Add auxiliary basis set info to BasisSet

docs/source/_static/examples/cpp/basis_set.cpp

@@ -30,6 +30,14 @@ int main() {
   // end-cell-loading
   // --------------------------------------------------------------------------------------------
 
+  // --------------------------------------------------------------------------------------------
+  // start-cell-loading-with-aux
+  // Load a primary basis set with an auxiliary basis set for density fitting
+  auto basis_with_aux =
+      BasisSet::from_basis_name("def2-svp", "def2-universal-jfit", structure);
+  // end-cell-loading-with-aux
+  // --------------------------------------------------------------------------------------------
+
   // --------------------------------------------------------------------------------------------
   // start-cell-create
   // Create a shell with multiple primitives
@@ -163,5 +171,53 @@ int main() {
   // end-cell-library
   // --------------------------------------------------------------------------------------------
 
+  // --------------------------------------------------------------------------------------------
+  // start-cell-ecp
+  // Create an ECP shell with radial powers (r^n terms)
+  Eigen::VectorXd ecp_exp(2), ecp_coeff(2);
+  Eigen::VectorXi ecp_rpow(2);
+  ecp_exp << 10.0, 5.0;
+  ecp_coeff << 50.0, 20.0;
+  ecp_rpow << 0, 2;
+  Shell ecp_shell(0, OrbitalType::S, ecp_exp, ecp_coeff, ecp_rpow);
+
+  // Create a basis set with ECP data
+  std::vector<Shell> ecp_shells = {ecp_shell};
+  std::vector<size_t> ecp_electrons = {28, 0, 0};
+  BasisSet basis_with_ecp("my-basis", shells, "my-ecp", ecp_shells,
+                          ecp_electrons, structure);
+
+  // Query ECP data
+  bool has_ecp = basis_with_ecp.has_ecp_shells();
+  std::string ecp_name = basis_with_ecp.get_ecp_name();
+  size_t num_ecp_shells = basis_with_ecp.get_num_ecp_shells();
+  // end-cell-ecp
+  // --------------------------------------------------------------------------------------------
+
+  // --------------------------------------------------------------------------------------------
+  // start-cell-auxiliary
+  // Create auxiliary shells for density fitting
+  std::vector<Shell> aux_shells;
+  aux_shells.emplace_back(0, OrbitalType::S, std::vector{5.0},
+                          std::vector{2.0});
+  aux_shells.emplace_back(1, OrbitalType::S, std::vector{4.0},
+                          std::vector{1.5});
+
+  // Construct a basis set with a named auxiliary basis
+  BasisSet basis_with_aux_manual("my-basis", shells, "my-aux-fit", aux_shells,
+                                 structure);
+
+  // Query auxiliary data
+  bool has_aux = basis_with_aux_manual.has_aux_basis();
+  std::string aux_name = basis_with_aux_manual.get_aux_name();
+  size_t num_aux = basis_with_aux_manual.get_num_aux_shells();
+
+  // Retrieve auxiliary shell data
+  auto all_aux_shells = basis_with_aux_manual.get_aux_shells();
+  const Shell& aux_s = basis_with_aux_manual.get_aux_shell(0);
+  const auto& atom0_aux = basis_with_aux_manual.get_aux_shells_for_atom(0);
+  // end-cell-auxiliary
+  // --------------------------------------------------------------------------------------------
+
   return 0;
 }

docs/source/_static/examples/python/basis_set.py

@@ -29,6 +29,16 @@
 # end-cell-loading
 ################################################################################
 
+################################################################################
+# start-cell-loading-with-aux
+# Load a primary basis set with an auxiliary basis set for density fitting
+basis_with_aux = BasisSet.from_basis_name("def2-svp", "def2-universal-jfit", structure)
+print(f"Primary shells: {basis_with_aux.get_num_shells()}")
+print(f"Auxiliary shells: {basis_with_aux.get_num_aux_shells()}")
+print(f"Auxiliary name: {basis_with_aux.get_aux_name()}")
+# end-cell-loading-with-aux
+################################################################################
+
 ################################################################################
 # start-cell-create
 # Create a shell with multiple primitives
@@ -120,6 +130,54 @@
 Path("molecule.basis_set.h5").unlink()
 ################################################################################
 
