void Main()
{
IAtomContainer molecule = null;
#region 1
StructureResonanceGenerator sRG = new StructureResonanceGenerator();
IChemObjectSet <IAtomContainer> setOf = sRG.GetContainers(molecule);
#endregion
#region 2
molecule.Atoms[0].IsReactiveCenter = true;
#endregion
}
/// <summary>
/// Main method which assigns Gasteiger partial pi charges.
/// </summary>
/// <param name="ac">AtomContainer</param>
/// <param name="setCharge">currently unused</param>
/// <returns>AtomContainer with partial charges</returns>
public IAtomContainer AssignGasteigerPiPartialCharges(IAtomContainer ac, bool setCharge)
{
// we save the aromaticity flags for the input molecule so that
// we can add them back before we return
var oldBondAromaticity = new bool[ac.Bonds.Count];
var oldAtomAromaticity = new bool[ac.Atoms.Count];
for (int i = 0; i < ac.Atoms.Count; i++)
{
oldAtomAromaticity[i] = ac.Atoms[i].IsAromatic;
}
for (int i = 0; i < ac.Bonds.Count; i++)
{
oldBondAromaticity[i] = ac.Bonds[i].IsAromatic;
}
/* 0: remove charge, and possible flag ac */
for (int j = 0; j < ac.Atoms.Count; j++)
{
ac.Atoms[j].Charge = 0.0;
ac.Atoms[j].IsPlaced = false;
}
for (int j = 0; j < ac.Bonds.Count; j++)
{
ac.Bonds[j].IsPlaced = false;
}
/* 1: detect resonance structure */
var gR1 = new StructureResonanceGenerator(); // according G. should be integrated the breaking bonding
var reactionList1 = gR1.Reactions.ToList();
var paramList1 = new List <IParameterReaction>();
var param = new SetReactionCenter {
IsSetParameter = true
};
paramList1.Add(param);
var reactionHCPB = new HeterolyticCleavagePBReaction {
ParameterList = paramList1
};
reactionList1.Add(new SharingAnionReaction());
foreach (var reaction in reactionList1)
{
reaction.ParameterList = paramList1;
}
gR1.Reactions = reactionList1;
// according G. should be integrated the breaking bonding
var gR2 = new StructureResonanceGenerator {
MaximalStructures = MaxResonanceStructures
};
var reactionList2 = gR2.Reactions.ToList();
var paramList = new List <IParameterReaction>();
var paramA = new SetReactionCenter {
IsSetParameter = true
};
paramList.Add(paramA);
reactionList2.Add(new HeterolyticCleavagePBReaction());
reactionList2.Add(new SharingAnionReaction());
foreach (var reaction in reactionList2)
{
reaction.ParameterList = paramList;
}
gR2.Reactions = reactionList2;
/* find resonance containers, which eliminates the repetitions */
StructureResonanceGenerator gRN = new StructureResonanceGenerator(); // according G. should be integrated the breaking bonding
var acSet = gRN.GetContainers(RemovingFlagsAromaticity(ac));
var iSet = ac.Builder.NewAtomContainerSet();
iSet.Add(ac);
if (acSet != null)
{
foreach (var container in acSet)
{
ac = SetFlags(container, ac, true);
// Aromatic don't break its double bond homolytically
if (Aromaticity.CDKLegacy.Apply(ac))
{
reactionList1.Remove(reactionHCPB);
}
else
{
reactionList1.Add(reactionHCPB);
}
var a = gR1.GetStructures(RemovingFlagsAromaticity(ac));
if (a.Count > 1)
{
for (int j = 1; j < a.Count; j++)
{ // the first is already added
iSet.Add(a[j]);
}
}
ac = SetFlags(container, ac, false);
/* processing for bonds which are not in resonance */
for (int number = 0; number < ac.Bonds.Count; number++)
{
IAtomContainer aa = SetAntiFlags(container, ac, number, true);
if (aa != null)
{
var ab = gR2.GetStructures(aa);
if (ab.Count > 1)
{
for (int j = 1; j < ab.Count; j++)
{ // the first is already added
iSet.Add(ab[j]);
}
}
ac = SetAntiFlags(container, aa, number, false);
}
}
}
}
/* detect hyperconjugation interactions */
var setHI = GetHyperconjugationInteractions(ac, iSet);
if (setHI != null)
{
if (setHI.Count != 0)
{
iSet.AddRange(setHI);
}
Debug.WriteLine($"setHI: {iSet.Count}");
}
if (iSet.Count < 2)
{
