439 lines
17 KiB
C++
439 lines
17 KiB
C++
/**
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* @file vcs_elem.cpp
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* This file contains the algorithm for checking the satisfaction of the
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* element abundances constraints and the algorithm for fixing violations
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* of the element abundances constraints.
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*/
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// This file is part of Cantera. See License.txt in the top-level directory or
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// at http://www.cantera.org/license.txt for license and copyright information.
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#include "cantera/equil/vcs_solve.h"
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#include "cantera/base/ctexceptions.h"
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#include "cantera/numerics/DenseMatrix.h"
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namespace Cantera
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{
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void VCS_SOLVE::vcs_elab()
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{
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for (size_t j = 0; j < m_numElemConstraints; ++j) {
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m_elemAbundances[j] = 0.0;
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for (size_t i = 0; i < m_numSpeciesTot; ++i) {
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if (m_speciesUnknownType[i] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
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m_elemAbundances[j] += m_formulaMatrix(i,j) * m_molNumSpecies_old[i];
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}
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}
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}
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}
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bool VCS_SOLVE::vcs_elabcheck(int ibound)
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{
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size_t top = m_numComponents;
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if (ibound) {
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top = m_numElemConstraints;
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}
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for (size_t i = 0; i < top; ++i) {
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// Require 12 digits of accuracy on non-zero constraints.
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if (m_elementActive[i] && fabs(m_elemAbundances[i] - m_elemAbundancesGoal[i]) > fabs(m_elemAbundancesGoal[i]) * 1.0e-12) {
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// This logic is for charge neutrality condition
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if (m_elType[i] == VCS_ELEM_TYPE_CHARGENEUTRALITY &&
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m_elemAbundancesGoal[i] != 0.0) {
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throw CanteraError("VCS_SOLVE::vcs_elabcheck",
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"Problem with charge neutrality condition");
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}
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if (m_elemAbundancesGoal[i] == 0.0 || (m_elType[i] == VCS_ELEM_TYPE_ELECTRONCHARGE)) {
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double scale = VCS_DELETE_MINORSPECIES_CUTOFF;
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// Find out if the constraint is a multisign constraint. If it
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// is, then we have to worry about roundoff error in the
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// addition of terms. We are limited to 13 digits of finite
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// arithmetic accuracy.
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bool multisign = false;
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for (size_t kspec = 0; kspec < m_numSpeciesTot; kspec++) {
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double eval = m_formulaMatrix(kspec,i);
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if (eval < 0.0) {
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multisign = true;
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}
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if (eval != 0.0) {
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scale = std::max(scale, fabs(eval * m_molNumSpecies_old[kspec]));
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}
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}
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if (multisign) {
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if (fabs(m_elemAbundances[i] - m_elemAbundancesGoal[i]) > 1e-11 * scale) {
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return false;
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}
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} else {
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if (fabs(m_elemAbundances[i] - m_elemAbundancesGoal[i]) > VCS_DELETE_MINORSPECIES_CUTOFF) {
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return false;
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}
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}
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} else {
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// For normal element balances, we require absolute compliance
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// even for ridiculously small numbers.
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if (m_elType[i] == VCS_ELEM_TYPE_ABSPOS) {
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return false;
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} else {
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return false;
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}
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}
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}
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}
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return true;
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}
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void VCS_SOLVE::vcs_elabPhase(size_t iphase, double* const elemAbundPhase)
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{
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for (size_t j = 0; j < m_numElemConstraints; ++j) {
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elemAbundPhase[j] = 0.0;
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for (size_t i = 0; i < m_numSpeciesTot; ++i) {
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if (m_speciesUnknownType[i] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE && m_phaseID[i] == iphase) {
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elemAbundPhase[j] += m_formulaMatrix(i,j) * m_molNumSpecies_old[i];
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}
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}
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}
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}
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int VCS_SOLVE::vcs_elcorr(double aa[], double x[])
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{
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int retn = 0;
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vector_fp ga_save(m_elemAbundances);
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if (m_debug_print_lvl >= 2) {
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plogf(" --- vcsc_elcorr: Element abundances correction routine");
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if (m_numElemConstraints != m_numComponents) {
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plogf(" (m_numComponents != m_numElemConstraints)");
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}
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plogf("\n");
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}
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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x[i] = m_elemAbundances[i] - m_elemAbundancesGoal[i];
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}
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double l2before = 0.0;
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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l2before += x[i] * x[i];
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}
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l2before = sqrt(l2before/m_numElemConstraints);
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// Special section to take out single species, single component,
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// moles. These are species which have non-zero entries in the
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// formula matrix, and no other species have zero values either.
