hsosscf.cc

大型并行量子化学软件；支持密度泛函（DFT）。可以进行各种量子化学计算。支持CHARMM并行计算。非常具有应用价值。

//
// hsosscf.cc --- implementation of the high-spin open shell SCF class
//
// Copyright (C) 1996 Limit Point Systems, Inc.
//
// Author: Edward Seidl <[e-mail]>
// Maintainer: LPS
//
// This file is part of the SC Toolkit.
//
// The SC Toolkit is free software; you can redistribute it and/or modify
// it under the terms of the GNU Library General Public License as published by
// the Free Software Foundation; either version 2, or (at your option)
// any later version.
//
// The SC Toolkit is distributed in the hope that it will be useful,
// but WITHOUT ANY WARRANTY; without even the implied warranty of
// MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE.  See the
// GNU Library General Public License for more details.
//
// You should have received a copy of the GNU Library General Public License
// along with the SC Toolkit; see the file COPYING.LIB.  If not, write to
// the Free Software Foundation, 675 Mass Ave, Cambridge, MA 02139, USA.
//
// The U.S. Government is granted a limited license as per AL 91-7.
//

#ifdef __GNUC__
#pragma implementation
#endif

#include <math.h>

#include <util/misc/timer.h>
#include <util/misc/formio.h>
#include <util/state/stateio.h>

#include <math/scmat/block.h>
#include <math/scmat/blocked.h>
#include <math/scmat/blkiter.h>
#include <math/scmat/local.h>

#include <math/optimize/scextrapmat.h>

#include <chemistry/qc/basis/petite.h>

#include <chemistry/qc/scf/scflocal.h>
#include <chemistry/qc/scf/scfops.h>
#include <chemistry/qc/scf/effh.h>
#include <chemistry/qc/scf/hsosscf.h>

#include <chemistry/qc/scf/ltbgrad.h>
#include <chemistry/qc/scf/hsoshftmpl.h>

using namespace std;
using namespace sc;

///////////////////////////////////////////////////////////////////////////
// HSOSSCF

static ClassDesc HSOSSCF_cd(
  typeid(HSOSSCF),"HSOSSCF",2,"public SCF",
  0, 0, 0);

HSOSSCF::HSOSSCF(StateIn& s) :
  SavableState(s),
  SCF(s),
  cl_fock_(this),
  op_fock_(this)
{
  cl_fock_.result_noupdate() =
    basis_matrixkit()->symmmatrix(so_dimension());
  cl_fock_.restore_state(s);
  cl_fock_.result_noupdate().restore(s);
  
  op_fock_.result_noupdate() =
    basis_matrixkit()->symmmatrix(so_dimension());
  op_fock_.restore_state(s);
  op_fock_.result_noupdate().restore(s);
  
  s.get(user_occupations_);
  s.get(tndocc_);
  s.get(tnsocc_);
  s.get(nirrep_);
  s.get(ndocc_);
  s.get(nsocc_);
  if (s.version(::class_desc<HSOSSCF>()) >= 2) {
    s.get(initial_ndocc_);
    s.get(initial_nsocc_);
    most_recent_pg_ << SavableState::restore_state(s);
  } else {
    initial_ndocc_ = new int[nirrep_];
    memcpy(initial_ndocc_, ndocc_, sizeof(int)*nirrep_);
    initial_nsocc_ = new int[nirrep_];
    memcpy(initial_nsocc_, nsocc_, sizeof(int)*nirrep_);
  }

  // now take care of memory stuff
  init_mem(4);
}

HSOSSCF::HSOSSCF(const Ref<KeyVal>& keyval) :
  SCF(keyval),
  cl_fock_(this),
  op_fock_(this)
{
  int i;
  
  cl_fock_.compute()=0;
  cl_fock_.computed()=0;
  
  op_fock_.compute()=0;
  op_fock_.computed()=0;
  
  // calculate the total nuclear charge
  double Znuc=molecule()->nuclear_charge();

  // check to see if this is to be a charged molecule
  double charge = keyval->doublevalue("total_charge");
  int nelectrons = (int)(Znuc-charge+1.0e-4);

  // first let's try to figure out how many open shells there are
  if (keyval->exists("nsocc")) {
    tnsocc_ = keyval->intvalue("nsocc");
  } else if (keyval->exists("multiplicity")) {
    tnsocc_ = keyval->intvalue("multiplicity")-1;
  } else {
    // if there's an odd number of electrons, then do a doublet, otherwise
    // do a triplet
    if (nelectrons%2)
      tnsocc_=1;
    else
      tnsocc_=2;
  }
  
