diabatization.cc

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/*
 * Copyright 2009-2022 The VOTCA Development Team (http://www.votca.org)
 *
 * Licensed under the Apache License, Version 2.0 (the "License");
 * you may not use this file except in compliance with the License.
 * You may obtain a copy of the License at
 *
 *     http://www.apache.org/licenses/LICENSE-2.0
 *
 * Unless required by applicable law or agreed to in writing, software
 * distributed under the License is distributed on an "AS IS" BASIS,
 * WITHOUT WARRANTIES OR CONDITIONS OF ANY KIND, either express or implied.
 * See the License for the specific language governing permissions and
 * limitations under the License.
 *
 */
 
#include "diabatization.h"
 
using boost::format;
using std::flush;
 
namespace votca {
namespace xtp {
 
void Diabatization::ParseOptions(const tools::Property& user_options) {
 
  log_.setReportLevel(Log::current_level);
  log_.setMultithreading(true);
  log_.setCommonPreface("\n...");
 
  tools::Property options = user_options;
 
  // getting diabatization method and checking validity
  method_ = options.get(".method").as<std::string>();
  if (method_ == "er") {
    XTP_LOG(Log::error, log_) << "Method : Edminston-Rudenberg" << flush;
  } else if (method_ == "gmh") {
    XTP_LOG(Log::error, log_) << "Method : Generalized Mulliken-Hush" << flush;
  } else if (method_ == "fcd") {
    XTP_LOG(Log::error, log_) << "Method : Fragment Charge Difference" << flush;
  } else {
    throw std::runtime_error("Diabatization method unknown!");
  }
 
  // getting orbfiles
  orbfile1_ = options.get(".orb_file").as<std::string>();
  // checking if this is QMMM
  if (options.exists(".orb_file2")) {
    orbfile2_ = options.get(".orb_file2").as<std::string>();
    E1_ = options.get(".E1").as<double>();
    E2_ = options.get(".E2").as<double>();
    isQMMM_ = true;
  } else {
    orbfile2_ = orbfile1_;
    isQMMM_ = false;
  }
 
  // getting state options and checking validity
  state_idx_1_ = options.get(".state_idx_1").as<Index>();
  state_idx_2_ = options.get(".state_idx_2").as<Index>();
  qmtype_ = options.get(".qmtype").as<std::string>();
  XTP_LOG(Log::error, log_) << "Type : " << qmtype_ << flush;
 
  if (state_idx_1_ < 1) {
    throw std::runtime_error("State idx 1 must start from 1.");
  } else {
    XTP_LOG(Log::error, log_) << "State 1 : " << state_idx_1_ << flush;
  }
 
  if (state_idx_2_ < 1) {
    throw std::runtime_error("State idx 2 must start from 1.");
  } else {
    XTP_LOG(Log::error, log_) << "State 2 : " << state_idx_2_ << flush;
  }
 
  useRI_ = options.get(".use_RI").as<bool>();
 
  if (options.exists(".fragments")) {
    std::vector<tools::Property*> prop_region =
        options.Select("fragments.fragment");
    Index index = 0;
    for (tools::Property* prop : prop_region) {
      std::string indices = prop->get("indices").as<std::string>();
      fragments_.push_back(QMFragment<BSE_Population>(index, indices));
      index++;
    }
  }
 
  XTP_LOG(Log::error, log_) << flush;
}
 
bool Diabatization::Run() {
 
  OPENMP::setMaxThreads(nThreads_);
 
  // set logger
  log_.setReportLevel(Log::current_level);
  // log_.setReportLevel(Log::error);
  log_.setMultithreading(true);
  log_.setCommonPreface("\n...");
 
  XTP_LOG(Log::error, log_)
      << TimeStamp() << " Reading from orbitals from files: " << orbfile1_
      << " and " << orbfile2_ << flush;
 
  // Get orbitals objects
  Orbitals orbitals1;
  Orbitals orbitals2;
 
  orbitals1.ReadFromCpt(orbfile1_);
  orbitals2.ReadFromCpt(orbfile2_);
 
  if (orbitals1.getTDAApprox()) {
    XTP_LOG(Log::error, log_)
        << TimeStamp() << " " << orbfile1_ << "  was done with TDA." << flush;
  }
  if (orbitals2.getTDAApprox()) {
    XTP_LOG(Log::error, log_)
        << TimeStamp() << " " << orbfile2_ << "  was done with TDA. " << flush;
  }
 
  double QMMM_correction;
  double J;
  double J_QMMM;
  double E1ad = 0.0;
  double E2ad = 0.0;
 
  if (method_ == "er") {
    ERDiabatization ERDiabatization(orbitals1, orbitals2, &log_, state_idx_1_,
                                    state_idx_2_, qmtype_, useRI_);
    ERDiabatization.configure();
    ERDiabatization.setUpMatrices();
 