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bool changed = false;
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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int numNonZero = 0;
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bool multisign = false;
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for (size_t kspec = 0; kspec < m_numSpeciesTot; kspec++) {
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if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
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double eval = m_formulaMatrix(kspec,i);
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if (eval < 0.0) {
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multisign = true;
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}
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if (eval != 0.0) {
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numNonZero++;
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}
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}
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}
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if (!multisign) {
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if (numNonZero < 2) {
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for (size_t kspec = 0; kspec < m_numSpeciesTot; kspec++) {
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if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
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double eval = m_formulaMatrix(kspec,i);
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if (eval > 0.0) {
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m_molNumSpecies_old[kspec] = m_elemAbundancesGoal[i] / eval;
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changed = true;
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}
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}
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}
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} else {
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int numCompNonZero = 0;
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size_t compID = npos;
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for (size_t kspec = 0; kspec < m_numComponents; kspec++) {
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if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
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double eval = m_formulaMatrix(kspec,i);
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if (eval > 0.0) {
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compID = kspec;
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numCompNonZero++;
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}
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}
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}
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if (numCompNonZero == 1) {
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double diff = m_elemAbundancesGoal[i];
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for (size_t kspec = m_numComponents; kspec < m_numSpeciesTot; kspec++) {
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if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
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double eval = m_formulaMatrix(kspec,i);
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diff -= eval * m_molNumSpecies_old[kspec];
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}
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m_molNumSpecies_old[compID] = std::max(0.0,diff/m_formulaMatrix(compID,i));
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changed = true;
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}
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}
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}
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}
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}
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if (changed) {
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vcs_elab();
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}
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// Section to check for maximum bounds errors on all species due to
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// elements. This may only be tried on element types which are
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// VCS_ELEM_TYPE_ABSPOS. This is because no other species may have a
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// negative number of these.
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//
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// Note, also we can do this over ne, the number of elements, not just the
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// number of components.
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changed = false;
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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int elType = m_elType[i];
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if (elType == VCS_ELEM_TYPE_ABSPOS) {
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for (size_t kspec = 0; kspec < m_numSpeciesTot; kspec++) {
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if (m_speciesUnknownType[kspec] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
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double atomComp = m_formulaMatrix(kspec,i);
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if (atomComp > 0.0) {
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double maxPermissible = m_elemAbundancesGoal[i] / atomComp;
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if (m_molNumSpecies_old[kspec] > maxPermissible) {
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if (m_debug_print_lvl >= 3) {
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plogf(" --- vcs_elcorr: Reduced species %s from %g to %g "
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"due to %s max bounds constraint\n",
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m_speciesName[kspec], m_molNumSpecies_old[kspec],
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maxPermissible, m_elementName[i]);
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}
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m_molNumSpecies_old[kspec] = maxPermissible;
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changed = true;
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if (m_molNumSpecies_old[kspec] < VCS_DELETE_MINORSPECIES_CUTOFF) {
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m_molNumSpecies_old[kspec] = 0.0;
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if (m_SSPhase[kspec]) {
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m_speciesStatus[kspec] = VCS_SPECIES_ZEROEDSS;
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} else {
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m_speciesStatus[kspec] = VCS_SPECIES_ACTIVEBUTZERO;
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}
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if (m_debug_print_lvl >= 2) {
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plogf(" --- vcs_elcorr: Zeroed species %s and changed "
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"status to %d due to max bounds constraint\n",
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m_speciesName[kspec], m_speciesStatus[kspec]);
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}
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}
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}
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}
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}
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}
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}
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}
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// Recalculate the element abundances if something has changed.
