[0b990d] | 1 | //
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| 2 | // hsosscf.cc --- implementation of the high-spin open shell SCF class
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| 3 | //
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| 4 | // Copyright (C) 1996 Limit Point Systems, Inc.
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| 5 | //
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| 6 | // Author: Edward Seidl <seidl@janed.com>
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| 7 | // Maintainer: LPS
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| 8 | //
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| 9 | // This file is part of the SC Toolkit.
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| 10 | //
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| 11 | // The SC Toolkit is free software; you can redistribute it and/or modify
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| 12 | // it under the terms of the GNU Library General Public License as published by
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| 13 | // the Free Software Foundation; either version 2, or (at your option)
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| 14 | // any later version.
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| 15 | //
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| 16 | // The SC Toolkit is distributed in the hope that it will be useful,
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| 17 | // but WITHOUT ANY WARRANTY; without even the implied warranty of
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| 18 | // MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE. See the
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| 19 | // GNU Library General Public License for more details.
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| 20 | //
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| 21 | // You should have received a copy of the GNU Library General Public License
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| 22 | // along with the SC Toolkit; see the file COPYING.LIB. If not, write to
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| 23 | // the Free Software Foundation, 675 Mass Ave, Cambridge, MA 02139, USA.
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| 24 | //
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| 25 | // The U.S. Government is granted a limited license as per AL 91-7.
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| 26 | //
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| 27 |
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| 28 | #ifdef __GNUC__
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| 29 | #pragma implementation
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| 30 | #endif
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| 31 |
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| 32 | #include <math.h>
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| 33 |
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| 34 | #include <util/misc/timer.h>
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| 35 | #include <util/misc/formio.h>
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| 36 | #include <util/state/stateio.h>
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| 37 |
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| 38 | #include <math/scmat/block.h>
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| 39 | #include <math/scmat/blocked.h>
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| 40 | #include <math/scmat/blkiter.h>
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| 41 | #include <math/scmat/local.h>
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| 42 |
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| 43 | #include <math/optimize/scextrapmat.h>
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| 44 |
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| 45 | #include <chemistry/qc/basis/petite.h>
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| 46 |
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| 47 | #include <chemistry/qc/scf/scflocal.h>
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| 48 | #include <chemistry/qc/scf/scfops.h>
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| 49 | #include <chemistry/qc/scf/effh.h>
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| 50 | #include <chemistry/qc/scf/hsosscf.h>
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| 51 |
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| 52 | #include <chemistry/qc/scf/ltbgrad.h>
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| 53 | #include <chemistry/qc/scf/hsoshftmpl.h>
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| 54 |
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| 55 | using namespace std;
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| 56 | using namespace sc;
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| 57 |
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| 58 | ///////////////////////////////////////////////////////////////////////////
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| 59 | // HSOSSCF
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| 60 |
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| 61 | static ClassDesc HSOSSCF_cd(
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| 62 | typeid(HSOSSCF),"HSOSSCF",2,"public SCF",
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| 63 | 0, 0, 0);
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| 64 |
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| 65 | HSOSSCF::HSOSSCF(StateIn& s) :
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| 66 | SavableState(s),
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| 67 | SCF(s),
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| 68 | cl_fock_(this),
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| 69 | op_fock_(this)
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| 70 | {
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| 71 | cl_fock_.result_noupdate() =
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| 72 | basis_matrixkit()->symmmatrix(so_dimension());
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| 73 | cl_fock_.restore_state(s);
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| 74 | cl_fock_.result_noupdate().restore(s);
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| 75 |
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| 76 | op_fock_.result_noupdate() =
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| 77 | basis_matrixkit()->symmmatrix(so_dimension());
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| 78 | op_fock_.restore_state(s);
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| 79 | op_fock_.result_noupdate().restore(s);
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| 80 |
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| 81 | s.get(user_occupations_);
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| 82 | s.get(tndocc_);
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| 83 | s.get(tnsocc_);
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| 84 | s.get(nirrep_);
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| 85 | s.get(ndocc_);
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| 86 | s.get(nsocc_);
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| 87 | if (s.version(::class_desc<HSOSSCF>()) >= 2) {
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| 88 | s.get(initial_ndocc_);
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| 89 | s.get(initial_nsocc_);
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| 90 | most_recent_pg_ << SavableState::restore_state(s);
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| 91 | } else {
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| 92 | initial_ndocc_ = new int[nirrep_];
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| 93 | memcpy(initial_ndocc_, ndocc_, sizeof(int)*nirrep_);
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| 94 | initial_nsocc_ = new int[nirrep_];