+################################################################################
+# start-cell-ecp
+# Create an ECP shell with radial powers (r^n terms)
+ecp_exponents = np.array([10.0, 5.0])
+ecp_coefficients = np.array([50.0, 20.0])
+ecp_rpowers = np.array([0, 2], dtype=np.int32)
+ecp_shell = Shell(0, OrbitalType.S, ecp_exponents, ecp_coefficients, ecp_rpowers)
+
+# Create a basis set with ECP data
+ecp_shells = [ecp_shell]
+ecp_electrons = [28, 0, 0]  # 28 core electrons replaced on the first atom
+basis_with_ecp = BasisSet(
+    "my-basis", [shell1, shell2], "my-ecp", ecp_shells, ecp_electrons, structure
+)
+
+# Query ECP data
+print(f"Has ECP shells: {basis_with_ecp.has_ecp_shells()}")
+print(f"ECP name: {basis_with_ecp.get_ecp_name()}")
+print(f"ECP electrons: {list(basis_with_ecp.get_ecp_electrons())}")
+print(f"Num ECP shells: {basis_with_ecp.get_num_ecp_shells()}")
+# end-cell-ecp
+################################################################################
+
+################################################################################
+# start-cell-auxiliary
+# Create auxiliary shells for density fitting
+aux_shells = [
+    Shell(0, OrbitalType.S, np.array([5.0]), np.array([2.0])),
+    Shell(1, OrbitalType.S, np.array([4.0]), np.array([1.5])),
+]
+
+# Construct a basis set with a named auxiliary basis
+basis_with_aux_manual = BasisSet(
+    "my-basis", [shell1, shell2], "my-aux-fit", aux_shells, structure
+)
+
+# Query auxiliary data
+print(f"Has auxiliary: {basis_with_aux_manual.has_aux_basis()}")
+print(f"Auxiliary name: {basis_with_aux_manual.get_aux_name()}")
+print(f"Num aux shells: {basis_with_aux_manual.get_num_aux_shells()}")
+
+# Retrieve auxiliary shell data
+for i in range(basis_with_aux_manual.get_num_aux_shells()):
+    s = basis_with_aux_manual.get_aux_shell(i)
+    print(f"  Aux shell {i}: atom={s.atom_index}, type={s.orbital_type}")
+# end-cell-auxiliary
+################################################################################
+
 ################################################################################
 # start-cell-utility-functions
 # Convert orbital type to string (returns str)

docs/source/user/comprehensive/data/basis_set.rst

@@ -19,6 +19,8 @@ Key features of the :class:`~qdk_chemistry.data.BasisSet` class include:
 - Basis set metadata (name, parameters)
 - Integration with molecular structure information
 - On-demand expansion of shells to individual basis functions
+- Effective Core Potentials (ECP) with radial powers
+- Auxiliary basis sets for density fitting
 
 Usage
 -----
@@ -98,6 +100,22 @@ The library supports three methods for loading basis sets:
 .. seealso::
    For a complete list of available basis sets, see the :doc:`Supported Basis Sets <../basis_functionals>` documentation.
 
+The library also supports loading an auxiliary basis set alongside the primary basis set in a single call:
+
+.. tab:: C++ API
+
+   .. literalinclude:: ../../../_static/examples/cpp/basis_set.cpp
+      :language: cpp
+      :start-after: // start-cell-loading-with-aux
+      :end-before: // end-cell-loading-with-aux
+
+.. tab:: Python API
+
+   .. literalinclude:: ../../../_static/examples/python/basis_set.py
+      :language: python
+      :start-after: # start-cell-loading-with-aux
+      :end-before: # end-cell-loading-with-aux
+
 Creating a basis set
 --------------------
 
@@ -162,6 +180,55 @@ The ``Shell`` structure contains information about a group of basis functions:
       :start-after: # start-cell-shells
       :end-before: # end-cell-shells
 