  // now do the same for the number of doubly occupied shells
  if (keyval->exists("ndocc")) {
    tndocc_ = keyval->intvalue("ndocc");
  } else {
    tndocc_ = (nelectrons-tnsocc_)/2;
    if ((nelectrons-tnsocc_)%2) {
      ExEnv::err0() << endl << indent
           << "HSOSSCF::init: Warning, there's a leftover electron.\n"
           << incindent << indent << "total_charge = " << charge << endl
           << indent << "total nuclear charge = " << Znuc << endl
           << indent << "ndocc_ = " << tndocc_ << endl
           << indent << "nsocc_ = " << tnsocc_ << endl << decindent;
    }
  }

  ExEnv::out0() << endl << indent
       << "HSOSSCF::init: total charge = " << Znuc-2*tndocc_-tnsocc_
       << endl << endl;

  nirrep_ = molecule()->point_group()->char_table().ncomp();

  ndocc_ = read_occ(keyval, "docc", nirrep_);
  nsocc_ = read_occ(keyval, "socc", nirrep_);
  if (ndocc_ && nsocc_) {
    user_occupations_=1;
    initial_ndocc_ = new int[nirrep_];
    memcpy(initial_ndocc_, ndocc_, sizeof(int)*nirrep_);
    initial_nsocc_ = new int[nirrep_];
    memcpy(initial_nsocc_, nsocc_, sizeof(int)*nirrep_);
  }
  else if (ndocc_ && !nsocc_ || !ndocc_ && nsocc_) {
    ExEnv::outn() << "ERROR: HSOSSCF: only one of docc and socc specified: "
                 << "give both or none" << endl;
    abort();
  }
  else {
    ndocc_=0;
    nsocc_=0;
    initial_ndocc_=0;
    initial_nsocc_=0;
    user_occupations_=0;
    set_occupations(0);
  }

  ExEnv::out0() << indent << "docc = [";
  for (i=0; i < nirrep_; i++)
    ExEnv::out0() << " " << ndocc_[i];
  ExEnv::out0() << " ]\n";

  ExEnv::out0() << indent << "socc = [";
  for (i=0; i < nirrep_; i++)
    ExEnv::out0() << " " << nsocc_[i];
  ExEnv::out0() << " ]\n";

  // check to see if this was done in SCF(keyval)
  if (!keyval->exists("maxiter"))
    maxiter_ = 100;

  if (!keyval->exists("level_shift"))
    level_shift_ = 0.25;

  // now take care of memory stuff
  init_mem(4);
}

HSOSSCF::~HSOSSCF()
{
  if (ndocc_) {
    delete[] ndocc_;
    ndocc_=0;
  }
  if (nsocc_) {
    delete[] nsocc_;
    nsocc_=0;
  }
  delete[] initial_ndocc_;
  delete[] initial_nsocc_;
}

void
HSOSSCF::save_data_state(StateOut& s)
{
  SCF::save_data_state(s);

  cl_fock_.save_data_state(s);
  cl_fock_.result_noupdate().save(s);
  
  op_fock_.save_data_state(s);
  op_fock_.result_noupdate().save(s);
  
  s.put(user_occupations_);
  s.put(tndocc_);
  s.put(tnsocc_);
  s.put(nirrep_);
  s.put(ndocc_,nirrep_);
  s.put(nsocc_,nirrep_);
  s.put(initial_ndocc_,nirrep_);
  s.put(initial_nsocc_,nirrep_);
  SavableState::save_state(most_recent_pg_.pointer(),s);
}

double
HSOSSCF::occupation(int ir, int i)
{
  if (i < ndocc_[ir]) return 2.0;
  else if (i < ndocc_[ir] + nsocc_[ir]) return 1.0;
  return 0.0;
}

double
HSOSSCF::alpha_occupation(int ir, int i)
{
  if (i < ndocc_[ir] + nsocc_[ir]) return 1.0;
  return 0.0;
}

double
HSOSSCF::beta_occupation(int ir, int i)
{
  if (i < ndocc_[ir]) return 1.0;
  return 0.0;
}

int
HSOSSCF::n_fock_matrices() const
{
  return 2;
}

RefSymmSCMatrix
HSOSSCF::fock(int n)
{
  if (n > 1) {
    ExEnv::err0() << indent
         << "HSOSSCF::fock: there are only two fock matrices, "
         << scprintf("but fock(%d) was requested\n",n);
    abort();
  }

  if (n==0)
    return cl_fock_.result();
  else
    return op_fock_.result();
}

int
HSOSSCF::spin_polarized()
{
  return 1;
}

void
HSOSSCF::print(ostream&o) const
{
  int i;
  