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| 95 | memcpy(initial_nsocc_, nsocc_, sizeof(int)*nirrep_);
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| 96 | }
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| 97 |
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| 98 | // now take care of memory stuff
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| 99 | init_mem(4);
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| 100 | }
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| 101 |
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| 102 | HSOSSCF::HSOSSCF(const Ref<KeyVal>& keyval) :
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| 103 | SCF(keyval),
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| 104 | cl_fock_(this),
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| 105 | op_fock_(this)
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| 106 | {
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| 107 | int i;
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| 108 |
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| 109 | cl_fock_.compute()=0;
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| 110 | cl_fock_.computed()=0;
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| 111 |
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| 112 | op_fock_.compute()=0;
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| 113 | op_fock_.computed()=0;
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| 114 |
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| 115 | // calculate the total nuclear charge
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| 116 | double Znuc=molecule()->nuclear_charge();
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| 117 |
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| 118 | // check to see if this is to be a charged molecule
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| 119 | double charge = keyval->doublevalue("total_charge");
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| 120 | int nelectrons = (int)(Znuc-charge+1.0e-4);
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| 121 |
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| 122 | // first let's try to figure out how many open shells there are
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| 123 | if (keyval->exists("nsocc")) {
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| 124 | tnsocc_ = keyval->intvalue("nsocc");
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| 125 | } else if (keyval->exists("multiplicity")) {
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| 126 | tnsocc_ = keyval->intvalue("multiplicity")-1;
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| 127 | } else {
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| 128 | // if there's an odd number of electrons, then do a doublet, otherwise
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| 129 | // do a triplet
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| 130 | if (nelectrons%2)
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| 131 | tnsocc_=1;
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| 132 | else
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| 133 | tnsocc_=2;
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| 134 | }
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| 135 |
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| 136 | // now do the same for the number of doubly occupied shells
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| 137 | if (keyval->exists("ndocc")) {
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| 138 | tndocc_ = keyval->intvalue("ndocc");
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| 139 | } else {
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| 140 | tndocc_ = (nelectrons-tnsocc_)/2;
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| 141 | if ((nelectrons-tnsocc_)%2) {
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| 142 | ExEnv::err0() << endl << indent
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| 143 | << "HSOSSCF::init: Warning, there's a leftover electron.\n"
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| 144 | << incindent << indent << "total_charge = " << charge << endl
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| 145 | << indent << "total nuclear charge = " << Znuc << endl
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| 146 | << indent << "ndocc_ = " << tndocc_ << endl
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| 147 | << indent << "nsocc_ = " << tnsocc_ << endl << decindent;
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| 148 | }
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| 149 | }
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| 150 |
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| 151 | ExEnv::out0() << endl << indent
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| 152 | << "HSOSSCF::init: total charge = " << Znuc-2*tndocc_-tnsocc_
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| 153 | << endl << endl;
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| 154 |
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| 155 | nirrep_ = molecule()->point_group()->char_table().ncomp();
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| 156 |
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| 157 | ndocc_ = read_occ(keyval, "docc", nirrep_);
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| 158 | nsocc_ = read_occ(keyval, "socc", nirrep_);
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| 159 | if (ndocc_ && nsocc_) {
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| 160 | user_occupations_=1;
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| 161 | initial_ndocc_ = new int[nirrep_];
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| 162 | memcpy(initial_ndocc_, ndocc_, sizeof(int)*nirrep_);
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| 163 | initial_nsocc_ = new int[nirrep_];
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| 164 | memcpy(initial_nsocc_, nsocc_, sizeof(int)*nirrep_);
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| 165 | }
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| 166 | else if (ndocc_ && !nsocc_ || !ndocc_ && nsocc_) {
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| 167 | ExEnv::outn() << "ERROR: HSOSSCF: only one of docc and socc specified: "
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| 168 | << "give both or none" << endl;
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| 169 | abort();
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| 170 | }
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| 171 | else {
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| 172 | ndocc_=0;
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| 173 | nsocc_=0;
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| 174 | initial_ndocc_=0;
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| 175 | initial_nsocc_=0;
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| 176 | user_occupations_=0;
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| 177 | set_occupations(0);
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| 178 | }
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| 179 |
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| 180 | ExEnv::out0() << indent << "docc = [";
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| 181 | for (i=0; i < nirrep_; i++)
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| 182 | ExEnv::out0() << " " << ndocc_[i];
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| 183 | ExEnv::out0() << " ]\n";
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| 184 |
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| 185 | ExEnv::out0() << indent << "socc = [";
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| 186 | for (i=0; i < nirrep_; i++)
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| 187 | ExEnv::out0() << " " << nsocc_[i];
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| 188 | ExEnv::out0() << " ]\n";
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| 189 |
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| 190 | // check to see if this was done in SCF(keyval)