+Working with ECP shells
+-----------------------
+
+Effective Core Potentials (ECPs) replace inner-core electrons with a pseudopotential, reducing computational cost for heavy atoms.
+ECP shells are stored alongside primary shells but include an additional **radial powers** vector (:math:`r^n` terms).
+
+ECP data is specified at construction time via dedicated constructors that accept ``ecp_shells``, ``ecp_electrons``, and an optional ``ecp_name``.
+The ``ecp_electrons`` vector records how many core electrons each atom has replaced.
+
+.. tab:: C++ API
+
+   .. literalinclude:: ../../../_static/examples/cpp/basis_set.cpp
+      :language: cpp
+      :start-after: // start-cell-ecp
+      :end-before: // end-cell-ecp
+
+.. tab:: Python API
+
+   .. literalinclude:: ../../../_static/examples/python/basis_set.py
+      :language: python
+      :start-after: # start-cell-ecp
+      :end-before: # end-cell-ecp
+
+.. note::
+   If a basis set from the library includes an ECP, it will be loaded automatically.
+   Manual ECP construction is only needed for custom basis sets.
+
+Auxiliary basis sets
+--------------------
+
+Auxiliary basis sets are used in density-fitting (DF) and resolution-of-the-identity (RI) approximations to speed up two-electron integral evaluation.
+The auxiliary shells are stored inside the same :class:`~qdk_chemistry.data.BasisSet` object as supplementary data alongside the primary shells.
+
+Auxiliary basis data can be attached at construction time or loaded from the library using ``from_basis_name`` with an auxiliary name.
+
+.. tab:: C++ API
+
+   .. literalinclude:: ../../../_static/examples/cpp/basis_set.cpp
+      :language: cpp
+      :start-after: // start-cell-auxiliary
+      :end-before: // end-cell-auxiliary
+
+.. tab:: Python API
+
+   .. literalinclude:: ../../../_static/examples/python/basis_set.py
+      :language: python
+      :start-after: # start-cell-auxiliary
+      :end-before: # end-cell-auxiliary
+
 Serialization
 -------------
 
@@ -193,24 +260,43 @@ JSON representation of a :class:`~qdk_chemistry.data.BasisSet` has the following
              "coefficients": [0.1543289673, 0.5353281423, 0.4446345422],
              "exponents": [3.425250914, 0.6239137298, 0.168855404],
              "orbital_type": "s"
-           },
-           {
-             "coefficients": [0.1559162750, 0.6076837186],
-             "exponents": [0.7868272350, 0.1881288540],
-             "orbital_type": "p"
            }
          ]
-       },
-       {
-         "atom_index": 1,
-         "shells": ["..."]
        }
      ],
      "basis_type": "spherical",
      "name": "6-31G",
      "num_atoms": 2,
      "num_basis_functions": 9,
-     "num_shells": 3
+     "num_shells": 3,
+     "ecp_name": "my-ecp",
+     "ecp_electrons": [28, 0],
+     "ecp_atoms": [
+       {
+         "atom_index": 0,
+         "shells": [
+           {
+             "coefficients": [50.0, 20.0],
+             "exponents": [10.0, 5.0],
+             "orbital_type": "s",
+             "rpowers": [0, 2]
+           }
+         ]
+       }
+     ],
+     "aux_name": "my-aux-fit",
+     "aux_atoms": [
+       {
+         "atom_index": 0,
+         "shells": [
+           {
+             "coefficients": [2.0],
+             "exponents": [5.0],
+             "orbital_type": "s"
+           }
+         ]
+       }
+     ]
    }
 
 HDF5 format
@@ -227,8 +313,24 @@ HDF5 representation of a :class:`~qdk_chemistry.data.BasisSet` has the following
    │   ├── exponents       # Dataset: float64, 1D Array of orbital exponents
    │   ├── num_primitives  # Dataset: uint32, 1D Array of number of primitives per orbital
    │   └── orbital_types   # Dataset: int32, 1D Array of orbital type per orbital
+   ├── ecp_shells/         # Group (present when ECP is defined)
+   │   ├── atom_indices    # Dataset: uint32
+   │   ├── coefficients    # Dataset: float64
+   │   ├── exponents       # Dataset: float64
+   │   ├── rpowers         # Dataset: int32, 1D Array of radial powers per primitive
+   │   ├── num_primitives  # Dataset: uint32
+   │   └── orbital_types   # Dataset: int32
+   ├── aux_shells/         # Group (present when auxiliary basis is defined)
+   │   ├── atom_indices    # Dataset: uint32
+   │   ├── coefficients    # Dataset: float64
+   │   ├── exponents       # Dataset: float64
+   │   ├── num_primitives  # Dataset: uint32
+   │   └── orbital_types   # Dataset: int32
    └── metadata/           # Group
-       └── name            # Attribute: string value of the basis set name
+       ├── name            # Attribute: string value of the basis set name
+       ├── ecp_name        # Attribute: string (optional)
+       ├── ecp_electrons   # Dataset: uint64 (optional)
+       └── aux_name        # Attribute: string (optional)
 
 .. tab:: C++ API