Add harmonic models

atomistics/calculators/einstein.py

@@ -0,0 +1,93 @@
+import numpy as np
+import scipy
+
+from atomistics.calculators.wrapper import as_task_dict_evaluator
+from atomistics.calculators.hessian import get_displacement
+
+
+kb = scipy.constants.physical_constants["Boltzmann constant in eV/K"][0] * 1000
+hartree = scipy.constants.physical_constants["atomic unit of energy"][0]  # J
+bohr_r = scipy.constants.physical_constants["Bohr radius"][0]  # in m
+hbar_str = "Planck constant over 2 pi in eV s"
+hbar = scipy.constants.physical_constants[hbar_str][0]  # eV s
+u = scipy.constants.physical_constants["atomic mass constant"][0]  # in kg
+
+
+def get_free_energy_classical(structure, force_constant, temperature):
+    frequency_dict = get_einstein_frequencies(
+        structure=structure, force_constant=force_constant
+    )
+
+    def get_free_energy(frequency, temperature):
+        return kb * temperature * np.log(frequency / (kb * temperature))
+
+    return {
+        el: get_free_energy(frequency=frequency, temperature=temperature)
+        for el, frequency in frequency_dict.items()
+    }
+
+
+def get_free_energy_quantum_mechanical(structure, force_constant, temperature):
+    frequency_dict = get_einstein_frequencies(
+        structure=structure, force_constant=force_constant
+    )
+
+    def get_free_energy(frequency, temperature):
+        return frequency / 2 + kb * temperature * np.log(
+            1 - np.exp(-(frequency / (kb * temperature)))
+        )
+
+    return {
+        el: get_free_energy(frequency=frequency, temperature=temperature)
+        for el, frequency in frequency_dict.items()
+    }
+
+
+def get_einstein_frequencies(structure, force_constant):
+    return {
+        el: 1000
+        * np.sqrt(hbar * hbar * force_constant * hartree / u / mass / bohr_r / bohr_r)
+        for el, mass in zip(structure.get_chemical_symbols(), structure.get_masses())
+    }
+
+
+def get_energy_pot(structure, structure_equilibrium, force_constant):
+    dis = get_displacement(
+        structure_equilibrium=structure_equilibrium, structure=structure
+    )
+    return sum(
+        0.5 * force_constant * hartree / bohr_r / bohr_r * np.linalg.norm(dis, axis=1)
+    )
+
+
+def get_forces(structure, structure_equilibrium, force_constant):
+    dis = get_displacement(
+        structure_equilibrium=structure_equilibrium, structure=structure
+    )
+    return dis * force_constant * hartree / bohr_r / bohr_r
+
+
+@as_task_dict_evaluator
+def evaluate_with_einstein_model(
+    structure,
+    structure_equilibrium,
+    force_constant,
+    tasks,
+):
+    results = {}
+    if "calc_energy" in tasks or "calc_forces" in tasks:
+        if "calc_energy" in tasks:
+            results["energy"] = get_energy_pot(
+                structure=structure,
+                structure_equilibrium=structure_equilibrium,
+                force_constant=force_constant,
+            )
+        if "calc_forces" in tasks:
+            results["forces"] = get_forces(
+                structure=structure,
+                structure_equilibrium=structure_equilibrium,
+                force_constant=force_constant,
+            )
+    else:
+        raise ValueError("The ASE calculator does not implement:", tasks)
+    return results