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| 191 | if (!keyval->exists("maxiter"))
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| 192 | maxiter_ = 100;
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| 193 |
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| 194 | if (!keyval->exists("level_shift"))
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| 195 | level_shift_ = 0.25;
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| 196 |
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| 197 | // now take care of memory stuff
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| 198 | init_mem(4);
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| 199 | }
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| 200 |
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| 201 | HSOSSCF::~HSOSSCF()
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| 202 | {
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| 203 | if (ndocc_) {
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| 204 | delete[] ndocc_;
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| 205 | ndocc_=0;
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| 206 | }
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| 207 | if (nsocc_) {
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| 208 | delete[] nsocc_;
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| 209 | nsocc_=0;
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| 210 | }
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| 211 | delete[] initial_ndocc_;
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| 212 | delete[] initial_nsocc_;
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| 213 | }
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| 214 |
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| 215 | void
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| 216 | HSOSSCF::save_data_state(StateOut& s)
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| 217 | {
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| 218 | SCF::save_data_state(s);
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| 219 |
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| 220 | cl_fock_.save_data_state(s);
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| 221 | cl_fock_.result_noupdate().save(s);
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| 222 |
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| 223 | op_fock_.save_data_state(s);
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| 224 | op_fock_.result_noupdate().save(s);
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| 225 |
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| 226 | s.put(user_occupations_);
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| 227 | s.put(tndocc_);
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| 228 | s.put(tnsocc_);
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| 229 | s.put(nirrep_);
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| 230 | s.put(ndocc_,nirrep_);
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| 231 | s.put(nsocc_,nirrep_);
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| 232 | s.put(initial_ndocc_,nirrep_);
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| 233 | s.put(initial_nsocc_,nirrep_);
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| 234 | SavableState::save_state(most_recent_pg_.pointer(),s);
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| 235 | }
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| 236 |
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| 237 | double
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| 238 | HSOSSCF::occupation(int ir, int i)
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| 239 | {
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| 240 | if (i < ndocc_[ir]) return 2.0;
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| 241 | else if (i < ndocc_[ir] + nsocc_[ir]) return 1.0;
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| 242 | return 0.0;
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| 243 | }
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| 244 |
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| 245 | double
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| 246 | HSOSSCF::alpha_occupation(int ir, int i)
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| 247 | {
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| 248 | if (i < ndocc_[ir] + nsocc_[ir]) return 1.0;
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| 249 | return 0.0;
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| 250 | }
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| 251 |
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| 252 | double
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| 253 | HSOSSCF::beta_occupation(int ir, int i)
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| 254 | {
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| 255 | if (i < ndocc_[ir]) return 1.0;
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| 256 | return 0.0;
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| 257 | }
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| 258 |
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| 259 | int
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| 260 | HSOSSCF::n_fock_matrices() const
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| 261 | {
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| 262 | return 2;
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| 263 | }
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| 264 |
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| 265 | RefSymmSCMatrix
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| 266 | HSOSSCF::fock(int n)
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| 267 | {
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| 268 | if (n > 1) {
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| 269 | ExEnv::err0() << indent
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| 270 | << "HSOSSCF::fock: there are only two fock matrices, "
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| 271 | << scprintf("but fock(%d) was requested\n",n);
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| 272 | abort();
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| 273 | }
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| 274 |
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| 275 | if (n==0)
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| 276 | return cl_fock_.result();
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| 277 | else
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| 278 | return op_fock_.result();
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| 279 | }
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| 280 |
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| 281 | int
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| 282 | HSOSSCF::spin_polarized()
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| 283 | {
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| 284 | return 1;
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| 285 | }
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| 286 |
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| 287 | void
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| 288 | HSOSSCF::print(ostream&o) const
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| 289 | {
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| 290 | int i;
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| 291 |
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| 292 | SCF::print(o);
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| 293 | o << indent << "HSOSSCF Parameters:\n" << incindent
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| 294 | << indent << "charge = " << molecule()->nuclear_charge()
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| 295 | - 2*tndocc_ - tnsocc_ << endl
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| 296 | << indent << "ndocc = " << tndocc_ << endl
