diff --git a/CMakeLists.txt b/CMakeLists.txt index 0e52554fb..291c574ac 100644 --- a/CMakeLists.txt +++ b/CMakeLists.txt @@ -59,6 +59,7 @@ include(${PROJECT_SOURCE_DIR}/cmake/custom/mpi.cmake) include(${PROJECT_SOURCE_DIR}/cmake/custom/omp.cmake) include(${PROJECT_SOURCE_DIR}/cmake/custom/sad_basis.cmake) include(${PROJECT_SOURCE_DIR}/cmake/custom/hirshfeld.cmake) +include(${PROJECT_SOURCE_DIR}/cmake/custom/azora_potentials.cmake) include(${PROJECT_SOURCE_DIR}/cmake/custom/main.cmake) include(${PROJECT_SOURCE_DIR}/cmake/custom/feature_summary.cmake) include(${PROJECT_SOURCE_DIR}/cmake/custom/tests.cmake) diff --git a/cmake/custom/azora_potentials.cmake b/cmake/custom/azora_potentials.cmake new file mode 100644 index 000000000..1478838ff --- /dev/null +++ b/cmake/custom/azora_potentials.cmake @@ -0,0 +1,7 @@ +set(AZORA_POTENTIALS_SOURCE_DIR ${PROJECT_SOURCE_DIR}/share/azora_potentials CACHE STRING "Path to azora potentials") +set(AZORA_POTENTIALS_INSTALL_DIR ${CMAKE_INSTALL_PREFIX}/share/${PROJECT_NAME}/azora_potentials) +install( + DIRECTORY share/azora_potentials + DESTINATION share/${PROJECT_NAME} + ) + diff --git a/doc/users/user_ref.rst b/doc/users/user_ref.rst index 5095d996f..dafff9294 100644 --- a/doc/users/user_ref.rst +++ b/doc/users/user_ref.rst @@ -326,14 +326,14 @@ User input reference **Default** ``True`` - :relativity: Set method for relativistic treatment. ``ZORA`` for fully self-consistent ZORA potential, by default including all potentials (``V_nuc``, ``J``, ``V_xc``) but this can be overwritten in the ``ZORA`` section. ``nZORA`` is shortcut for nuclear-ZORA, i.e. only ``V_nuc`` is included (this keyword takes precedence over keywords in the ``ZORA`` section). + :relativity: Set method for relativistic treatment. ``ZORA`` for fully self-consistent ZORA potential, by default including all potentials (``V_nuc``, ``J``, ``V_xc``) but this can be overwritten in the ``ZORA`` section. ``nZORA`` is shortcut for nuclear-ZORA, i.e. only ``V_nuc`` is included (this keyword takes precedence over keywords in the ``ZORA`` section). ``azora`` uses atomic ZORA potentials, which are precomputed and read from the directory specified in the ``azora_potential_path`` keyword. **Type** ``str`` **Default** ``none`` **Predicates** - - ``value.lower() in ['none', 'zora', 'nzora']`` + - ``value.lower() in ['none', 'zora', 'nzora', 'azora']`` :environment: Set method for treatment of environment. ``none`` for vacuum calculation. ``PCM`` for Polarizable Continuum Model, which will activate the ``PCM`` input section for further parametrization options. The ``PB`` and ``LPB`` variants add the Poisson-Boltzmann and Linearized Poisson-Boltzmann solvers, respectively. @@ -374,6 +374,12 @@ User input reference **Default** ``True`` + :azora_potential_path: Path to the directory containing the AZORA potentials. If not specified, the default potentials will be used. Look into the readme file in the share/azora_potentials directory for information about the potential file format. + + **Type** ``str`` + + **Default** ``none`` + :DFT: Define the exchange-correlation functional in case of DFT. :red:`Keywords` diff --git a/python/mrchem/helpers.py b/python/mrchem/helpers.py index 360ce75a5..de7731dc8 100644 --- a/python/mrchem/helpers.py +++ b/python/mrchem/helpers.py @@ -59,7 +59,19 @@ def write_scf_fock(user_dict, wf_dict, origin): "include_nuclear": user_dict["ZORA"]["include_nuclear"], "include_coulomb": user_dict["ZORA"]["include_coulomb"], "include_xc": user_dict["ZORA"]["include_xc"], + "isAZORA": False, + "azora_potential_path": user_dict["ZORA"]["azora_potential_path"] } + # AZORA + if user_dict["WaveFunction"]["relativity"].lower() == "azora": + fock_dict["zora_operator"] = { + "include_nuclear": False, + "include_coulomb": False, + "include_xc": False, + "isAZORA": True + } + if user_dict["ZORA"]["azora_potential_path"].lower() != "none": + fock_dict["zora_operator"]["azora_potential_path"] = user_dict["ZORA"]["azora_potential_path"] # Kinetic fock_dict["kinetic_operator"] = {"derivative": user_dict["Derivatives"]["kinetic"]} @@ -513,12 +525,21 @@ def parse_wf_method(user_dict): # Determine relativity name label for print outs to the output file relativity_name = "None" + wf_dict = dict() if user_dict["WaveFunction"]["relativity"].lower() in ["none"]: user_dict["WaveFunction"]["relativity"] = "off" user_dict["ZORA"]["include_nuclear"] = False user_dict["ZORA"]["include_coulomb"] = False user_dict["ZORA"]["include_xc"] = False + if user_dict["WaveFunction"]["relativity"].lower() in ["azora"]: + relativity_name = "AZORA" + user_dict["WaveFunction"]["relativity"] = "azora" + user_dict["ZORA"]["include_nuclear"] = False + user_dict["ZORA"]["include_coulomb"] = False + user_dict["ZORA"]["include_xc"] = False + user_dict["ZORA"]["isAZORA"] = True + if user_dict["WaveFunction"]["relativity"].lower() in ["nzora"]: user_dict["WaveFunction"]["relativity"] = "zora" user_dict["ZORA"]["include_nuclear"] = True @@ -541,10 +562,10 @@ def parse_wf_method(user_dict): else: raise RuntimeError("ZORA selected, but no ZORA potential included") - if user_dict["ZORA"]["include_xc"] and not restricted: - raise RuntimeError( - "ZORA (V_xc) not available for unrestricted wavefunctions" - ) + # if user_dict["ZORA"]["include_xc"] and not restricted: + # raise RuntimeError( + # "ZORA (V_xc) not available for unrestricted wavefunctions" + # ) # Determine environment name label for print outs to the output file environment_name = "None" @@ -567,14 +588,12 @@ def parse_wf_method(user_dict): # Labels to aggregate external_name = f"Electric field ({x}, {y}, {z})" - wf_dict = { - "relativity_name": relativity_name, - "environment_name": environment_name, - "external_name": external_name, - "method_name": method_name, - "method_type": method_type, - "dft_funcs": dft_funcs, - } + wf_dict["relativity_name"] = relativity_name + wf_dict["environment_name"] = environment_name + wf_dict["external_name"] = external_name + wf_dict["method_name"] = method_name + wf_dict["method_type"] = method_type + wf_dict["dft_funcs"] = dft_funcs return wf_dict diff --git a/python/mrchem/input_parser/api.py b/python/mrchem/input_parser/api.py index 062022f1a..d16a573ac 100644 --- a/python/mrchem/input_parser/api.py +++ b/python/mrchem/input_parser/api.py @@ -297,7 +297,8 @@ def stencil() -> JSONDict: 'predicates': [ 'value.lower() ' "in ['none', " "'zora', " - "'nzora']"], + "'nzora', " + "'azora']"], 'type': 'str'}, { 'default': 'none', 'name': 'environment', @@ -326,7 +327,10 @@ def stencil() -> JSONDict: 'type': 'bool'}, { 'default': True, 'name': 'include_xc', - 'type': 'bool'}], + 'type': 'bool'}, + { 'default': 'none', + 'name': 'azora_potential_path', + 'type': 'str'}], 'name': 'ZORA'}, { 'keywords': [ { 'default': 0.0, 'name': 'density_cutoff', diff --git a/python/mrchem/input_parser/docs/user_ref.rst b/python/mrchem/input_parser/docs/user_ref.rst index 5095d996f..dafff9294 100644 --- a/python/mrchem/input_parser/docs/user_ref.rst +++ b/python/mrchem/input_parser/docs/user_ref.rst @@ -326,14 +326,14 @@ User input reference **Default** ``True`` - :relativity: Set method for relativistic treatment. ``ZORA`` for fully self-consistent ZORA potential, by default including all potentials (``V_nuc``, ``J``, ``V_xc``) but this can be overwritten in the ``ZORA`` section. ``nZORA`` is shortcut for nuclear-ZORA, i.e. only ``V_nuc`` is included (this keyword takes precedence over keywords in the ``ZORA`` section). + :relativity: Set method for relativistic treatment. ``ZORA`` for fully self-consistent ZORA potential, by default including all potentials (``V_nuc``, ``J``, ``V_xc``) but this can be overwritten in the ``ZORA`` section. ``nZORA`` is shortcut for nuclear-ZORA, i.e. only ``V_nuc`` is included (this keyword takes precedence over keywords in the ``ZORA`` section). ``azora`` uses atomic ZORA potentials, which are precomputed and read from the directory specified in the ``azora_potential_path`` keyword. **Type** ``str`` **Default** ``none`` **Predicates** - - ``value.lower() in ['none', 'zora', 'nzora']`` + - ``value.lower() in ['none', 'zora', 'nzora', 'azora']`` :environment: Set method for treatment of environment. ``none`` for vacuum calculation. ``PCM`` for Polarizable Continuum Model, which will activate the ``PCM`` input section for further parametrization options. The ``PB`` and ``LPB`` variants add the Poisson-Boltzmann and Linearized Poisson-Boltzmann solvers, respectively. @@ -374,6 +374,12 @@ User input reference **Default** ``True`` + :azora_potential_path: Path to the directory containing the AZORA potentials. If not specified, the default potentials will be used. Look into the readme file in the share/azora_potentials directory for information about the potential file format. + + **Type** ``str`` + + **Default** ``none`` + :DFT: Define the exchange-correlation functional in case of DFT. :red:`Keywords` diff --git a/python/template.yml b/python/template.yml index 224cc003c..86735123c 100644 --- a/python/template.yml +++ b/python/template.yml @@ -290,12 +290,14 @@ sections: type: str default: none predicates: - - value.lower() in ['none', 'zora', 'nzora'] + - value.lower() in ['none', 'zora', 'nzora', 'azora'] docstring: | Set method for relativistic treatment. ``ZORA`` for fully self-consistent ZORA potential, by default including all potentials (``V_nuc``, ``J``, ``V_xc``) but this can be overwritten in the ``ZORA`` section. ``nZORA`` is shortcut for nuclear-ZORA, i.e. only ``V_nuc`` is included (this keyword takes precedence over keywords in the ``ZORA`` section). + ``azora`` uses atomic ZORA potentials, which are precomputed and read from the directory + specified in the ``azora_potential_path`` keyword. - name: environment type: str default: none @@ -335,6 +337,12 @@ sections: default: true docstring: | Include the XC potential ``V_xc`` in the ZORA potential. + - name: azora_potential_path + type: str + default: none + docstring: | + Path to the directory containing the AZORA potentials. If not specified, the default potentials will be used. + Look into the readme file in the share/azora_potentials directory for information about the potential file format. - name: DFT docstring: | Define the exchange-correlation functional in case of DFT. diff --git a/share/azora_potentials/Ag.txt b/share/azora_potentials/Ag.txt new file mode 100644 index 000000000..54f407067 --- /dev/null +++ b/share/azora_potentials/Ag.txt @@ -0,0 +1,192 @@ + 0.33080451177886064E-01 0.97578195523695E-18 -0.53011488026212E+06 + 0.33976686288310895E-01 0.29483069282768E-04 -0.51514084356076E+06 + 0.36930869938621623E-01 0.61082173640461E-04 -0.47092923522000E+06 + 0.42336615774510249E-01 0.94949178290611E-04 -0.40600313414160E+06 + 0.50383327619280230E-01 0.13124684686428E-03 -0.33516210917034E+06 + 0.60751663960988619E-01 0.17014962340302E-03 -0.27155093372266E+06 + 0.72621275478470498E-01 0.21184447044981E-03 -0.22102855149454E+06 + 0.85167684844492553E-01 0.25653176725507E-03 -0.18293511952726E+06 + 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-0,0 +1,3 @@ +Data directory that contains the radial potentials and relativistic dampening functions for the azora method. +Format of the potential files: Data is stored columnwise. First column is the dampening function (not read), second column is radius, third is atomic zora potential. +The potentials were generated with a sperically symmetric LDA calculation and a gaussian nuclear potential of width 1e-4. \ No newline at end of file diff --git a/share/azora_potentials/Rb.txt b/share/azora_potentials/Rb.txt new file mode 100644 index 000000000..8de0eb374 --- /dev/null +++ b/share/azora_potentials/Rb.txt @@ -0,0 +1,192 @@ + 0.41281257466943562E-01 0.97578195523695E-18 -0.41734280412935E+06 + 0.42379457165528357E-01 0.29483069282768E-04 -0.40555474250379E+06 + 0.45991948913118363E-01 0.61082173640461E-04 -0.37074995042951E+06 + 0.52573036349195343E-01 0.94949178290611E-04 -0.31963803386233E+06 + 0.62299788845476343E-01 0.13124684686428E-03 -0.26386970840236E+06 + 0.74711808928044923E-01 0.17014962340302E-03 -0.21379297253070E+06 + 0.88756270457403696E-01 0.21184447044981E-03 -0.17402017294823E+06 + 0.10341377966405832E+00 0.25653176725507E-03 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AZORA_POTENTIALS_INSTALL_DIR="${AZORA_POTENTIALS_INSTALL_DIR}" +) + target_link_libraries(mrchem PRIVATE Eigen3::Eigen diff --git a/src/driver.cpp b/src/driver.cpp index 1d076c08b..a87e04e7b 100644 --- a/src/driver.cpp +++ b/src/driver.cpp @@ -56,6 +56,7 @@ #include "qmoperators/one_electron/NuclearGradientOperator.h" #include "qmoperators/one_electron/NuclearOperator.h" #include "qmoperators/one_electron/ZoraOperator.h" +#include "qmoperators/one_electron/AZoraPotential.h" #include "qmoperators/one_electron/H_BB_dia.h" #include "qmoperators/one_electron/H_BM_dia.h" @@ -1064,10 +1065,40 @@ void driver::build_fock_operator(const json &json_fock, Molecule &mol, FockBuild auto c = PhysicalConstants::get("light_speed"); F.setLightSpeed(c); - auto include_nuclear = json_fock["zora_operator"]["include_nuclear"]; - auto include_coulomb = json_fock["zora_operator"]["include_coulomb"]; - auto include_xc = json_fock["zora_operator"]["include_xc"]; - F.setZoraType(include_nuclear, include_coulomb, include_xc); + bool include_nuclear = json_fock["zora_operator"]["include_nuclear"]; + bool include_coulomb = json_fock["zora_operator"]["include_coulomb"]; + bool include_xc = json_fock["zora_operator"]["include_xc"]; + bool is_azora = json_fock["zora_operator"]["isAZORA"]; + F.setZoraType(include_nuclear, include_coulomb, include_xc, is_azora); + if (is_azora) { + std::string azora_dir_src = AZORA_POTENTIALS_SOURCE_DIR; + std::string azora_dir_install = AZORA_POTENTIALS_INSTALL_DIR; + std::string azora_dir = ""; + if (json_fock["zora_operator"].contains("azora_potential_path")) { + azora_dir = json_fock["zora_operator"]["azora_potential_path"]; + } + + std::string azora_dir_final; + if (azora_dir != "") { + azora_dir_final = azora_dir; + } else { + if (std::filesystem::exists(azora_dir_install)) { + azora_dir_final = azora_dir_install; + } else { + if (std::filesystem::exists(azora_dir_src)) { + azora_dir_final = azora_dir_src; + } else { + MSG_ABORT("AZORA: No directory provided and no default directories found."); + } + } + } + int adap = 0; + bool share = false; + + mrchem::Nuclei nuclei = mol.getNuclei(); + F.getAZoraChiPotential() = std::make_shared(nuclei, adap, azora_dir_final, share, c); + F.setNucs(nuclei); + } } /////////////////////////////////////////////////////////// ////////////////// Coulomb Operator /////////////////// diff --git a/src/qmoperators/one_electron/AZoraPotential.cpp b/src/qmoperators/one_electron/AZoraPotential.cpp new file mode 100644 index 000000000..3b2cb92ca --- /dev/null +++ b/src/qmoperators/one_electron/AZoraPotential.cpp @@ -0,0 +1,99 @@ +#include "AZoraPotential.h" + +#include "mrchem.h" +#include "chemistry/Molecule.h" +#include "chemistry/Nucleus.h" +#include +#include +#include +#include +#include "utils/PolyInterpolator.h" +#include "qmoperators/QMOperator.h" +#include "qmoperators/QMPotential.h" + +/** + * @brief Read ZORA potential from file. Check if file exists and abort if it does not. + * @param path Path to the file containing the ZORA potential + * @param rGrid Vector containing the radial grid + * @param vZora Vector containing the ZORA potential + * @param kappa Vector containing the kappa parameter +*/ +void readZoraPotential(const std::string path, Eigen::VectorXd &rGrid, Eigen::VectorXd &vZora, Eigen::VectorXd &kappa){ + std::vector r, v, k; + bool file_exists = std::filesystem::exists(path); + if (!file_exists) { + std::cerr << "File " << path << " does not exist." << std::endl; + std::cout << "File " << path << " does not exist." << std::endl; + exit(1); + } + std::ifstream file(path); + std::string line; + double r_, v_, k_; + while (std::getline(file, line)) { + std::istringstream iss(line); + iss >> k_ >> r_ >> v_; + r.push_back(r_); + v.push_back(v_); + k.push_back(k_); + } + file.close(); + rGrid = Eigen::Map(r.data(), r.size()); + vZora = Eigen::Map(v.data(), v.size()); + kappa = Eigen::Map(k.data(), k.size()); + // The kappa function is half of what is defined in the paper Scalar + // Relativistic Effects with Multiwavelets: Implementation and Benchmark + // it is not used in the code, only the potential is used +} + +namespace mrchem { + + /** + * Initialize the azora potential based on the molecule. + * This method would typically setup the real and imaginary function trees + * representing the potential. + */ + void AZoraPotential::initAzoraPotential() { + + int n = nucs.size(); + Eigen::VectorXd rGrid, vZora, kappa; + atomicPotentials.clear(); + + // std::vector atomicPotentials; + + std::string element; + std::string filename; + for (int i = 0; i < n; i++) { + element = nucs[i].getElement().getSymbol(); + filename = this->azora_dir + '/' + element + ".txt"; + readZoraPotential(filename, rGrid, vZora, kappa); + interpolation_utils::PolyInterpolator potential_interpolator(rGrid, vZora); + + atomicPotentials.push_back(potential_interpolator); + } + // project(this->prec); + } + + void AZoraPotential::project(double proj_prec){ + if (isProjected) free(mrchem::NUMBER::Total); + mrcpp::ComplexFunction vtot; + this->prec = proj_prec; + auto chi_analytic = [this](const mrcpp::Coord<3>& r) { + return this->evalf_analytic(r); + }; + mrcpp::cplxfunc::project(vtot, chi_analytic, mrcpp::NUMBER::Real, proj_prec); + this->add(1.0, vtot); + isProjected = true; + } + + double AZoraPotential::evalf_analytic(const mrcpp::Coord<3>& r){ + double V = 0.0; + // Loop over all atoms: + for (int i = 0; i < this->atomicPotentials.size(); i++) { + mrcpp::Coord<3> r_i = nucs[i].getCoord(); + double rr = std::sqrt((r[0] - r_i[0]) * (r[0] - r_i[0]) + (r[1] - r_i[1]) * (r[1] - r_i[1]) + (r[2] - r_i[2]) * (r[2] - r_i[2])); + V += this->atomicPotentials[i].evalfLeftNoRightConstant(rr); + } + return 1 / (1 - V / (2.0 * c * c)) - 1; + } + +} // namespace mrchem diff --git a/src/qmoperators/one_electron/AZoraPotential.h b/src/qmoperators/one_electron/AZoraPotential.h new file mode 100644 index 000000000..bb9dc7e16 --- /dev/null +++ b/src/qmoperators/one_electron/AZoraPotential.h @@ -0,0 +1,82 @@ +#pragma once +#include "chemistry/Nucleus.h" +#include +#include "utils/PolyInterpolator.h" +#include "qmoperators/QMPotential.h" + + +namespace mrchem { + +/** @class AZora + * + * @brief Operator defining the AZora potential based on molecular data. + * + * Inherits from QMPotential and adds functionality to utilize an mrchem::Molecule + * for constructing the potential. + * + */ +class AZoraPotential : public QMPotential { +public: + /** + * Constructor that takes a molecule and initializes the azora potential. + * @param molecule The molecule used to construct the potential. + * @param adap Adaptive parameter from QMPotential. + * @param shared Determines if the base potential is shared. + */ + AZoraPotential(Nuclei nucs, int adap, std::string azora_dir, bool shared = false, double c = 137.035999084) + : QMPotential(adap, shared) { + this->nucs = nucs; + this->c = c; + this->azora_dir = azora_dir; + initAzoraPotential(); + } + + /** + * Copy constructor. + * @param other The other instance to copy from. + */ + AZoraPotential(const AZoraPotential& other) + : QMPotential(other) { + this->nucs = other.nucs; + this->prec = other.prec; + this->c = other.c; + this->azora_dir = other.azora_dir; + initAzoraPotential(); + } + + /** + * Destructor. + */ + virtual ~AZoraPotential(){ + free(mrchem::NUMBER::Total); + isProjected = false; + } + + // Delete copy assignment to prevent copying + AZoraPotential& operator=(const AZoraPotential&) = delete; + + /** + * Project the potential from the analytic function stored in this object. + * @param prec Projection precision. + */ + void project(double prec); + +protected: + Nuclei nucs; // The nuclei of the molecule + double prec; // The precision parameter + double c; // The speed of light + std::string azora_dir; // The directory containing the azora potential data + std::vector atomicPotentials; + bool isProjected = false; + + double evalf_analytic(const mrcpp::Coord<3>& r); + + /** + * Initialize the azora potential based on the molecule. + * This method would typically setup the real and imaginary function trees + * representing the