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KEHANGconnie
KEHANG
authored and
connie
committed
Reduced the unnecessary calls to calculateSymmetryNumber when calculating radical thermo.
calculateSymmetryNumber for saturated structure was called too frequently when calculating entropy of radical.
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‎rmgpy/data/thermo.py

+79-59
Original file line numberDiff line numberDiff line change
@@ -821,9 +821,6 @@ def estimateRadicalThermoViaHBI(self, molecule, stableThermoEstimator ):
821821
return None
822822
assert thermoData is not None, "Thermo data of saturated {0} of molecule {1} is None!".format(saturatedStruct, molecule)
823823

824-
# Undo symmetry number correction for saturated structure
825-
saturatedStruct.calculateSymmetryNumber()
826-
thermoData.S298.value_si += constants.R * math.log(saturatedStruct.symmetryNumber)
827824
# Correct entropy for symmetry number of radical structure
828825
molecule.calculateSymmetryNumber()
829826
thermoData.S298.value_si -= constants.R * math.log(molecule.symmetryNumber)
@@ -878,71 +875,94 @@ def estimateThermoViaGroupAdditivity(self, molecule):
878875
)
879876

880877
if molecule.getRadicalCount() > 0: # radical species
881-
return self.estimateRadicalThermoViaHBI(molecule, self.estimateThermoViaGroupAdditivity )
878+
return self.estimateRadicalThermoViaHBI(molecule, self.estimateThermoViaGroupAdditivityForSaturatedStruct)
882879

883880
else: # non-radical species
884-
cyclic = molecule.isCyclic()
885-
# Generate estimate of thermodynamics
886-
for atom in molecule.atoms:
887-
# Iterate over heavy (non-hydrogen) atoms
888-
if atom.isNonHydrogen():
889-
# Get initial thermo estimate from main group database
890-
try:
891-
self.__addGroupThermoData(thermoData, self.groups['group'], molecule, {'*':atom})
892-
except KeyError:
893-
logging.error("Couldn't find in main thermo database:")
894-
logging.error(molecule)
895-
logging.error(molecule.toAdjacencyList())
896-
raise
897-
# Correct for gauche and 1,5- interactions
898-
if not cyclic:
899-
try:
900-
self.__addGroupThermoData(thermoData, self.groups['gauche'], molecule, {'*':atom})
901-
except KeyError: pass
902-
try:
903-
self.__addGroupThermoData(thermoData, self.groups['int15'], molecule, {'*':atom})
904-
except KeyError: pass
905-
try:
906-
self.__addGroupThermoData(thermoData, self.groups['other'], molecule, {'*':atom})
907-
except KeyError: pass
908-
909-
# Do ring corrections separately because we only want to match
910-
# each ring one time
911-
912-
if cyclic:
913-
if molecule.getAllPolycyclicVertices():
914-
# If the molecule has fused ring atoms, this implies that we are dealing
915-
# with a polycyclic ring system, for which separate ring strain corrections may not
916-
# be adequate. Therefore, we search the polycyclic thermo group corrections
917-
# instead of adding single ring strain corrections within the molecule.
918-
# For now, assume only one polycyclic RSC can be found per molecule
919-
try:
920-
self.__addGroupThermoData(thermoData, self.groups['polycyclic'], molecule, {})
921-
except:
922-
logging.error("Couldn't find in polycyclic ring database:")
923-
logging.error(molecule)
924-
logging.error(molecule.toAdjacencyList())
925-
raise
926-
else:
927-
rings = molecule.getSmallestSetOfSmallestRings()
928-
for ring in rings:
929-
# Make a temporary structure containing only the atoms in the ring
930-
# NB. if any of the ring corrections depend on ligands not in the ring, they will not be found!
931-
try:
932-
self.__addGroupThermoData(thermoData, self.groups['ring'], molecule, {})
933-
except KeyError:
934-
logging.error("Couldn't find in ring database:")
935-
logging.error(ring)
936-
logging.error(ring.toAdjacencyList())
937-
raise
938-
881+
thermoData = self.estimateThermoViaGroupAdditivityForSaturatedStruct(molecule)
939882