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if (changed) {
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vcs_elab();
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}
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// Ok, do the general case. Linear algebra problem is of length nc, not ne,
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// as there may be degenerate rows when nc .ne. ne.
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DenseMatrix A(m_numComponents, m_numComponents);
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for (size_t i = 0; i < m_numComponents; ++i) {
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x[i] = m_elemAbundances[i] - m_elemAbundancesGoal[i];
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if (fabs(x[i]) > 1.0E-13) {
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retn = 1;
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}
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for (size_t j = 0; j < m_numComponents; ++j) {
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A(j, i) = - m_formulaMatrix(i,j);
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}
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}
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solve(A, x, 1, m_numElemConstraints);
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// Now apply the new direction without creating negative species.
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double par = 0.5;
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for (size_t i = 0; i < m_numComponents; ++i) {
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if (m_molNumSpecies_old[i] > 0.0) {
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par = std::max(par, -x[i] / m_molNumSpecies_old[i]);
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}
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}
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par = std::min(par, 100.0);
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par = 1.0 / par;
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if (par < 1.0 && par > 0.0) {
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retn = 2;
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par *= 0.9999;
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for (size_t i = 0; i < m_numComponents; ++i) {
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double tmp = m_molNumSpecies_old[i] + par * x[i];
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if (tmp > 0.0) {
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m_molNumSpecies_old[i] = tmp;
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} else {
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if (m_SSPhase[i]) {
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m_molNumSpecies_old[i] = 0.0;
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} else {
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m_molNumSpecies_old[i] = m_molNumSpecies_old[i] * 0.0001;
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}
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}
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}
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} else {
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for (size_t i = 0; i < m_numComponents; ++i) {
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double tmp = m_molNumSpecies_old[i] + x[i];
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if (tmp > 0.0) {
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m_molNumSpecies_old[i] = tmp;
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} else {
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if (m_SSPhase[i]) {
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m_molNumSpecies_old[i] = 0.0;
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} else {
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m_molNumSpecies_old[i] = m_molNumSpecies_old[i] * 0.0001;
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}
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}
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}
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}
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// We have changed the element abundances. Calculate them again
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vcs_elab();
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// We have changed the total moles in each phase. Calculate them again
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vcs_tmoles();
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// Try some ad hoc procedures for fixing the problem
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if (retn >= 2) {
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// First find a species whose adjustment is a win-win situation.
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for (size_t kspec = 0; kspec < m_numSpeciesTot; kspec++) {
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if (m_speciesUnknownType[kspec] == VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
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continue;
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}
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double saveDir = 0.0;
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bool goodSpec = true;
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for (size_t i = 0; i < m_numComponents; ++i) {
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double dir = m_formulaMatrix(kspec,i) * (m_elemAbundancesGoal[i] - m_elemAbundances[i]);
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if (fabs(dir) > 1.0E-10) {
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if (dir > 0.0) {
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if (saveDir < 0.0) {
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goodSpec = false;
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break;
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}
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} else {
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if (saveDir > 0.0) {
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goodSpec = false;
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break;
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}
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}
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saveDir = dir;
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} else {
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if (m_formulaMatrix(kspec,i) != 0.) {
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goodSpec = false;
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break;
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}
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}
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}
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if (goodSpec) {
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int its = 0;
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double xx = 0.0;
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for (size_t i = 0; i < m_numComponents; ++i) {
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if (m_formulaMatrix(kspec,i) != 0.0) {
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xx += (m_elemAbundancesGoal[i] - m_elemAbundances[i]) / m_formulaMatrix(kspec,i);
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its++;
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}
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}
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if (its > 0) {
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xx /= its;
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}
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m_molNumSpecies_old[kspec] += xx;
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m_molNumSpecies_old[kspec] = std::max(m_molNumSpecies_old[kspec], 1.0E-10);
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// If we are dealing with a deleted species, then we need to
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// reinsert it into the active list.