  SCF::print(o);
  o << indent << "HSOSSCF Parameters:\n" << incindent
    << indent << "charge = " << molecule()->nuclear_charge()
                                - 2*tndocc_ - tnsocc_ << endl
    << indent << "ndocc = " << tndocc_ << endl
    << indent << "nsocc = " << tnsocc_ << endl
    << indent << "docc = [";
  for (i=0; i < nirrep_; i++)
    o << " " << ndocc_[i];
  o << " ]" << endl;

  o << indent << "socc = [";
  for (i=0; i < nirrep_; i++)
    o << " " << nsocc_[i];
  o << " ]" << endl << decindent << endl;
}

//////////////////////////////////////////////////////////////////////////////

void
HSOSSCF::set_occupations(const RefDiagSCMatrix& ev)
{
  if (user_occupations_ || (initial_ndocc_ && initial_nsocc_ && ev.null())) {
    if (form_occupations(ndocc_, initial_ndocc_)
        &&form_occupations(nsocc_, initial_nsocc_)) {
      most_recent_pg_ = new PointGroup(molecule()->point_group());
      return;
    }
    delete[] ndocc_; ndocc_ = 0;
    delete[] nsocc_; nsocc_ = 0;
    ExEnv::out0() << indent
         << "HSOSSCF: WARNING: reforming occupation vectors from scratch"
         << endl;
  }
  
  if (nirrep_==1) {
    delete[] ndocc_;
    ndocc_=new int[1];
    ndocc_[0]=tndocc_;
    if (!initial_ndocc_) {
      initial_ndocc_=new int[1];
      initial_ndocc_[0]=tndocc_;
    }

    delete[] nsocc_;
    nsocc_=new int[1];
    nsocc_[0]=tnsocc_;
    if (!initial_nsocc_) {
      initial_nsocc_=new int[1];
      initial_nsocc_[0]=tnsocc_;
    }

    return;
  }
  
  int i,j;
  
  RefDiagSCMatrix evals;
  
  if (ev.null()) {
    initial_vector(0);
    evals = eigenvalues_.result_noupdate();
  }
  else
    evals = ev;

  // first convert evals to something we can deal with easily
  BlockedDiagSCMatrix *evalsb = require_dynamic_cast<BlockedDiagSCMatrix*>(evals,
                                                 "HSOSSCF::set_occupations");
  
  double **vals = new double*[nirrep_];
  for (i=0; i < nirrep_; i++) {
    int nf=oso_dimension()->blocks()->size(i);
    if (nf) {
      vals[i] = new double[nf];
      evalsb->block(i)->convert(vals[i]);
    } else {
      vals[i] = 0;
    }
  }

  // now loop to find the tndocc_ lowest eigenvalues and populate those
  // MO's
  int *newdocc = new int[nirrep_];
  memset(newdocc,0,sizeof(int)*nirrep_);

  for (i=0; i < tndocc_; i++) {
    // find lowest eigenvalue
    int lir=0,ln=0;
    double lowest=999999999;

    for (int ir=0; ir < nirrep_; ir++) {
      int nf=oso_dimension()->blocks()->size(ir);
      if (!nf)
        continue;
      for (j=0; j < nf; j++) {
        if (vals[ir][j] < lowest) {
          lowest=vals[ir][j];
          lir=ir;
          ln=j;
        }
      }
    }
    vals[lir][ln]=999999999;
    newdocc[lir]++;
  }

  int *newsocc = new int[nirrep_];
  memset(newsocc,0,sizeof(int)*nirrep_);

  for (i=0; i < tnsocc_; i++) {
    // find lowest eigenvalue
    int lir=0,ln=0;
    double lowest=999999999;

    for (int ir=0; ir < nirrep_; ir++) {
      int nf=oso_dimension()->blocks()->size(ir);
      if (!nf)
        continue;
      for (j=0; j < nf; j++) {
        if (vals[ir][j] < lowest) {
          lowest=vals[ir][j];
          lir=ir;
          ln=j;
        }
      }
    }
    vals[lir][ln]=999999999;
    newsocc[lir]++;
  }

  // get rid of vals
  for (i=0; i < nirrep_; i++)
    if (vals[i])
      delete[] vals[i];
  delete[] vals;

  if (!ndocc_) {
    ndocc_=newdocc;
    nsocc_=newsocc;
  } else if (most_recent_pg_.nonnull()
             && most_recent_pg_->equiv(molecule()->point_group())) {
    // test to see if newocc is different from ndocc_
    for (i=0; i < nirrep_; i++) {
      if (ndocc_[i] != newdocc[i]) {
        ExEnv::err0() << indent << "HSOSSCF::set_occupations:  WARNING!!!!\n"