atomistics/calculators/hessian.py

@@ -0,0 +1,132 @@
+import numpy as np
+
+from atomistics.calculators.wrapper import as_task_dict_evaluator
+
+
+def check_force_constants(structure, force_constants):
+    if structure is None:
+        raise ValueError("Set reference structure via set_reference_structure() first")
+    n_atom = len(structure.positions)
+    if len(np.array([force_constants]).flatten()) == 1:
+        return force_constants * np.eye(3 * n_atom)
+    elif np.array(force_constants).shape == (3 * n_atom, 3 * n_atom):
+        return force_constants
+    elif np.array(force_constants).shape == (n_atom, n_atom):
+        na = np.newaxis
+        return (
+            np.array(force_constants)[:, na, :, na] * np.eye(3)[na, :, na, :]
+        ).flatten()
+    elif len(np.shape(force_constants)) == 4:
+        force_shape = np.shape(force_constants)
+        if force_shape[2] == 3 and force_shape[3] == 3:
+            force_reshape = force_shape[0] * force_shape[2]
+            return np.transpose(force_constants, (0, 2, 1, 3)).reshape(
+                (force_reshape, force_reshape)
+            )
+        elif force_shape[1] == 3 and force_shape[3] == 3:
+            return np.array(force_constants).reshape(3 * n_atom, 3 * n_atom)
+        else:
+            raise AssertionError("force constant shape not recognized")
+    else:
+        raise AssertionError("force constant shape not recognized")
+
+
+def get_displacement(structure_equilibrium, structure):
+    displacements = structure.get_scaled_positions()
+    displacements -= structure_equilibrium.get_scaled_positions()
+    displacements -= np.rint(displacements)
+    return np.einsum("ji,ni->nj", structure.cell, displacements)
+
+
+def calc_forces_transformed(force_constants, structure_equilibrium, structure):
+    displacements = get_displacement(structure_equilibrium, structure)
+    position_transformed = displacements.reshape(
+        displacements.shape[0] * displacements.shape[1]
+    )
+    return -np.dot(force_constants, position_transformed), displacements
+
+
+def get_forces(force_constants, structure_equilibrium, structure):
+    displacements = get_displacement(structure_equilibrium, structure)
+    position_transformed = displacements.reshape(
+        displacements.shape[0] * displacements.shape[1]
+    )
+    forces_transformed = -np.dot(force_constants, position_transformed)
+    return forces_transformed.reshape(displacements.shape)
+
+
+def get_energy_pot(
+    force_constants, structure_equilibrium, structure, bulk_modulus=0, shear_modulus=0
+):
+    displacements = get_displacement(structure_equilibrium, structure)
+    position_transformed = displacements.reshape(
+        displacements.shape[0] * displacements.shape[1]
+    )
+    forces_transformed = -np.dot(force_constants, position_transformed)
+    energy_pot = -1 / 2 * np.dot(position_transformed, forces_transformed)
+    energy_pot += get_pressure_times_volume(
+        stiffness_tensor=get_stiffness_tensor(
+            bulk_modulus=bulk_modulus, shear_modulus=shear_modulus
+        ),
+        structure_equilibrium=structure_equilibrium,
+        structure=structure,
+    )
+    return energy_pot
+
+
+def get_stiffness_tensor(bulk_modulus=0, shear_modulus=0):
+    stiffness_tensor = np.zeros((6, 6))
+    stiffness_tensor[:3, :3] = bulk_modulus - 2 * shear_modulus / 3
+    stiffness_tensor[:3, :3] += np.eye(3) * 2 * shear_modulus
+    stiffness_tensor[3:, 3:] = np.eye(3) * shear_modulus
+    return stiffness_tensor
+
+
+def get_pressure_times_volume(stiffness_tensor, structure_equilibrium, structure):
+    if np.sum(stiffness_tensor) != 0:
+        epsilon = np.einsum(
+            "ij,jk->ik",
+            structure.cell,
+            np.linalg.inv(structure_equilibrium.cell),
+        ) - np.eye(3)
+        epsilon = (epsilon + epsilon.T) * 0.5
+        epsilon = np.append(epsilon.diagonal(), np.roll(epsilon, -1, axis=0).diagonal())
+        pressure = -np.einsum("ij,j->i", stiffness_tensor, epsilon)
+        pressure = pressure[3:] * np.roll(np.eye(3), -1, axis=1)
+        pressure += pressure.T + np.eye(3) * pressure[:3]
+        return -np.sum(epsilon * pressure) * structure.get_volume()
+    else:
+        return np.zeros((6, 6))
+
+
+@as_task_dict_evaluator
+def evaluate_with_hessian(
+    structure,
+    structure_equilibrium,
+    force_constants,
+    tasks,
+    bulk_modulus=0,
+    shear_modulus=0,
+):
+    results = {}
+    if "calc_energy" in tasks or "calc_forces" in tasks:
+        force_constants = check_force_constants(
+            structure=structure, force_constants=force_constants
+        )
+        if "calc_energy" in tasks:
+            results["energy"] = get_energy_pot(
+                structure=structure,
+                structure_equilibrium=structure_equilibrium,
+                force_constants=force_constants,
+                bulk_modulus=bulk_modulus,
+                shear_modulus=shear_modulus,
+            )
+        if "calc_forces" in tasks:
+            results["forces"] = get_forces(
+                structure=structure,
+                structure_equilibrium=structure_equilibrium,
+                force_constants=force_constants,
+            )
+    else:
+        raise ValueError("The ASE calculator does not implement:", tasks)
+    return results