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if (kspec >= m_numSpeciesRdc) {
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vcs_reinsert_deleted(kspec);
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m_molNumSpecies_old[m_numSpeciesRdc - 1] = xx;
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vcs_elab();
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goto L_CLEANUP;
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}
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vcs_elab();
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}
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}
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}
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if (vcs_elabcheck(0)) {
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retn = 1;
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goto L_CLEANUP;
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}
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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if (m_elType[i] == VCS_ELEM_TYPE_CHARGENEUTRALITY ||
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(m_elType[i] == VCS_ELEM_TYPE_ABSPOS && m_elemAbundancesGoal[i] == 0.0)) {
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for (size_t kspec = 0; kspec < m_numSpeciesRdc; kspec++) {
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if (m_elemAbundances[i] > 0.0 && m_formulaMatrix(kspec,i) < 0.0) {
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m_molNumSpecies_old[kspec] -= m_elemAbundances[i] / m_formulaMatrix(kspec,i);
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m_molNumSpecies_old[kspec] = std::max(m_molNumSpecies_old[kspec], 0.0);
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vcs_elab();
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break;
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}
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if (m_elemAbundances[i] < 0.0 && m_formulaMatrix(kspec,i) > 0.0) {
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m_molNumSpecies_old[kspec] -= m_elemAbundances[i] / m_formulaMatrix(kspec,i);
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m_molNumSpecies_old[kspec] = std::max(m_molNumSpecies_old[kspec], 0.0);
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vcs_elab();
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break;
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}
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}
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}
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}
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if (vcs_elabcheck(1)) {
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retn = 1;
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goto L_CLEANUP;
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}
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// For electron charges element types, we try positive deltas in the species
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// concentrations to match the desired electron charge exactly.
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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double dev = m_elemAbundancesGoal[i] - m_elemAbundances[i];
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if (m_elType[i] == VCS_ELEM_TYPE_ELECTRONCHARGE && (fabs(dev) > 1.0E-300)) {
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bool useZeroed = true;
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for (size_t kspec = 0; kspec < m_numSpeciesRdc; kspec++) {
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if (dev < 0.0) {
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if (m_formulaMatrix(kspec,i) < 0.0 && m_molNumSpecies_old[kspec] > 0.0) {
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useZeroed = false;
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}
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} else {
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if (m_formulaMatrix(kspec,i) > 0.0 && m_molNumSpecies_old[kspec] > 0.0) {
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useZeroed = false;
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}
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}
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}
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for (size_t kspec = 0; kspec < m_numSpeciesRdc; kspec++) {
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if (m_molNumSpecies_old[kspec] > 0.0 || useZeroed) {
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if (dev < 0.0 && m_formulaMatrix(kspec,i) < 0.0) {
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double delta = dev / m_formulaMatrix(kspec,i);
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m_molNumSpecies_old[kspec] += delta;
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m_molNumSpecies_old[kspec] = std::max(m_molNumSpecies_old[kspec], 0.0);
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vcs_elab();
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break;
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}
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if (dev > 0.0 && m_formulaMatrix(kspec,i) > 0.0) {
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double delta = dev / m_formulaMatrix(kspec,i);
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m_molNumSpecies_old[kspec] += delta;
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m_molNumSpecies_old[kspec] = std::max(m_molNumSpecies_old[kspec], 0.0);
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vcs_elab();
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break;
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}
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}
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}
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}
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}
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if (vcs_elabcheck(1)) {
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retn = 1;
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goto L_CLEANUP;
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}
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L_CLEANUP:
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;
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vcs_tmoles();
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double l2after = 0.0;
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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l2after += pow(m_elemAbundances[i] - m_elemAbundancesGoal[i], 2);
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}
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l2after = sqrt(l2after/m_numElemConstraints);
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if (m_debug_print_lvl >= 2) {
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plogf(" --- Elem_Abund: Correct Initial "
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" Final\n");
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for (size_t i = 0; i < m_numElemConstraints; ++i) {
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plogf(" --- ");
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plogf("%-2.2s", m_elementName[i]);
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plogf(" %20.12E %20.12E %20.12E\n", m_elemAbundancesGoal[i], ga_save[i], m_elemAbundances[i]);
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}
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plogf(" --- Diff_Norm: %20.12E %20.12E\n",
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l2before, l2after);
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}
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return retn;
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}
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}
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