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| 297 | << indent << "nsocc = " << tnsocc_ << endl
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| 298 | << indent << "docc = [";
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| 299 | for (i=0; i < nirrep_; i++)
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| 300 | o << " " << ndocc_[i];
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| 301 | o << " ]" << endl;
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| 302 |
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| 303 | o << indent << "socc = [";
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| 304 | for (i=0; i < nirrep_; i++)
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| 305 | o << " " << nsocc_[i];
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| 306 | o << " ]" << endl << decindent << endl;
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| 307 | }
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| 308 |
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| 309 | //////////////////////////////////////////////////////////////////////////////
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| 310 |
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| 311 | void
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| 312 | HSOSSCF::set_occupations(const RefDiagSCMatrix& ev)
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| 313 | {
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| 314 | if (user_occupations_ || (initial_ndocc_ && initial_nsocc_ && ev.null())) {
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| 315 | if (form_occupations(ndocc_, initial_ndocc_)
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| 316 | &&form_occupations(nsocc_, initial_nsocc_)) {
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| 317 | most_recent_pg_ = new PointGroup(molecule()->point_group());
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| 318 | return;
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| 319 | }
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| 320 | delete[] ndocc_; ndocc_ = 0;
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| 321 | delete[] nsocc_; nsocc_ = 0;
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| 322 | ExEnv::out0() << indent
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| 323 | << "HSOSSCF: WARNING: reforming occupation vectors from scratch"
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| 324 | << endl;
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| 325 | }
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| 326 |
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| 327 | if (nirrep_==1) {
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| 328 | delete[] ndocc_;
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| 329 | ndocc_=new int[1];
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| 330 | ndocc_[0]=tndocc_;
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| 331 | if (!initial_ndocc_) {
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| 332 | initial_ndocc_=new int[1];
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| 333 | initial_ndocc_[0]=tndocc_;
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| 334 | }
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| 335 |
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| 336 | delete[] nsocc_;
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| 337 | nsocc_=new int[1];
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| 338 | nsocc_[0]=tnsocc_;
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| 339 | if (!initial_nsocc_) {
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| 340 | initial_nsocc_=new int[1];
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| 341 | initial_nsocc_[0]=tnsocc_;
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| 342 | }
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| 343 |
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| 344 | return;
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| 345 | }
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| 346 |
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| 347 | int i,j;
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| 348 |
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| 349 | RefDiagSCMatrix evals;
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| 350 |
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| 351 | if (ev.null()) {
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| 352 | initial_vector(0);
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| 353 | evals = eigenvalues_.result_noupdate();
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| 354 | }
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| 355 | else
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| 356 | evals = ev;
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| 357 |
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| 358 | // first convert evals to something we can deal with easily
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| 359 | BlockedDiagSCMatrix *evalsb = require_dynamic_cast<BlockedDiagSCMatrix*>(evals,
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| 360 | "HSOSSCF::set_occupations");
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| 361 |
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| 362 | double **vals = new double*[nirrep_];
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| 363 | for (i=0; i < nirrep_; i++) {
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| 364 | int nf=oso_dimension()->blocks()->size(i);
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| 365 | if (nf) {
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| 366 | vals[i] = new double[nf];
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| 367 | evalsb->block(i)->convert(vals[i]);
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| 368 | } else {
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| 369 | vals[i] = 0;
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| 370 | }
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| 371 | }
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| 372 |
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| 373 | // now loop to find the tndocc_ lowest eigenvalues and populate those
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| 374 | // MO's
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| 375 | int *newdocc = new int[nirrep_];
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| 376 | memset(newdocc,0,sizeof(int)*nirrep_);
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| 377 |
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| 378 | for (i=0; i < tndocc_; i++) {
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| 379 | // find lowest eigenvalue
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| 380 | int lir=0,ln=0;
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| 381 | double lowest=999999999;
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| 382 |
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| 383 | for (int ir=0; ir < nirrep_; ir++) {
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| 384 | int nf=oso_dimension()->blocks()->size(ir);
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| 385 | if (!nf)
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| 386 | continue;
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| 387 | for (j=0; j < nf; j++) {
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| 388 | if (vals[ir][j] < lowest) {
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| 389 | lowest=vals[ir][j];
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| 390 | lir=ir;
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| 391 | ln=j;
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| 392 | }
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| 393 | }
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| 394 | }
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| 395 | vals[lir][ln]=999999999;
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| 396 | newdocc[lir]++;
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| 397 | }
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| 398 |
