords = dict_.values_by_key(bnd_ord_dct, bnd_inc_keys)
new_bnd_ords = numpy.add(bnd_ords, bnd_incs)
not_too_many = numpy.all(numpy.less(new_bnd_ords, 4))
return enough_elecs and not_too_many
def _bond_value_dictionary(bnd_vals):
return dict(zip(bnd_keys, bnd_vals))
bnd_ord_incs_itr = itertools.product(*map(_inc_range, bnd_caps))
bnd_ord_inc_dct_itr = map(_bond_value_dictionary, bnd_ord_incs_itr)
bnd_ord_inc_dct_itr = filter(_is_valid, bnd_ord_inc_dct_itr)
rgrs = tuple(sorted(map(add_pi_bonds_, bnd_ord_inc_dct_itr), key=_frozen))
return rgrs