potential. + */ + void initAzoraPotential(); +}; + +} // namespace mrchem \ No newline at end of file diff --git a/src/qmoperators/one_electron/CMakeLists.txt b/src/qmoperators/one_electron/CMakeLists.txt index 264297579..e7ded7e56 100644 --- a/src/qmoperators/one_electron/CMakeLists.txt +++ b/src/qmoperators/one_electron/CMakeLists.txt @@ -1,4 +1,5 @@ target_sources(mrchem PRIVATE ${CMAKE_CURRENT_SOURCE_DIR}/NuclearOperator.cpp ${CMAKE_CURRENT_SOURCE_DIR}/ZoraOperator.cpp + ${CMAKE_CURRENT_SOURCE_DIR}/AZoraPotential.cpp ) diff --git a/src/qmoperators/one_electron/ZoraOperator.cpp b/src/qmoperators/one_electron/ZoraOperator.cpp index d4ed96a81..1a28d8ea0 100644 --- a/src/qmoperators/one_electron/ZoraOperator.cpp +++ b/src/qmoperators/one_electron/ZoraOperator.cpp @@ -30,6 +30,7 @@ #include "qmoperators/QMPotential.h" #include "utils/print_utils.h" +#include using mrcpp::Printer; using mrcpp::Timer; @@ -40,10 +41,10 @@ ZoraOperator::ZoraOperator(QMPotential &vz, double c, double proj_prec, bool inv Timer timer; double two_cc = 2.0 * c * c; - auto k = std::make_shared(1); + std::shared_ptr k = std::make_shared(1); mrcpp::cplxfunc::deep_copy(*k, vz); - if (k->hasImag()) MSG_ERROR("Inverse of complex function"); + if (k->hasImag()) MSG_ERROR("Inverse of complex function in zora potential"); if (k->hasReal()) { mrcpp::refine_grid(k->real(), 1); if (inverse) { @@ -65,4 +66,15 @@ ZoraOperator::ZoraOperator(QMPotential &vz, double c, double proj_prec, bool inv print_utils::qmfunction(2, "ZORA operator (" + chi.name() + ")", *k, timer); } +/** + * @brief Constructor for ZoraOperator used to construct an atomic zora operator + * @param relativisticDampening shared pointer to QMPotential that contains the precompouted kappa function + * @param name name of the operator should be either "kappa" or "kappa_inv" +*/ +ZoraOperator::ZoraOperator(std::shared_ptr relativisticDampening, std::string name) { + RankZeroOperator &kappa = (*this); + kappa = relativisticDampening; + kappa.name() = name; +} + } // namespace mrchem diff --git a/src/qmoperators/one_electron/ZoraOperator.h b/src/qmoperators/one_electron/ZoraOperator.h index 2cadfb83c..239ad87ff 100644 --- a/src/qmoperators/one_electron/ZoraOperator.h +++ b/src/qmoperators/one_electron/ZoraOperator.h @@ -26,6 +26,7 @@ #pragma once #include "tensor/RankZeroOperator.h" +#include namespace mrchem { @@ -48,6 +49,9 @@ class ZoraOperator final : public RankZeroOperator { * @param inverse If true, the inverse of the chi function is calculated. */ ZoraOperator(QMPotential &vz, double c, double proj_prec, bool inverse = false); + + ZoraOperator(std::shared_ptr relativisticDampening, std::string name); + }; } // namespace mrchem diff --git a/src/qmoperators/two_electron/FockBuilder.cpp b/src/qmoperators/two_electron/FockBuilder.cpp index e36df3d1f..450aa1abd 100644 --- a/src/qmoperators/two_electron/FockBuilder.cpp +++ b/src/qmoperators/two_electron/FockBuilder.cpp @@ -47,6 +47,10 @@ #include "qmoperators/qmoperator_utils.h" #include "utils/math_utils.h" +#include "qmoperators/one_electron/AZoraPotential.h" + +#include + using mrcpp::Printer; using mrcpp::Timer; @@ -90,7 +94,7 @@ void FockBuilder::setup(double prec) { if (isZora()) { Timer t_zora; - auto c = getLightSpeed(); + double c = getLightSpeed(); mrcpp::print::header(3, "Building ZORA operators"); mrcpp::print::value(3, "Precision", prec, "(rel)", 5); mrcpp::print::value(3, "Light speed", c, "(au)", 5); @@ -104,7 +108,30 @@ void FockBuilder::setup(double prec) { this->chi_inv->setup(prec); this->zora_base.setup(prec); mrcpp::print::footer(3, t_zora, 2); - }; + } + if (isAZora()) { + Timer t_zora; + double c = getLightSpeed(); + mrcpp::print::header(3, "Building AZORA operators"); + mrcpp::print::value(3, "Precision", prec, "(rel)", 5); + mrcpp::print::value(3, "Light speed", c, "(au)", 5); + mrcpp::print::separator(3, '-'); + int adap = 0; + + chiPot->project(prec); + chiInvPot = std::make_shared(adap); + + mrcpp::cplxfunc::deep_copy(*chiInvPot, *chiPot); + + chiInvPot->real().map([](double val) { return 1.0 / (val + 1) - 1; }); + + this->chi = std::make_shared(chiPot, "kappa"); + this->chi_inv = std::make_shared(chiInvPot, "kappa_inv"); + this->chi->setup(prec); + this->chi_inv->setup(prec); + + mrcpp::print::footer(3, t_zora, 2); + } t_tot.stop(); if (plevel == 2) mrcpp::print::footer(2, t_tot, 2); @@ -125,6 +152,12 @@ void FockBuilder::clear() { this->chi_inv->clear(); this->zora_base.clear(); } + if (isAZora()) { + chi->clear(); + chi_inv->clear(); + chiPot->free(mrchem::NUMBER::Total); + chiInvPot->free(mrchem::NUMBER::Total); + } } /** @brief rotate orbitals of two-electron operators @@ -180,7 +213,7 @@ SCFEnergy FockBuilder::trace(OrbitalVector &Phi, const Nuclei &nucs) { } // Kinetic part - if (isZora()) { + if (isZora() || isAZora()) { E_kin = qmoperator::calc_kinetic_trace(momentum(), *this->chi, Phi).real() + qmoperator::calc_kinetic_trace(momentum(), Phi); } else { E_kin = qmoperator::calc_kinetic_trace(momentum(), Phi); @@ -205,7 +238,7 @@ ComplexMatrix FockBuilder::operator()(OrbitalVector &bra, OrbitalVector &ket) { mrcpp::print::header(2, "Computing Fock matrix"); ComplexMatrix T_mat = ComplexMatrix::Zero(bra.size(), ket.size()); - if (isZora()) { + if (isZora() || isAZora()) { T_mat = qmoperator::calc_kinetic_matrix(momentum(), *this->chi, bra, ket) + qmoperator::calc_kinetic_matrix(momentum(), bra, ket); } else { T_mat = qmoperator::calc_kinetic_matrix(momentum(), bra, ket); @@ -229,7 +262,7 @@ OrbitalVector FockBuilder::buildHelmholtzArgument(double prec, OrbitalVector Phi mrcpp::print::time(2, "Rotating orbitals", t_rot); OrbitalVector out; - if (isZora()) { + if (isZora() || isAZora()) { out = buildHelmholtzArgumentZORA(Phi, Psi, F_mat.real().diagonal(), prec); } else { out = buildHelmholtzArgumentNREL(Phi, Psi); @@ -241,7 +274,9 @@ OrbitalVector FockBuilder::buildHelmholtzArgument(double prec, OrbitalVector Phi return out; } -// Take 1 in notes on Overleaf +/** + * @brief Build the Helmholtz argument for the ZORA operator. Eq. 17 in J. Chem. Theory and Comput. 