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| 399 | int *newsocc = new int[nirrep_];
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| 400 | memset(newsocc,0,sizeof(int)*nirrep_);
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| 401 |
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| 402 | for (i=0; i < tnsocc_; i++) {
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| 403 | // find lowest eigenvalue
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| 404 | int lir=0,ln=0;
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| 405 | double lowest=999999999;
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| 406 |
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| 407 | for (int ir=0; ir < nirrep_; ir++) {
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| 408 | int nf=oso_dimension()->blocks()->size(ir);
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| 409 | if (!nf)
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| 410 | continue;
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| 411 | for (j=0; j < nf; j++) {
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| 412 | if (vals[ir][j] < lowest) {
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| 413 | lowest=vals[ir][j];
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| 414 | lir=ir;
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| 415 | ln=j;
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| 416 | }
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| 417 | }
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| 418 | }
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| 419 | vals[lir][ln]=999999999;
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| 420 | newsocc[lir]++;
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| 421 | }
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| 422 |
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| 423 | // get rid of vals
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| 424 | for (i=0; i < nirrep_; i++)
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| 425 | if (vals[i])
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| 426 | delete[] vals[i];
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| 427 | delete[] vals;
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| 428 |
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| 429 | if (!ndocc_) {
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| 430 | ndocc_=newdocc;
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| 431 | nsocc_=newsocc;
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| 432 | } else if (most_recent_pg_.nonnull()
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| 433 | && most_recent_pg_->equiv(molecule()->point_group())) {
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| 434 | // test to see if newocc is different from ndocc_
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| 435 | for (i=0; i < nirrep_; i++) {
|
---|
| 436 | if (ndocc_[i] != newdocc[i]) {
|
---|
| 437 | ExEnv::err0() << indent << "HSOSSCF::set_occupations: WARNING!!!!\n"
|
---|
| 438 | << incindent << indent
|
---|
| 439 | << scprintf("occupations for irrep %d have changed\n",i+1)
|
---|
| 440 | << indent
|
---|
| 441 | << scprintf("ndocc was %d, changed to %d", ndocc_[i], newdocc[i])
|
---|
| 442 | << endl << decindent;
|
---|
| 443 | }
|
---|
| 444 | if (nsocc_[i] != newsocc[i]) {
|
---|
| 445 | ExEnv::err0() << indent << "HSOSSCF::set_occupations: WARNING!!!!\n"
|
---|
| 446 | << incindent << indent
|
---|
| 447 | << scprintf("occupations for irrep %d have changed\n",i+1)
|
---|
| 448 | << indent
|
---|
| 449 | << scprintf("nsocc was %d, changed to %d", nsocc_[i], newsocc[i])
|
---|
| 450 | << endl << decindent;
|
---|
| 451 | }
|
---|
| 452 | }
|
---|
| 453 |
|
---|
| 454 | memcpy(ndocc_,newdocc,sizeof(int)*nirrep_);
|
---|
| 455 | memcpy(nsocc_,newsocc,sizeof(int)*nirrep_);
|
---|
| 456 | delete[] newdocc;
|
---|
| 457 | delete[] newsocc;
|
---|
| 458 | }
|
---|
| 459 |
|
---|
| 460 | if (!initial_ndocc_
|
---|
| 461 | || initial_pg_->equiv(molecule()->point_group())) {
|
---|
| 462 | delete[] initial_ndocc_;
|
---|
| 463 | initial_ndocc_ = new int[nirrep_];
|
---|
| 464 | memcpy(initial_ndocc_,ndocc_,sizeof(int)*nirrep_);
|
---|
| 465 | }
|
---|
| 466 |
|
---|
| 467 | if (!initial_nsocc_
|
---|
| 468 | || initial_pg_->equiv(molecule()->point_group())) {
|
---|
| 469 | delete[] initial_nsocc_;
|
---|
| 470 | initial_nsocc_ = new int[nirrep_];
|
---|
| 471 | memcpy(initial_nsocc_,nsocc_,sizeof(int)*nirrep_);
|
---|
| 472 | }
|
---|
| 473 |
|
---|
| 474 | most_recent_pg_ = new PointGroup(molecule()->point_group());
|
---|
| 475 | }
|
---|
| 476 |
|
---|
| 477 | void
|
---|
| 478 | HSOSSCF::symmetry_changed()
|
---|
| 479 | {
|
---|
| 480 | SCF::symmetry_changed();
|
---|
| 481 | cl_fock_.result_noupdate()=0;
|
---|
| 482 | op_fock_.result_noupdate()=0;
|
---|
| 483 | nirrep_ = molecule()->point_group()->char_table().ncomp();
|
---|
| 484 | set_occupations(0);
|
---|
| 485 | }
|
---|
| 486 |
|
---|
| 487 | //////////////////////////////////////////////////////////////////////////////
|
---|
| 488 | //
|
---|
| 489 | // scf things
|
---|
| 490 | //
|
---|
| 491 |
|
---|
| 492 | void
|
---|
| 493 | HSOSSCF::init_vector()
|
---|
| 494 | {
|
---|
| 495 | init_threads();
|
---|
| 496 |
|
---|
| 497 | // allocate storage for other temp matrices
|
---|
| 498 | cl_dens_ = hcore_.clone();
|
---|
| 499 | cl_dens_.assign(0.0);
|
---|
| 500 |
|
---|
| 501 | cl_dens_diff_ = hcore_.clone();
|
---|
| 502 | cl_dens_diff_.assign(0.0);
|
---|
| 503 |
|
---|
| 504 | op_dens_ = hcore_.clone();
|
---|
| 505 | op_dens_.assign(0.0);
|
---|
| 506 |
|
---|
| 507 | op_dens_diff_ = hcore_.clone();
|
---|
| 508 | op_dens_diff_.assign(0.0);
|
---|
| 509 |
|
---|
| 510 | // gmat is in AO basis
|
---|
| 511 | cl_gmat_ = basis()->matrixkit()->symmmatrix(basis()->basisdim());
|
---|
| 512 | cl_gmat_.assign(0.0);
|
---|
| 513 |
|
---|
| 514 | op_gmat_ = cl_gmat_.clone();
|
---|
| 515 | op_gmat_.assign(0.0);
|
---|
| 516 |
|
---|
| 517 | if (cl_fock_.result_noupdate().null()) {
|
---|
| 518 | cl_fock_ = hcore_.clone();
|
---|
| 519 | cl_fock_.result_noupdate().assign(0.0);
|
---|
| 520 | op_fock_ = hcore_.clone();
|
---|
| 521 | op_fock_.result_noupdate().assign(0.0);
|
---|
| 522 | }
|
---|
| 523 |
|
---|
| 524 | // set up trial vector
|
---|
| 525 | initial_vector(1);
|
---|
| 526 |
|
---|
| 527 | oso_scf_vector_ = oso_eigenvectors_.result_noupdate();
|
---|
| 528 | }
|
---|
| 529 |
|
---|
| 530 | void
|
---|
| 531 | HSOSSCF::done_vector()
|
---|
| 532 | {
|
---|
| 533 | done_threads();
|
---|
| 534 |
|
---|
| 535 | cl_gmat_ = 0;
|
---|
| 536 | cl_dens_ = 0;
|
---|
| 537 | cl_dens_diff_ = 0;
|
---|
| 538 | op_gmat_ = 0;
|
---|
| 539 | op_dens_ = 0;
|
---|
| 540 | op_dens_diff_ = 0;
|
---|
| 541 |
|
---|
| 542 | oso_scf_vector_ = 0;
|
---|
| 543 | }
|
---|
| 544 |
|
---|
| 545 | RefSymmSCMatrix
|
---|
| 546 | HSOSSCF::alpha_density()
|
---|
| 547 | {
|
---|
| 548 | RefSymmSCMatrix dens1(so_dimension(), basis_matrixkit());
|
---|
| 549 | RefSymmSCMatrix dens2(so_dimension(), basis_matrixkit());
|
---|
| 550 |
|
---|
| 551 | so_density(dens1, 2.0);
|
---|
| 552 | so_density(dens2, 1.0);
|
---|
| 553 | dens1.accumulate(dens2);
|
---|
| 554 | dens2=0;
|
---|
| 555 |
|
---|
| 556 | return dens1;
|
---|
| 557 | }
|
---|
| 558 |
|
---|
| 559 | RefSymmSCMatrix
|
---|
| 560 | HSOSSCF::beta_density()
|
---|
| 561 | {
|
---|
| 562 | RefSymmSCMatrix dens(so_dimension(), basis_matrixkit());
|
---|
| 563 | so_density(dens, 2.0);
|
---|
| 564 | return dens;
|
---|
| 565 | }
|
---|
| 566 |
|
---|
| 567 | void
|
---|
| 568 | HSOSSCF::reset_density()
|
---|
| 569 | {
|
---|
| 570 | cl_gmat_.assign(0.0);
|
---|
| 571 | cl_dens_diff_.assign(cl_dens_);
|
---|
| 572 |
|
---|
| 573 | op_gmat_.assign(0.0);
|
---|
| 574 | op_dens_diff_.assign(op_dens_);
|
---|
| 575 | }
|
---|
| 576 |
|
---|
| 577 | double
|
---|
| 578 | HSOSSCF::new_density()
|
---|
| 579 | {
|
---|
| 580 | // copy current density into density diff and scale by -1. later we'll
|
---|
| 581 | // add the new density to this to get the density difference.