for (int i = 0; i < ac.Atoms.Count; i++)
{
ac.Atoms[i].IsAromatic = oldAtomAromaticity[i];
}
for (int i = 0; i < ac.Bonds.Count; i++)
{
ac.Bonds[i].IsAromatic = oldBondAromaticity[i];
}
return(ac);
}
/* 2: search whose atoms which don't keep their formal charge and set flags */
var sumCharges = Arrays.CreateJagged <double>(iSet.Count, ac.Atoms.Count);
for (int i = 1; i < iSet.Count; i++)
{
var iac = iSet[i];
for (int j = 0; j < iac.Atoms.Count; j++)
{
sumCharges[i][j] = iac.Atoms[j].FormalCharge.Value;
}
}
for (int i = 1; i < iSet.Count; i++)
{
var iac = iSet[i];
int count = 0;
for (int j = 0; j < ac.Atoms.Count; j++)
{
if (count < 2)
{
if (sumCharges[i][j] != ac.Atoms[j].FormalCharge)
{
ac.Atoms[j].IsPlaced = true;
iac.Atoms[j].IsPlaced = true;
count++; /* TODO- error */
}
}
}
}
/* 3: set sigma charge (PEOE). Initial start point */
var peoe = new GasteigerMarsiliPartialCharges();;
peoe.MaxGasteigerIterations = 6;
IAtomContainer acCloned;
var gasteigerFactors = AssignPiFactors(iSet);//a,b,c,deoc,chi,q
/* 4: calculate topological weight factors Wt=fQ*fB*fA */
var Wt = new double[iSet.Count - 1];
for (int i = 1; i < iSet.Count; i++)
{
Wt[i - 1] = GetTopologicalFactors(iSet[i], ac);
Debug.WriteLine($", W:{Wt[i - 1]}");
acCloned = (IAtomContainer)iSet[i].Clone();
acCloned = peoe.AssignGasteigerMarsiliSigmaPartialCharges(acCloned, true);
for (int j = 0; j < acCloned.Atoms.Count; j++)
{
if (iSet[i].Atoms[j].IsPlaced)
{
gasteigerFactors[i][StepSize * j + j + 5] = acCloned.Atoms[j].Charge.Value;
}
}
}
// calculate electronegativity for changed atoms and make the difference
// between whose atoms which change their formal charge
for (int iter = 0; iter < MaxGasteigerIterations; iter++)
{
for (int k = 1; k < iSet.Count; k++)
{
IAtomContainer iac = iSet[k];
double[] electronegativity = new double[2];
int count = 0;
int atom1 = 0;
int atom2 = 0;
for (int j = 0; j < iac.Atoms.Count; j++)
{
if (count == 2) // The change of sign is product of only two atoms, is not true
{
break;
}
if (iac.Atoms[j].IsPlaced)
{
Debug.WriteLine("Atom: " + j + ", S:" + iac.Atoms[j].Symbol + ", C:"
+ iac.Atoms[j].FormalCharge);
if (count == 0)
{
atom1 = j;
}
else
{
atom2 = j;
}
double q1 = gasteigerFactors[k][StepSize * j + j + 5];
electronegativity[count] =
gasteigerFactors[k][StepSize * j + j + 2] * q1 * q1
+ gasteigerFactors[k][StepSize * j + j + 1] * q1
+ gasteigerFactors[k][StepSize * j + j];
Debug.WriteLine("e:" + electronegativity[count] + ",q1: " + q1 + ", c:"
+ gasteigerFactors[k][StepSize * j + j + 2] + ", b:"
+ gasteigerFactors[k][StepSize * j + j + 1] + ", a:"
+ gasteigerFactors[k][StepSize * j + j]);
count++;
}
}
Debug.WriteLine("Atom1:" + atom1 + ",Atom2:" + atom2);
/* difference of electronegativity 1 lower */
var max1 = Math.Max(electronegativity[0], electronegativity[1]);
var min1 = Math.Min(electronegativity[0], electronegativity[1]);
double DX = 1.0;
if (electronegativity[0] < electronegativity[1])
{
DX = gasteigerFactors[k][StepSize * atom1 + atom1 + 3];
}
else
{
DX = gasteigerFactors[k][StepSize * atom2 + atom2 + 3];
}
var Dq = (max1 - min1) / DX;
Debug.WriteLine("Dq : " + Dq + " = (" + max1 + "-" + min1 + ")/" + DX);
var epN1 = GetElectrostaticPotentialN(iac, atom1, gasteigerFactors[k]);
var epN2 = GetElectrostaticPotentialN(iac, atom2, gasteigerFactors[k]);
var SumQN = Math.Abs(epN1 - epN2);
Debug.WriteLine("sum(" + SumQN + ") = (" + epN1 + ") - (" + epN2 + ")");
/* electronic weight */
var WE = Dq + fE * SumQN;
Debug.WriteLine("WE : " + WE + " = Dq(" + Dq + ")+FE(" + fE + ")*SumQN(" + SumQN);
var iTE = iter + 1;
/* total topological */
var W = WE * Wt[k - 1] * fS / (iTE);
Debug.WriteLine("W : " + W + " = WE(" + WE + ")*Wt(" + Wt[k - 1] + ")*FS(" + fS + ")/iter(" + iTE
+ "), atoms: " + atom1 + ", " + atom2);