2024, 20, 728-737 +*/ OrbitalVector FockBuilder::buildHelmholtzArgumentZORA(OrbitalVector &Phi, OrbitalVector &Psi, DoubleVector eps, double prec) { // Get necessary operators double c = getLightSpeed(); @@ -249,11 +284,29 @@ OrbitalVector FockBuilder::buildHelmholtzArgumentZORA(OrbitalVector &Phi, Orbita MomentumOperator &p = momentum(); RankZeroOperator &V = potential(); RankZeroOperator &chi = *this->chi; - RankZeroOperator &chi_inv = *this->chi_inv; - RankZeroOperator &V_zora = this->zora_base; - + RankZeroOperator &chi_m1 = *this->chi_inv; RankZeroOperator operOne = 0.5 * tensor::dot(p(chi), p); - RankZeroOperator operThree = chi * V_zora + V_zora; + + std::shared_ptr operThreePtr = nullptr; + + if (isZora()) { + RankZeroOperator &V_zora = this->zora_base; + operThreePtr = std::make_shared(V_zora * chi + V_zora); + } else if (isAZora()) { + /* + Note that V_z * kappa = 2 c^2 * (kappa - 1) + With this trick, the expensive projection of the potential is avoided + */ + std::shared_ptr vTimesKappa = std::make_shared(0); + mrcpp::cplxfunc::deep_copy(*vTimesKappa, *chiPot); + vTimesKappa->real().map([two_cc](double val) { return two_cc * (val); }); + operThreePtr = std::make_shared(vTimesKappa); + } else { + MSG_ABORT("At this point, the ZORA or AZORA operator should be set. Exiting."); + } + + RankZeroOperator operThree = *operThreePtr; + operOne.setup(prec); operThree.setup(prec); @@ -297,7 +350,7 @@ OrbitalVector FockBuilder::buildHelmholtzArgumentZORA(OrbitalVector &Phi, Orbita operOne.clear(); Timer t_kappa; - mrchem::OrbitalVector out = chi_inv(arg); + mrchem::OrbitalVector out = chi_m1(arg); for (int i = 0; i < arg.size(); i++) { if (not mrcpp::mpi::my_orb(out[i])) continue; out[i].add(1.0, arg[i]); @@ -328,10 +381,11 @@ OrbitalVector FockBuilder::buildHelmholtzArgumentNREL(OrbitalVector &Phi, Orbita return out; } -void FockBuilder::setZoraType(bool has_nuc, bool has_coul, bool has_xc) { +void FockBuilder::setZoraType(bool has_nuc, bool has_coul, bool has_xc, bool is_azora) { this->zora_has_nuc = has_nuc; this->zora_has_coul = has_coul; this->zora_has_xc = has_xc; + this->zora_is_azora = is_azora; } std::shared_ptr FockBuilder::collectZoraBasePotential() { @@ -357,7 +411,7 @@ std::shared_ptr FockBuilder::collectZoraBasePotential() { } if (zora_has_xc) { if (getXCOperator() != nullptr) { - getXCOperator()->setSpin(SPIN::Alpha); + getXCOperator()->setSpin(SPIN::Paired); auto &xc = static_cast(getXCOperator()->getRaw(0, 0)); if (not xc.hasReal()) MSG_ERROR("ZORA: Adding empty XC potential"); vz->add(1.0, xc); diff --git a/src/qmoperators/two_electron/FockBuilder.h b/src/qmoperators/two_electron/FockBuilder.h index 34cb0ca41..0e3aa06b7 100644 --- a/src/qmoperators/two_electron/FockBuilder.h +++ b/src/qmoperators/two_electron/FockBuilder.h @@ -1,3 +1,4 @@ + /* * MRChem, a numerical real-space code for molecular electronic structure * calculations within the self-consistent field (SCF) approximations of quantum @@ -28,6 +29,8 @@ #include "qmoperators/QMPotential.h" #include "tensor/RankOneOperator.h" #include "tensor/RankZeroOperator.h" +#include +#include "chemistry/Nucleus.h" /** @class FockOperator * @@ -46,6 +49,7 @@ class MomentumOperator; class KineticOperator; class ZoraKineticOperator; class ZoraOperator; +class AZoraPotential; class NuclearOperator; class CoulombOperator; class ExchangeOperator; @@ -66,6 +70,7 @@ class FockBuilder final { std::shared_ptr &getXCOperator() { return this->xc; } std::shared_ptr &getExtOperator() { return this->ext; } std::shared_ptr &getReactionOperator() { return this->Ro; } + std::shared_ptr &getAZoraChiPotential() { return this->chiPot; } void rotate(const ComplexMatrix &U); @@ -76,8 +81,11 @@ class FockBuilder final { void setLightSpeed(double c) { this->light_speed = c; } double getLightSpeed() const { return this->light_speed; } + bool isAZora() const { return zora_is_azora; } bool isZora() const { return (zora_has_nuc || zora_has_coul || zora_has_xc); } - void setZoraType(bool has_nuc, bool has_coul, bool has_xc); + void setZoraType(bool has_nuc, bool has_coul, bool has_xc, bool is_azora); + void setAZORADirectory(const std::string &dir) {azora_dir = dir;} + void setNucs(const Nuclei &nucs) { this->nucs = nucs;} SCFEnergy trace(OrbitalVector &Phi, const Nuclei &nucs); ComplexMatrix operator()(OrbitalVector &bra, OrbitalVector &ket); @@ -88,12 +96,17 @@ class FockBuilder final { bool zora_has_nuc{false}; bool zora_has_coul{false}; bool zora_has_xc{false}; + bool zora_is_azora{false}; + std::string azora_dir = ""; + std::string azora_dir_src = ""; + std::string azora_dir_install = ""; double light_speed{-1.0}; double exact_exchange{1.0}; RankZeroOperator zora_base; double prec; + Nuclei nucs; RankZeroOperator V; ///< Total potential energy operator RankZeroOperator H_1; ///< Perturbation operators @@ -111,6 +124,8 @@ class FockBuilder final { std::shared_ptr collectZoraBasePotential(); OrbitalVector buildHelmholtzArgumentZORA(OrbitalVector &Phi, OrbitalVector &Psi, DoubleVector eps, double prec); OrbitalVector buildHelmholtzArgumentNREL(OrbitalVector &Phi, OrbitalVector &Psi); + std::shared_ptr chiPot{nullptr}; // Potential for AZORA chi operator + std::shared_ptr chiInvPot{nullptr}; // Potential for AZORA chi_inv operator }; } // namespace mrchem diff --git a/src/qmoperators/two_electron/XCPotential.cpp b/src/qmoperators/two_electron/XCPotential.cpp index 8d06a336d..763a87db2 100644 --- a/src/qmoperators/two_electron/XCPotential.cpp +++ b/src/qmoperators/two_electron/XCPotential.cpp @@ -144,6 +144,10 @@ FunctionTree<3> &XCPotential::getPotential(int spin) { pot_idx = 1; } else if (not spinFunctional) { pot_idx = 0; + } else if (spinFunctional and spin == SPIN::Paired) { + this->v_tot = std::make_shared>(*MRA); + mrcpp::add(prec(), *this->v_tot, this->potentials); + return *this->v_tot; } else { NOT_IMPLEMENTED_ABORT; } diff --git a/src/qmoperators/two_electron/XCPotential.h b/src/qmoperators/two_electron/XCPotential.h index ef0c257fd..307477690 100644 --- a/src/qmoperators/two_electron/XCPotential.h +++ b/src/qmoperators/two_electron/XCPotential.h @@ -69,6 +69,7 @@ class XCPotential : public QMPotential { double energy; ///< XC energy std::vector densities; ///< XC densities (total or alpha/beta) mrcpp::FunctionTreeVector<3> potentials; ///< XC Potential functions collected in a vector + std::shared_ptr> v_tot{nullptr}; ///< Total XC potential std::shared_ptr orbitals; ///< External set of orbitals used to build the density std::unique_ptr mrdft; ///< External XC functional to be used diff --git a/src/utils/PolyInterpolator.h b/src/utils/PolyInterpolator.h index 26bf2cd98..aa00162d3 100644 --- a/src/utils/PolyInterpolator.h +++ b/src/utils/PolyInterpolator.h @@ -124,6 +124,28 @@ class PolyInterpolator { y = polynomialInterpolate5(x_in_poly, y_in_poly, xval); return y; } + + /** + * @brief Evaluate the interpolated function at x. + * No extrapolation for x < xmin (meaning that the polynomial is evaluated at x < xmin), the last value is returned for x > xmax. + */ + double evalfLeftNoRightConstant(const double &xval) const { + double y; + if (xval > xmax) { // constant + y = this->y(n - 1); + return y; + } + + Eigen::VectorXd x_in_poly(5), y_in_poly(5); + int i = adjustIndexToBoundaries(binarySearch(this->x, xval)); + for (int k = 0; k < 5; k++) { + x_in_poly(k) = this->x(i - 2 + k); + y_in_poly(k) = this->y(i - 2 + k); + } + y = polynomialInterpolate5(x_in_poly, y_in_poly, xval); + return y; + } + private: int adjustIndexToBoundaries(int i) const { int j = i; diff --git a/tests/CMakeLists.txt b/tests/CMakeLists.txt index 42e7f36e4..ed4f2f4b4 100644 --- a/tests/CMakeLists.txt +++ b/tests/CMakeLists.txt @@ -34,5 +34,6 @@ add_subdirectory(li_solv) add_subdirectory(h_pb) add_subdirectory(h_lpb) add_subdirectory(he_zora_scf_lda) +add_subdirectory(he_azora_scf_lda) add_subdirectory(cavity_input_parser) add_subdirectory(h2_pol_solv) diff --git a/tests/he_azora_scf_lda/CMakeLists.txt b/tests/he_azora_scf_lda/CMakeLists.txt new file mode 100644 index 000000000..18aa7bafe --- /dev/null +++ b/tests/he_azora_scf_lda/CMakeLists.txt @@ -0,0 +1,10 @@ +if(ENABLE_MPI) + set(_he_azora_scf_lda_launcher "${MPIEXEC} ${MPIEXEC_NUMPROC_FLAG} 1") +endif() + +add_integration_test( + NAME "He_AZORA_SCF_LDA" + LABELS "mrchem;he_azora_scf_lda;He_AZORA_SCF_LDA;energy;lda;scf;zora;azora;he;helium" + COST 100 + LAUNCH_AGENT ${_he_azora_scf_lda_launcher} + ) diff --git a/tests/he_azora_scf_lda/he.inp b/tests/he_azora_scf_lda/he.inp new file mode 100644 index 000000000..3e1d0da66 --- /dev/null +++ b/tests/he_azora_scf_lda/he.inp @@ -0,0 +1,14 @@ +world_prec = 1.0e-4 + +WaveFunction { + method = LDA + restricted = true + relativity = azora +} + + +Molecule { +$coords +He 0.0 0.0 0.0 +$end +} diff --git a/tests/he_azora_scf_lda/reference/he.json b/tests/he_azora_scf_lda/reference/he.json new file mode 100644 index 000000000..9b19c6480 --- /dev/null +++ b/tests/he_azora_scf_lda/reference/he.json @@ -0,0 +1,372 @@ +{ + "input": { + "constants": { + "N_a": 6.02214076e+23, + "angstrom2bohrs": 1.8897261246257702, + "boltzmann_constant": 1.380649e-23, + "dipmom_au2debye": 2.5417464739297717, + "e0": 8.8541878128e-12, + "electron_g_factor": -2.00231930436256, + "elementary_charge": 1.602176634e-19, + "fine_structure_constant": 0.0072973525693, + "hartree2ev": 27.211386245988, + "hartree2kcalmol": 627.5094740630558, + "hartree2kjmol": 2625.4996394798254, + "hartree2simagnetizability": 78.9451185, + "hartree2wavenumbers": 219474.6313632, + "light_speed": 137.035999084, + "meter2bohr": 18897261246.2577 + }, + "geom_opt": { + "init_step_size": -0.5, + "max_force_component": 0.005, + "max_history_length": 10, + "max_iter": 100, + "minimal_step_size": 0.01, + "run": false, + "subspace_tolerance": 0.001, + "use_previous_guess": false + }, + "molecule": { + "charge": 0, + "coords": [ + { + "atom": "he", + "r_rms": 3.5849373401e-05, + "xyz": [ + 0.0, + 0.0, + 0.0 + ] + } + ], + "multiplicity": 1 + }, + "mpi": { + "bank_size": -1, + "numerically_exact": false, + "omp_threads": -1, + "shared_memory_size": 10000 + }, + "mra": { + "basis_order": 6, + "basis_type": "interpolating", + "boxes": [ + 2, + 2, + 2 + ], + "corner": [ + -1, + -1, + -1 + ], + "max_scale": 20, + "min_scale": -4 + }, + "printer": { + "file_name": "he", + "print_constants": false, + "print_level": 0, + "print_mpi": false, + "print_prec": 6, + "print_width": 75 + }, + "rsp_calculations": {}, + "scf_calculation": { + "fock_operator": { + "coulomb_operator": { + "poisson_prec": 0.0001, + "shared_memory": false + }, + "exchange_operator": { + "exchange_prec": -1.0, + "poisson_prec": 0.0001 + }, + "kinetic_operator": { + "derivative": "abgv_55" + }, + "nuclear_operator": { + "nuclear_model": "point_like", + "proj_prec": 0.0001, + "shared_memory": false, + "smooth_prec": 0.0001 + }, + "xc_operator": { + "shared_memory": false, + "xc_functional": { + "cutoff": 0.0, + "functionals": [ + { + "coef": 1.0, + "name": "svwn5" + } + ], + "spin": false + } + }, + "zora_operator": { + "include_coulomb": false, + "include_nuclear": false, + "include_xc": false, + "isAZORA": true + } + }, + "initial_guess": { + "environment": "None", + "external_field": "None", + "file_CUBE_a": "cube_vectors/CUBE_a_vector.json", + "file_CUBE_b": "cube_vectors/CUBE_b_vector.json", + "file_CUBE_p": "cube_vectors/CUBE_p_vector.json", + "file_basis": "initial_guess/mrchem.bas", + "file_chk": "checkpoint/phi_scf", + "file_gto_a": "initial_guess/mrchem.moa", + "file_gto_b": "initial_guess/mrchem.mob", + "file_gto_p": "initial_guess/mrchem.mop", + "file_phi_a": "initial_guess/phi_a_scf", + "file_phi_b": "initial_guess/phi_b_scf", + "file_phi_p": "initial_guess/phi_p_scf", + "localize": false, + "method": "DFT (SVWN5)", + "prec": 0.001, + "relativity": "AZORA", + "restricted": true, + "rotate": true, + "screen": 12.0, + "type": "sad_gto", + "zeta": 0 + }, + "properties": { + "dipole_moment": { + "dip-1": { + "operator": "h_e_dip", + "precision": 0.0001, + "r_O": [ + 0.0, + 0.0, + 0.0 + ] + } + } + }, + "scf_solver": { + "checkpoint": false, + "energy_thrs": -1.0, + "environment": "None", + "external_field": "None", + "file_chk": "checkpoint/phi_scf", + "final_prec": 0.0001, + "helmholtz_prec": -1.0, + "kain": 5, + "localize": false, + "max_iter": 100, + "method": "DFT (SVWN5)", + "orbital_thrs": 0.001, + "relativity": "AZORA", + "rotation": 0, + "start_prec": 0.0001 + } + }, + "schema_name": "mrchem_input", + "schema_version": 1 + }, + "output": { + "properties": { + "center_of_mass": [ + 0.0, + 0.0, + 0.0 + ], + "charge": 0, + "dipole_moment": { + "dip-1": { + "magnitude": 1.5414130052328172e-12, + "r_O": [ + 0.0, + 0.0, + 0.0 + ], + "vector": [ + 0.0, + 0.0, + 0.0 + ], + "vector_el": [ + 0.0, + 0.0, + 0.0 + ], + "vector_nuc": [ + 0.0, + 0.0, + 0.0 + ] + } + }, + "geometry": [ + { + "symbol": "He", + "xyz": [ + 0.0, + 0.0, + 0.0 + ] + } + ], + "multiplicity": 1, + "orbital_energies": { + "energy": [ + -0.570464666039006 + ], + "occupation": [ + 2.0 + ], + "spin": [ + "p" + ], + "sum_occupied": -1.140929332078012 + }, + "scf_energy": { + "E_ee": 1.9962222364216329, + "E_eext": 0.0, + "E_el": -2.835003921655858, + "E_en": -6.625820552295827, + "E_kin": 2.7679525130939138, + "E_next": 0.0, + "E_nn": 0.0, + "E_nuc": 0.0, + "E_tot": -2.835003921655858, + "E_x": 0.0, + "E_xc": -0.9733581188755775, + "Er_el": 0.0, + "Er_nuc": 0.0, + "Er_tot": 0.0 + } + }, + "provenance": { + "creator": "MRChem", + "mpi_processes": 1, + "nthreads": 8, + "routine": "mrchem.x", + "total_cores": 8, + "version": "1.2.0-alpha" + }, + "rsp_calculations": null, + "scf_calculation": { + "initial_energy": { + "E_ee": 2.0262673615492934, + "E_eext": 0.0, + "E_el": -2.8061198579393087, + "E_en": -6.595209258134876, + "E_kin": 2.7470772638332845, + "E_next": 0.0, + "E_nn": 0.0, + "E_nuc": 0.0, + "E_tot": -2.8061198579393087, + "E_x": 0.0, + "E_xc": -0.9842552251870108, + "Er_el": 0.0, + "Er_nuc": 0.0, + "Er_tot": 0.0 + }, + "scf_solver": { + "converged": true, + "cycles": [ + { + "energy_terms": { + "E_ee": 1.973384349083191, + "E_eext": 0.0, + "E_el": -2.8339954491064434, + "E_en": -6.528192694988571, + "E_kin": 2.683318941139394, + "E_next": 0.0, + "E_nn": 0.0, + "E_nuc": 0.0, + "E_tot": -2.8339954491064434, + "E_x": 0.0, + "E_xc": -0.9625060443404567, + "Er_el": 0.0, + "Er_nuc": 0.0, + "Er_tot": 0.0 + }, + "energy_total": -2.8339954491064434, + "energy_update": 0.027875591167134672, + "mo_residual": 0.0708364444278362, + "wall_time": 1.743911586 + }, + { + "energy_terms": { + "E_ee": 1.994312226962929, + "E_eext": 0.0, + "E_el": -2.8349265026797847, + "E_en": -6.6081583679284135, + "E_kin": 2.7511471759544044, + "E_next": 0.0, + "E_nn": 0.0, + "E_nuc": 0.0, + "E_tot": -2.8349265026797847, + "E_x": 0.0, + "E_xc": -0.9722275376687047, + "Er_el": 0.0, + "Er_nuc": 0.0, + "Er_tot": 0.0 + }, + "energy_total": -2.8349265026797847, + "energy_update": 0.0009310535733413339, + "mo_residual": 0.008304451068131975, + "wall_time": 1.454814606 + }, + { + "energy_terms": { + "E_ee": 1.9954809275242602, + "E_eext": 0.0, + "E_el": -2.834996526943462, + "E_en": -6.620132609175466, + "E_kin": 2.7626021706049264, + "E_next": 0.0, + "E_nn": 0.0, + "E_nuc": 0.0, + "E_tot": -2.834996526943462, + "E_x": 0.0, + "E_xc": -0.9729470158971822, + "Er_el": 0.0, + "Er_nuc": 0.0, + "Er_tot": 0.0 + }, + "energy_total": -2.834996526943462, + "energy_update": 7.002426367730408e-05, + "mo_residual": 0.0016099564962614482, + "wall_time": 1.523955258 + }, + { + "energy_terms": { + "E_ee": 1.9962222364216329, + "E_eext": 0.0, + "E_el": -2.835003921655858, + "E_en": -6.625820552295827, + "E_kin": 2.7679525130939138, + "E_next": 0.0, + "E_nn": 0.0, + "E_nuc": 0.0, + "E_tot": -2.835003921655858, + "E_x": 0.0, + "E_xc": -0.9733581188755775, + "Er_el": 0.0, + "Er_nuc": 0.0, + "Er_tot": 0.0 + }, + "energy_total": -2.835003921655858, + "energy_update": 7.394712395747405e-06, + "mo_residual": 0.0005919718940979519, + "wall_time": 1.566191235 + } + ], + "wall_time": 6.289502326 + }, + "success": true + }, + "schema_name": "mrchem_output", + "schema_version": 1, + "success": true + } +} diff --git a/tests/he_azora_scf_lda/reference/he.out b/tests/he_azora_scf_lda/reference/he.out new file mode 100644 index 000000000..8bc4fec38 --- /dev/null +++ b/tests/he_azora_scf_lda/reference/he.out @@ -0,0 +1,296 @@ + + +*************************************************************************** +*** *** +*** *** +*** __ __ ____ ____ _ *** +*** | \/ | _ \ / ___| |__ ___ _ __ ___ *** +*** | |\/| | |_) | | | '_ \ / _ \ '_ ` _ \ *** +*** | | | | _ <| |___| | | | __/ | | | | | *** +*** |_| |_|_| \_\\____|_| |_|\___|_| |_| |_| *** +*** *** +*** VERSION 1.2.0-alpha *** +*** *** +*** Git branch azora_all_potentials *** +*** Git commit hash fdae9976706e98637414 *** +*** Git commit author moritzgubler *** +*** Git commit date Tue Oct 22 11:38:42 2024 +0200 *** +*** *** +*** Contact: luca.frediani@uit.no *** +*** *** +*** Radovan Bast Magnar Bjorgve *** +*** Roberto Di Remigio Antoine Durdek *** +*** Luca Frediani Gabriel Gerez *** +*** Stig Rune Jensen Jonas Juselius *** +*** Rune Monstad Peter Wind *** +*** *** +*************************************************************************** + +--------------------------------------------------------------------------- + + MPI processes : (no bank) 1 + OpenMP threads : 8 + Total cores : 8 + +--------------------------------------------------------------------------- + +XCFun DFT library Copyright 2009-2020 Ulf Ekstrom and contributors. +See http://dftlibs.org/xcfun/ for more information. + +This is free software; see the source code for copying conditions. +There is ABSOLUTELY NO WARRANTY; not even for MERCHANTABILITY or +FITNESS FOR A PARTICULAR PURPOSE. For details see the documentation. +Scientific users of this library should cite +U. Ekstrom, L. Visscher, R. Bast, A. J. Thorvaldsen and K. Ruud; +J.Chem.Theor.Comp. 2010, DOI: 10.1021/ct100117s + +--------------------------------------------------------------------------- + + MRCPP version : 1.6.0-alpha + Git branch : HEAD + Git commit hash : 720133372c9717134c5a + Git commit author : gitpeterwind + Git commit date : Thu Feb 15 13:44:31 2024 +0100 + + Linear algebra : EIGEN v3.4.0 + Parallelization : MPI/OpenMP (8 threads) + +--------------------------------------------------------------------------- + + + +=========================================================================== + MultiResolution Analysis +--------------------------------------------------------------------------- + polynomial order : 6 + polynomial type : Interpolating +--------------------------------------------------------------------------- + total boxes : 8 + boxes : [ 2 2 2 ] + unit lengths : [ 16.00000 16.00000 16.00000 ] + scaling factor : [ 1.00000 1.00000 1.00000 ] + lower bounds : [ -16.00000 -16.00000 -16.00000 ] + upper bounds : [ 16.00000 16.00000 16.00000 ] + total length : [ 32.00000 32.00000 32.00000 ] +=========================================================================== + + + +*************************************************************************** +*** *** +*** Initializing Molecule *** +*** *** +*************************************************************************** + + +=========================================================================== + Molecule +--------------------------------------------------------------------------- + Charge : 0 + Multiplicity : 1 +--------------------------------------------------------------------------- + N Atom : x y z +--------------------------------------------------------------------------- + 0 He : 0.000000 0.000000 0.000000 +--------------------------------------------------------------------------- + Center of mass : 0.000000 0.000000 0.000000 +=========================================================================== + + + +*************************************************************************** +*** *** +*** Computing Initial Guess Wavefunction *** +*** *** +*************************************************************************** + + +~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ + Calculation : Compute initial orbitals + Method : Diagonalize SAD Hamiltonian + Precision : 1.00000e-03 + Screening : 1.20000e+01 StdDev + Restricted : True + Functional : LDA (SVWN5) + AO basis : 3-21G +~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ + + +=========================================================================== + Molecular Orbitals +--------------------------------------------------------------------------- + Alpha electrons : 1 + Beta electrons : 1 + Total electrons : 2 +--------------------------------------------------------------------------- + n Occ Spin : Norm +--------------------------------------------------------------------------- + 0 2 p : 9.999999998814e-01 +=========================================================================== + + +~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ + Calculation : Compute initial energy + Method : DFT (SVWN5) + Relativity : AZORA + Environment : None + External fields : None + Precision : 1.00000e-03 + Localization : Off +~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ + + +=========================================================================== + Molecular Energy (initial) +--------------------------------------------------------------------------- + Kinetic energy : (au) 2.747077263833 + E-N energy : (au) -6.595209258135 + Coulomb energy : (au) 2.026267361549 + Exchange energy : (au) 0.000000000000 + X-C energy : (au) -0.984255225187 + N-N energy : (au) 0.000000000000 +--------------------------------------------------------------------------- + Electronic energy : (au) -2.806119857939 + Nuclear energy : (au) 0.000000000000 +--------------------------------------------------------------------------- + Total energy : (au) -2.806119857939e+00 + : (kcal/mol) -1.760866796213e+03 + : (kJ/mol) -7.367466675357e+03 + : (eV) -7.635841130692e+01 +=========================================================================== + + +=========================================================================== + Orbital Energies (initial) +--------------------------------------------------------------------------- + n Occ Spin : Epsilon +--------------------------------------------------------------------------- + 0 2 p : (au) -0.542683110301 +--------------------------------------------------------------------------- + Sum occupied : (au) -1.085366220603 +=========================================================================== + + + +*************************************************************************** +*** *** +*** Computing Ground State Wavefunction *** +*** *** +*************************************************************************** + + +~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ + Calculation : Optimize ground state orbitals + Method : DFT (SVWN5) + Relativity : AZORA + Environment : None + External fields : None + Checkpointing : Off + Max iterations : 100 + KAIN solver : 5 + Localization : Off + Diagonalization : First two iterations + Start precision : 1.00000e-04 + Final precision : 1.00000e-04 + Helmholtz precision : Dynamic + Energy threshold : Off + Orbital threshold : 1.00000e-03 +~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ + + +=========================================================================== + Iter MO residual Total energy Update +--------------------------------------------------------------------------- + 0 1.000000e+00 -2.806119857939 -2.806120e+00 + 1 7.083644e-02 -2.833995449106 -2.787559e-02 + 2 8.304451e-03 -2.834926502680 -9.310536e-04 + 3 1.609956e-03 -2.834996526943 -7.002426e-05 + 4 5.919719e-04 -2.835003921656 -7.394712e-06 +--------------------------------------------------------------------------- + SCF converged in 4 iterations! +=========================================================================== + + + +*************************************************************************** +*** *** +*** Printing Molecular Properties *** +*** *** +*************************************************************************** + + +=========================================================================== + Molecule +--------------------------------------------------------------------------- + Charge : 0 + Multiplicity : 1 +--------------------------------------------------------------------------- + N Atom : x y z +--------------------------------------------------------------------------- + 0 He : 0.000000 0.000000 0.000000 +--------------------------------------------------------------------------- + Center of mass : 0.000000 0.000000 0.000000 +=========================================================================== + + +=========================================================================== + Molecular Energy (final) +--------------------------------------------------------------------------- + Kinetic energy : (au) 2.767952513094 + E-N energy : (au) -6.625820552296 + Coulomb energy : (au) 1.996222236422 + Exchange energy : (au) 0.000000000000 + X-C energy : (au) -0.973358118876 + N-N energy : (au) 0.000000000000 +--------------------------------------------------------------------------- + Electronic energy : (au) -2.835003921656 + Nuclear energy : (au) 0.000000000000 +--------------------------------------------------------------------------- + Total energy : (au) -2.835003921656e+00 + : (kcal/mol) -1.778991819845e+03 + : (kJ/mol) -7.443301774231e+03 + : (eV) -7.714438672107e+01 +=========================================================================== + + +=========================================================================== + Orbital Energies (final) +--------------------------------------------------------------------------- + n Occ Spin : Epsilon +--------------------------------------------------------------------------- + 0 2 p : (au) -0.570464666039 +--------------------------------------------------------------------------- + Sum occupied : (au) -1.140929332078 +=========================================================================== + + +=========================================================================== + Dipole Moment (dip-1) +--------------------------------------------------------------------------- + r_O : 0.000000 0.000000 0.000000 +--------------------------------------------------------------------------- + Electronic vector : 0.000000 0.000000 0.000000 + Magnitude : (au) 0.000000 + : (Debye) 0.000000 +--------------------------------------------------------------------------- + Nuclear vector : -0.000000 -0.000000 -0.000000 + Magnitude : (au) 0.000000 + : (Debye) 0.000000 +--------------------------------------------------------------------------- + Total vector : -0.000000 -0.000000 -0.000000 + Magnitude : (au) 0.000000 + : (Debye) 0.000000 +=========================================================================== + + + + +*************************************************************************** +*** *** +*** Exiting MRChem *** +*** *** +*** Wall time : 0h 0m 7s *** +*** *** +*************************************************************************** + + diff --git a/tests/he_azora_scf_lda/test b/tests/he_azora_scf_lda/test new file mode 100755 index 000000000..29564cb9d --- /dev/null +++ b/tests/he_azora_scf_lda/test @@ -0,0 +1,26 @@ +#!/usr/bin/env python3 + +import sys +from pathlib import Path + +sys.path.append(str(Path(__file__).resolve().parents[1])) + +from tester import * # isort:skip + +options = script_cli() + +filters = { + SUM_OCCUPIED: rel_tolerance(1.0e-6), + E_KIN: rel_tolerance(1.0e-6), + E_EN: rel_tolerance(1.0e-6), + E_EE: rel_tolerance(1.0e-6), + E_X: rel_tolerance(1.0e-6), + E_XC: rel_tolerance(1.0e-6), + E_EEXT: rel_tolerance(1.0e-6), + E_NEXT: rel_tolerance(1.0e-6), + E_EL: rel_tolerance(1.0e-6), +} + +ierr = run(options, input_file="he", filters=filters) + +sys.exit(ierr)