|
---|
| 582 | cl_dens_diff_.assign(cl_dens_);
|
---|
| 583 | cl_dens_diff_.scale(-1.0);
|
---|
| 584 |
|
---|
| 585 | op_dens_diff_.assign(op_dens_);
|
---|
| 586 | op_dens_diff_.scale(-1.0);
|
---|
| 587 |
|
---|
| 588 | so_density(cl_dens_, 2.0);
|
---|
| 589 | cl_dens_.scale(2.0);
|
---|
| 590 |
|
---|
| 591 | so_density(op_dens_, 1.0);
|
---|
| 592 |
|
---|
| 593 | cl_dens_.accumulate(op_dens_);
|
---|
| 594 |
|
---|
| 595 | cl_dens_diff_.accumulate(cl_dens_);
|
---|
| 596 | op_dens_diff_.accumulate(op_dens_);
|
---|
| 597 |
|
---|
| 598 | Ref<SCElementScalarProduct> sp(new SCElementScalarProduct);
|
---|
| 599 | cl_dens_diff_.element_op(sp.pointer(), cl_dens_diff_);
|
---|
| 600 |
|
---|
| 601 | double delta = sp->result();
|
---|
| 602 | delta = sqrt(delta/i_offset(cl_dens_diff_.n()));
|
---|
| 603 |
|
---|
| 604 | return delta;
|
---|
| 605 | }
|
---|
| 606 |
|
---|
| 607 | RefSymmSCMatrix
|
---|
| 608 | HSOSSCF::density()
|
---|
| 609 | {
|
---|
| 610 | if (!density_.computed()) {
|
---|
| 611 | RefSymmSCMatrix dens(so_dimension(), basis_matrixkit());
|
---|
| 612 | RefSymmSCMatrix dens1(so_dimension(), basis_matrixkit());
|
---|
| 613 | so_density(dens, 2.0);
|
---|
| 614 | dens.scale(2.0);
|
---|
| 615 |
|
---|
| 616 | so_density(dens1, 1.0);
|
---|
| 617 | dens.accumulate(dens1);
|
---|
| 618 | dens1=0;
|
---|
| 619 |
|
---|
| 620 | density_ = dens;
|
---|
| 621 | // only flag the density as computed if the calc is converged
|
---|
| 622 | if (!value_needed()) density_.computed() = 1;
|
---|
| 623 | }
|
---|
| 624 |
|
---|
| 625 | return density_.result_noupdate();
|
---|
| 626 | }
|
---|
| 627 |
|
---|
| 628 | double
|
---|
| 629 | HSOSSCF::scf_energy()
|
---|
| 630 | {
|
---|
| 631 | RefSymmSCMatrix t = cl_fock_.result_noupdate().copy();
|
---|
| 632 | t.accumulate(hcore_);
|
---|
| 633 |
|
---|
| 634 | RefSymmSCMatrix go = op_fock_.result_noupdate().copy();
|
---|
| 635 | go.scale(-1.0);
|
---|
| 636 | go.accumulate(cl_fock_.result_noupdate());
|
---|
| 637 |
|
---|
| 638 | SCFEnergy *eop = new SCFEnergy;
|
---|
| 639 | eop->reference();
|
---|
| 640 | Ref<SCElementOp2> op = eop;
|
---|
| 641 | t.element_op(op, cl_dens_);
|
---|
| 642 |
|
---|
| 643 | double cl_e = eop->result();
|
---|
| 644 |
|
---|
| 645 | eop->reset();
|
---|
| 646 | go.element_op(op, op_dens_);
|
---|
| 647 | double op_e = eop->result();
|
---|
| 648 |
|
---|
| 649 | op=0;
|
---|
| 650 | eop->dereference();
|
---|
| 651 | delete eop;
|
---|
| 652 |
|
---|
| 653 | return cl_e-op_e;
|
---|
| 654 | }
|
---|
| 655 |
|
---|
| 656 | Ref<SCExtrapData>
|
---|
| 657 | HSOSSCF::extrap_data()
|
---|
| 658 | {
|
---|
| 659 | Ref<SCExtrapData> data =
|
---|
| 660 | new SymmSCMatrix2SCExtrapData(cl_fock_.result_noupdate(),
|
---|
| 661 | op_fock_.result_noupdate());
|
---|
| 662 | return data;
|
---|
| 663 | }
|
---|
| 664 |
|
---|
| 665 | RefSymmSCMatrix
|
---|
| 666 | HSOSSCF::effective_fock()
|
---|
| 667 | {
|
---|
| 668 | // use fock() instead of cl_fock_ just in case this is called from
|
---|
| 669 | // someplace outside SCF::compute_vector()
|
---|
| 670 | RefSymmSCMatrix mofock(oso_dimension(), basis_matrixkit());
|
---|
| 671 | mofock.assign(0.0);
|
---|
| 672 |
|
---|
| 673 | RefSymmSCMatrix mofocko(oso_dimension(), basis_matrixkit());
|
---|
| 674 | mofocko.assign(0.0);
|
---|
| 675 |
|
---|
| 676 | // use eigenvectors if oso_scf_vector_ is null
|
---|
| 677 | if (oso_scf_vector_.null()) {
|
---|
| 678 | mofock.accumulate_transform(eigenvectors(), fock(0),
|
---|
| 679 | SCMatrix::TransposeTransform);
|
---|
| 680 | mofocko.accumulate_transform(eigenvectors(), fock(1),
|
---|
| 681 | SCMatrix::TransposeTransform);
|
---|