940883
# Correct entropy for symmetry number
941884
molecule.calculateSymmetryNumber()
942885
thermoData.S298.value_si -= constants.R * math.log(molecule.symmetryNumber)
943886

944887
return thermoData
945888

889+
def estimateThermoViaGroupAdditivityForSaturatedStruct(self, molecule):
890+
"""
891+
Return the set of thermodynamic parameters corresponding to a given
892+
:class:`Molecule` object `molecule` by estimation using the group
893+
additivity values. If no group additivity values are loaded, a
894+
:class:`DatabaseError` is raised.
895+
"""
896+
# For thermo estimation we need the atoms to already be sorted because we
897+
# iterate over them; if the order changes during the iteration then we
898+
# will probably not visit the right atoms, and so will get the thermo wrong
899+
molecule.sortVertices()
900+
901+
# Create the ThermoData object
902+
thermoData = ThermoData(
903+
Tdata = ([300,400,500,600,800,1000,1500],"K"),
904+
Cpdata = ([0.0,0.0,0.0,0.0,0.0,0.0,0.0],"J/(mol*K)"),
905+
H298 = (0.0,"kJ/mol"),
906+
S298 = (0.0,"J/(mol*K)"),
907+
)
908+
909+
cyclic = molecule.isCyclic()
910+
# Generate estimate of thermodynamics
911+
for atom in molecule.atoms:
912+
# Iterate over heavy (non-hydrogen) atoms
913+
if atom.isNonHydrogen():
914+
# Get initial thermo estimate from main group database
915+
try:
916+
self.__addGroupThermoData(thermoData, self.groups['group'], molecule, {'*':atom})
917+
except KeyError:
918+
logging.error("Couldn't find in main thermo database:")
919+
logging.error(molecule)
920+
logging.error(molecule.toAdjacencyList())
921+
raise
922+
# Correct for gauche and 1,5- interactions
923+
if not cyclic:
924+
try:
925+
self.__addGroupThermoData(thermoData, self.groups['gauche'], molecule, {'*':atom})
926+
except KeyError: pass
927+
try:
928+
self.__addGroupThermoData(thermoData, self.groups['int15'], molecule, {'*':atom})
929+
except KeyError: pass
930+
try:
931+
self.__addGroupThermoData(thermoData, self.groups['other'], molecule, {'*':atom})
932+
except KeyError: pass
933+
934+
# Do ring corrections separately because we only want to match
935+
# each ring one time
936+
937+
if cyclic:
938+
if molecule.getAllPolycyclicVertices():
939+
# If the molecule has fused ring atoms, this implies that we are dealing
940+
# with a polycyclic ring system, for which separate ring strain corrections may not
941+
# be adequate. Therefore, we search the polycyclic thermo group corrections
942+
# instead of adding single ring strain corrections within the molecule.
943+
# For now, assume only one polycyclic RSC can be found per molecule
944+
try:
945+
self.__addGroupThermoData(thermoData, self.groups['polycyclic'], molecule, {})
946+
except:
947+
logging.error("Couldn't find in polycyclic ring database:")
948+
logging.error(molecule)
949+
logging.error(molecule.toAdjacencyList())
950+
raise
951+
else:
952+
rings = molecule.getSmallestSetOfSmallestRings()
953+
for ring in rings:
954+
# Make a temporary structure containing only the atoms in the ring
955+
# NB. if any of the ring corrections depend on ligands not in the ring, they will not be found!
956+
try:
957+
self.__addGroupThermoData(thermoData, self.groups['ring'], molecule, {})
958+
except KeyError:
959+
logging.error("Couldn't find in ring database:")
960+
logging.error(ring)
961+
logging.error(ring.toAdjacencyList())
962+
raise
963+
964+
return thermoData
965+
946966
def __addThermoData(self, thermoData1, thermoData2):
947967
"""
948968
Add the thermodynamic data `thermoData2` to the data `thermoData1`,

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