/* iac == new structure, ac == old structure */
/* atom1 */
if (iac.Atoms[atom1].FormalCharge == 0)
{
if (ac.Atoms[atom1].FormalCharge < 0)
{
gasteigerFactors[k][StepSize * atom1 + atom1 + 5] = -1 * W;
}
else
{
gasteigerFactors[k][StepSize * atom1 + atom1 + 5] = W;
}
}
else if (iac.Atoms[atom1].FormalCharge > 0)
{
gasteigerFactors[k][StepSize * atom1 + atom1 + 5] = W;
}
else
{
gasteigerFactors[k][StepSize * atom1 + atom1 + 5] = -1 * W;
}
/* atom2 */
if (iac.Atoms[atom2].FormalCharge == 0)
{
if (ac.Atoms[atom2].FormalCharge < 0)
{
gasteigerFactors[k][StepSize * atom2 + atom2 + 5] = -1 * W;
}
else
{
gasteigerFactors[k][StepSize * atom2 + atom2 + 5] = W;
}
}
else if (iac.Atoms[atom2].FormalCharge > 0)
{
gasteigerFactors[k][StepSize * atom2 + atom2 + 5] = W;
}
else
{
gasteigerFactors[k][StepSize * atom2 + atom2 + 5] = -1 * W;
}
}
for (int k = 1; k < iSet.Count; k++)
{
for (int i = 0; i < ac.Atoms.Count; i++)
{
if (iSet[k].Atoms[i].IsPlaced)
{
var charge = ac.Atoms[i].Charge.Value;
double chargeT = 0.0;
chargeT = charge + gasteigerFactors[k][StepSize * i + i + 5];
Debug.WriteLine("i<|" + ac.Atoms[i].Symbol + ", " + chargeT + "=c:" + charge + "+g: "
+ gasteigerFactors[k][StepSize * i + i + 5]);
ac.Atoms[i].Charge = chargeT;
}
}
}
}// iterations
Debug.WriteLine("final");
// before getting back we should set back the aromatic flags
for (int i = 0; i < ac.Atoms.Count; i++)
{
ac.Atoms[i].IsAromatic = oldAtomAromaticity[i];
}
for (int i = 0; i < ac.Bonds.Count; i++)
{
ac.Bonds[i].IsAromatic = oldBondAromaticity[i];
}
return(ac);
}
/// <summary>
/// calculate the stabilization of orbitals when they contain deficiency of charge.
/// </summary>
/// <param name="atomContainer">the molecule to be considered</param>
/// <param name="atom">IAtom for which effective atom StabilizationCharges factor should be calculated</param>
/// <returns>stabilizationValue</returns>
public static double CalculatePositive(IAtomContainer atomContainer, IAtom atom)
{
/* restrictions */
// if(atomContainer.GetConnectedSingleElectronsCount(atom) > 0 || atom.FormalCharge != 1){
if (atom.FormalCharge != 1)
{
return(0.0);
}
// only must be generated all structures which stabilize the atom in question.
StructureResonanceGenerator gRI = new StructureResonanceGenerator();
var reactionList = gRI.Reactions.ToList();
reactionList.Add(new HyperconjugationReaction());
gRI.Reactions = reactionList;
var resonanceS = gRI.GetStructures(atomContainer);
var containerS = gRI.GetContainers(atomContainer);
if (resonanceS.Count < 2) // meaning it was not find any resonance structure
{
return(0.0);
}
int positionStart = atomContainer.Atoms.IndexOf(atom);
var result1 = new List <double>();
var distance1 = new List <int>();
resonanceS.RemoveAt(0);// the first is the initial structure
foreach (var resonance in resonanceS)
{
if (resonance.Atoms.Count < 2) // resonance with only one atom donnot have resonance
{
continue;
}
ShortestPaths shortestPaths = new ShortestPaths(resonance, resonance.Atoms[positionStart]);
/* search positive charge */
PiElectronegativity electronegativity = new PiElectronegativity();
foreach (var atomP in resonance.Atoms)
{
IAtom atomR = atomContainer.Atoms[resonance.Atoms.IndexOf(atomP)];
if (containerS[0].Contains(atomR))
{
electronegativity.MaxIterations = 6;
double result = electronegativity.CalculatePiElectronegativity(resonance, atomP);
result1.Add(result);
int dis = shortestPaths.GetDistanceTo(atomP);
distance1.Add(dis);
}
}
}
/* logarithm */
double value = 0.0;
double sum = 0.0;
var itDist = distance1.GetEnumerator();
foreach (var ee in result1)
{
double suM = ee;
if (suM < 0)
{
suM = -1 * suM;
}
itDist.MoveNext();
sum += suM * Math.Pow(0.67, itDist.Current);
}
value = sum;
return(value);
}