| 682 | } else {
|
---|
| 683 | RefSCMatrix so_to_oso_tr = so_to_orthog_so().t();
|
---|
| 684 | mofock.accumulate_transform(so_to_oso_tr * oso_scf_vector_, fock(0),
|
---|
| 685 | SCMatrix::TransposeTransform);
|
---|
| 686 | mofocko.accumulate_transform(so_to_oso_tr * oso_scf_vector_, fock(1),
|
---|
| 687 | SCMatrix::TransposeTransform);
|
---|
| 688 | }
|
---|
| 689 |
|
---|
| 690 | Ref<SCElementOp2> op = new GSGeneralEffH(this);
|
---|
| 691 | mofock.element_op(op, mofocko);
|
---|
| 692 |
|
---|
| 693 | return mofock;
|
---|
| 694 | }
|
---|
| 695 |
|
---|
| 696 | /////////////////////////////////////////////////////////////////////////////
|
---|
| 697 |
|
---|
| 698 | void
|
---|
| 699 | HSOSSCF::init_gradient()
|
---|
| 700 | {
|
---|
| 701 | // presumably the eigenvectors have already been computed by the time
|
---|
| 702 | // we get here
|
---|
| 703 | oso_scf_vector_ = oso_eigenvectors_.result_noupdate();
|
---|
| 704 | }
|
---|
| 705 |
|
---|
| 706 | void
|
---|
| 707 | HSOSSCF::done_gradient()
|
---|
| 708 | {
|
---|
| 709 | cl_dens_=0;
|
---|
| 710 | op_dens_=0;
|
---|
| 711 | oso_scf_vector_ = 0;
|
---|
| 712 | }
|
---|
| 713 |
|
---|
| 714 | /////////////////////////////////////////////////////////////////////////////
|
---|
| 715 |
|
---|
| 716 | // MO lagrangian
|
---|
| 717 | // c o v
|
---|
| 718 | // c |2*FC|2*FC|0|
|
---|
| 719 | // -------------
|
---|
| 720 | // o |2*FC| FO |0|
|
---|
| 721 | // -------------
|
---|
| 722 | // v | 0 | 0 |0|
|
---|
| 723 | //
|
---|
| 724 | RefSymmSCMatrix
|
---|
| 725 | HSOSSCF::lagrangian()
|
---|
| 726 | {
|
---|
| 727 | RefSCMatrix so_to_oso_tr = so_to_orthog_so().t();
|
---|
| 728 |
|
---|
| 729 | RefSymmSCMatrix mofock(oso_dimension(), basis_matrixkit());
|
---|
| 730 | mofock.assign(0.0);
|
---|
| 731 | mofock.accumulate_transform(so_to_oso_tr * oso_scf_vector_,
|
---|
| 732 | cl_fock_.result_noupdate(),
|
---|
| 733 | SCMatrix::TransposeTransform);
|
---|
| 734 |
|
---|
| 735 | RefSymmSCMatrix mofocko(oso_dimension(), basis_matrixkit());
|
---|
| 736 | mofocko.assign(0.0);
|
---|
| 737 | mofocko.accumulate_transform(so_to_oso_tr * oso_scf_vector_,
|
---|
| 738 | op_fock_.result_noupdate(),
|
---|
| 739 | SCMatrix::TransposeTransform);
|
---|
| 740 |
|
---|
| 741 | mofock.scale(2.0);
|
---|
| 742 |
|
---|
| 743 | Ref<SCElementOp2> op = new MOLagrangian(this);
|
---|
| 744 | mofock.element_op(op, mofocko);
|
---|
| 745 | mofocko=0;
|
---|
| 746 |
|
---|
| 747 | // transform MO lagrangian to SO basis
|
---|
| 748 | RefSymmSCMatrix so_lag(so_dimension(), basis_matrixkit());
|
---|
| 749 | so_lag.assign(0.0);
|
---|
| 750 | so_lag.accumulate_transform(so_to_oso_tr * oso_scf_vector_, mofock);
|
---|
| 751 |
|
---|
| 752 | // and then from SO to AO
|
---|
| 753 | Ref<PetiteList> pl = integral()->petite_list();
|
---|
| 754 | RefSymmSCMatrix ao_lag = pl->to_AO_basis(so_lag);
|
---|
| 755 |
|
---|
| 756 | ao_lag.scale(-1.0);
|
---|
| 757 |
|
---|
| 758 | return ao_lag;
|
---|
| 759 | }
|
---|
| 760 |
|
---|
| 761 | RefSymmSCMatrix
|
---|
| 762 | HSOSSCF::gradient_density()
|
---|
| 763 | {
|
---|
| 764 | cl_dens_ = basis_matrixkit()->symmmatrix(so_dimension());
|
---|
| 765 | op_dens_ = cl_dens_.clone();
|
---|
| 766 |
|
---|
| 767 | so_density(cl_dens_, 2.0);
|
---|
| 768 | cl_dens_.scale(2.0);
|
---|
| 769 |
|
---|
| 770 | so_density(op_dens_, 1.0);
|
---|
| 771 |
|
---|
| 772 | Ref<PetiteList> pl = integral()->petite_list(basis());
|
---|
| 773 |
|
---|
| 774 | cl_dens_ = pl->to_AO_basis(cl_dens_);
|
---|
| 775 | op_dens_ = pl->to_AO_basis(op_dens_);
|
---|
| 776 |
|
---|
| 777 | RefSymmSCMatrix tdens = cl_dens_.copy();
|
---|