    // Calculate optimal mixing angle
    double angle = ERDiabatization.Calculate_angle();
 
    // Calculate the diabatic Hamiltonian
    std::pair<Eigen::VectorXd, Eigen::MatrixXd> rotate_H =
        ERDiabatization.Calculate_diabatic_H(angle);
    E1ad = rotate_H.first(0);
    E2ad = rotate_H.first(1);
    Eigen::MatrixXd& diabatic_H = rotate_H.second;
 
    // Printing Output
    if (!isQMMM_) {
      XTP_LOG(Log::error, log_)
          << format("Diabatic Energy 1: %1$+1.12f eV") %
                 (diabatic_H(0, 0) * votca::tools::conv::hrt2ev)
          << flush;
      XTP_LOG(Log::error, log_)
          << format("Diabatic Energy 2: %1$+1.12f eV") %
                 (diabatic_H(1, 1) * votca::tools::conv::hrt2ev)
          << flush;
      E1_ = E1ad;
      E2_ = E2ad;
    }
 
    QMMM_correction = (E2_ - E1_) / (E2ad - E1ad);
    J = diabatic_H(1, 0) * votca::tools::conv::hrt2ev;
    J_QMMM = J * QMMM_correction;
 
    if (std::abs(diabatic_H(1, 0) - diabatic_H(0, 1)) >
        1e-4 * std::abs(diabatic_H(1, 0))) {
      XTP_LOG(Log::error, log_) << "Different offdiagonal "
                                << diabatic_H(0, 1) * votca::tools::conv::hrt2ev
                                << " --- Check carefully!" << flush;
    }
  } else if (method_ == "gmh") {
 
    GMHDiabatization GMHDiabatization(orbitals1, orbitals2, &log_, state_idx_1_,
                                      state_idx_2_, qmtype_);
 
    GMHDiabatization.configure();
    std::pair<double, double> coupling = GMHDiabatization.calculate_coupling();
 
    double J_unproj = coupling.first * votca::tools::conv::hrt2ev;
    J = coupling.second * votca::tools::conv::hrt2ev;
 
    XTP_LOG(Log::error, log_)
        << format("Unprojected diabatic Coupling: %1$+1.12f eV") % (J_unproj)
        << flush;
    std::pair<double, double> Ead = GMHDiabatization.adiabatic_energies();
 
    E1ad = Ead.first;
    E2ad = Ead.second;
 
    if (isQMMM_) {
      QMMM_correction = (E2_ - E1_) / (Ead.second - Ead.first);
      J_QMMM = J * QMMM_correction;
    }
 
  } else if (method_ == "fcd") {
 
    // check if fragments are empty
    if (fragments_.size() == 0) {
      throw std::runtime_error("Fragments are undefined in FCD!");
    }
 
    FCDDiabatization FCDDiabatization(orbitals1, orbitals2, &log_, state_idx_1_,
                                      state_idx_2_, qmtype_, fragments_);
 
    FCDDiabatization.configure();
 
    J = FCDDiabatization.calculate_coupling() * votca::tools::conv::hrt2ev;
    std::pair<double, double> Ead = FCDDiabatization.adiabatic_energies();
    E1ad = Ead.first;
    E2ad = Ead.second;
    if (isQMMM_) {
      QMMM_correction = (E2_ - E1_) / (Ead.second - Ead.first);
      J_QMMM = J * QMMM_correction;
    }
  }
 
  // print output
  XTP_LOG(Log::error, log_)
      << format("Internal adiabatic energies: %1$+1.12f eV and %2$+1.12f eV") %
             (E1ad * votca::tools::conv::hrt2ev) %
             (E2ad * votca::tools::conv::hrt2ev)
      << flush;
 
  XTP_LOG(Log::error, log_)
      << format("Diabatic Coupling: %1$+1.12f eV ") % (J) << flush;
  if (isQMMM_) {
 
    XTP_LOG(Log::error, log_)
        << format("QMMM adiabatic energies: %1$+1.12f eV and %2$+1.12f eV") %
               (E1_ * votca::tools::conv::hrt2ev) %
               (E2_ * votca::tools::conv::hrt2ev)
        << flush;
 
    XTP_LOG(Log::error, log_)
        << format("QMMM correction factor: %1$+1.12f ") % (QMMM_correction)
        << flush;
    XTP_LOG(Log::error, log_)
        << format("Diabatic Coupling with QMMM: %1$+1.12f eV ") % (J_QMMM)
        << flush;
  }
 
  return true;
}
}  // namespace xtp
}  // namespace votca