| 778 | tdens.accumulate(op_dens_);
|
---|
| 779 |
|
---|
| 780 | op_dens_.scale(2.0);
|
---|
| 781 |
|
---|
| 782 | return tdens;
|
---|
| 783 | }
|
---|
| 784 |
|
---|
| 785 | /////////////////////////////////////////////////////////////////////////////
|
---|
| 786 |
|
---|
| 787 | void
|
---|
| 788 | HSOSSCF::init_hessian()
|
---|
| 789 | {
|
---|
| 790 | }
|
---|
| 791 |
|
---|
| 792 | void
|
---|
| 793 | HSOSSCF::done_hessian()
|
---|
| 794 | {
|
---|
| 795 | }
|
---|
| 796 |
|
---|
| 797 | /////////////////////////////////////////////////////////////////////////////
|
---|
| 798 |
|
---|
| 799 | void
|
---|
| 800 | HSOSSCF::two_body_deriv_hf(double * tbgrad, double exchange_fraction)
|
---|
| 801 | {
|
---|
| 802 | Ref<SCElementMaxAbs> m = new SCElementMaxAbs;
|
---|
| 803 | cl_dens_.element_op(m.pointer());
|
---|
| 804 | op_dens_.element_op(m.pointer());
|
---|
| 805 | double pmax = m->result();
|
---|
| 806 | m=0;
|
---|
| 807 |
|
---|
| 808 | // now try to figure out the matrix specialization we're dealing with.
|
---|
| 809 | // if we're using Local matrices, then there's just one subblock, or
|
---|
| 810 | // see if we can convert P to local matrices
|
---|
| 811 |
|
---|
| 812 | if (local_ || local_dens_) {
|
---|
| 813 | // grab the data pointers from the P matrices
|
---|
| 814 | double *pmat, *pmato;
|
---|
| 815 | RefSymmSCMatrix ptmp = get_local_data(cl_dens_, pmat, SCF::Read);
|
---|
| 816 | RefSymmSCMatrix potmp = get_local_data(op_dens_, pmato, SCF::Read);
|
---|
| 817 |
|
---|
| 818 | Ref<PetiteList> pl = integral()->petite_list();
|
---|
| 819 | LocalHSOSGradContribution l(pmat,pmato);
|
---|
| 820 |
|
---|
| 821 | int i;
|
---|
| 822 | int na3 = molecule()->natom()*3;
|
---|
| 823 | int nthread = threadgrp_->nthread();
|
---|
| 824 | double **grads = new double*[nthread];
|
---|
| 825 | Ref<TwoBodyDerivInt> *tbis = new Ref<TwoBodyDerivInt>[nthread];
|
---|
| 826 | for (i=0; i < nthread; i++) {
|
---|
| 827 | tbis[i] = integral()->electron_repulsion_deriv();
|
---|
| 828 | grads[i] = new double[na3];
|
---|
| 829 | memset(grads[i], 0, sizeof(double)*na3);
|
---|
| 830 | }
|
---|
| 831 |
|
---|
| 832 | LocalTBGrad<LocalHSOSGradContribution> **tblds =
|
---|
| 833 | new LocalTBGrad<LocalHSOSGradContribution>*[nthread];
|
---|
| 834 |
|
---|
| 835 | for (i=0; i < nthread; i++) {
|
---|
| 836 | tblds[i] = new LocalTBGrad<LocalHSOSGradContribution>(
|
---|
| 837 | l, tbis[i], pl, basis(), scf_grp_, grads[i], pmax,
|
---|
| 838 | desired_gradient_accuracy(), nthread, i, exchange_fraction);
|
---|
| 839 | threadgrp_->add_thread(i, tblds[i]);
|
---|
| 840 | }
|
---|
| 841 |
|
---|
| 842 | if (threadgrp_->start_threads() < 0
|
---|
| 843 | ||threadgrp_->wait_threads() < 0) {
|
---|
| 844 | ExEnv::err0() << indent
|
---|
| 845 | << "HSOSSCF: error running threads" << endl;
|
---|
| 846 | abort();
|
---|
| 847 | }
|
---|
| 848 |
|
---|
| 849 | for (i=0; i < nthread; i++) {
|
---|
| 850 | for (int j=0; j < na3; j++)
|
---|
| 851 | tbgrad[j] += grads[i][j];
|
---|
| 852 |
|
---|
| 853 | delete[] grads[i];
|
---|
| 854 | delete tblds[i];
|
---|
| 855 | }
|
---|
| 856 |
|
---|
| 857 | scf_grp_->sum(tbgrad, na3);
|
---|
| 858 | }
|
---|
| 859 |
|
---|
| 860 | // for now quit
|
---|
| 861 | else {
|
---|
| 862 | ExEnv::err0() << indent
|
---|
| 863 | << "HSOSSCF::two_body_deriv: can't do gradient yet\n";
|
---|
| 864 | abort();
|
---|
| 865 | }
|
---|
| 866 | }
|
---|
| 867 |
|
---|
| 868 | /////////////////////////////////////////////////////////////////////////////
|
---|
| 869 |
|
---|
| 870 | // Local Variables:
|
---|
| 871 | // mode: c++
|
---|
| 872 | // c-file-style: "ETS"
|
---|
| 873 | // End:
|
---|