crfit ***** Charge-response parametrization of a molecule with xtpdft: the charge-response matrix Pi (Hirshfeld charges), the molecular polarizability and the residual polarizabilities, from the static response to Hirshfeld-localized potentials and uniform fields (coupled-perturbed Kohn-Sham, or finite differences of SCFs). Reads job_name.xyz; closed-shell molecules. The following table contains the defaults input options for the calculator, The default `OPTIONAL` means this option is switched off, if no input is given. `REQUIRED` arguments have to be specified, otherwise an error is thrown. .. list-table:: :header-rows: 1 :widths: 30 20 15 15 :align: center * - Property Name - Default Value - Description - Valid Input * - job_name - system - | Input file name without extension, also used for intermediate | files - * - dftpackage.name - xtp - Name of the DFT package - | xtp | orca * - dftpackage.charge - 0 - Molecular charge - int * - dftpackage.spin - 1 - Molecular multiplicity - int+ * - dftpackage.basisset - def2-tzvp - Basis set for MOs - * - dftpackage.auxbasisset - OPTIONAL - Auxiliary basis set for RI - * - dftpackage.externalfield - OPTIONAL - Field given in x y z components - * - dftpackage.executable - OPTIONAL - Path to executable for dftpackage - * - dftpackage.ecp - OPTIONAL - Effective Core Potentials for DFT Calculations - * - dftpackage.optimize - false - Perform a molecular geometry optimization - bool * - dftpackage.functional - XC_HYB_GGA_XC_PBEH - | Exchange correlation functional used. You can also specify | an exchange and a correlation functional - * - dftpackage.scratch - /tmp/qmpackage - path to the scratch folder - * - dftpackage.polarization - false - Calculate polarisation - bool * - dftpackage.dipole_spacing - 0.1 - Spacing for splitting multipoles into charges - float+ * - dftpackage.temporary_file - temp - Filename for temporary files without extension - * - dftpackage.convergence_tightness - tight - How accurate the dft self-consistency has to be - | low | normal | tight | verytight * - dftpackage.cleanup - - | files to remove after the calculation. Specify the fileextensions | - * - dftpackage.initial_guess - atom - | Method to use to make initial guess, independent(electrons) | or atom(densities) or previous calculation keyword orbfile | or dimer_guess (combine two monomer .orb files, see dimer_guess_orbA/orbB | below; closed-shell monomers work for restricted and unrestricted | runs, open-shell monomers need the unrestricted path) - | independent | atom | orbfile | huckel | huckel_dft | dimer_guess * - dftpackage.dimer_guess_orbA - - | Converged .orb file of monomer A, read only for initial_guess=dimer_guess. | Its atoms must match the first N_A atoms of the molecule | in internal geometry; translation and rotation are allowed. - * - dftpackage.dimer_guess_orbB - - | As dimer_guess_orbA, for monomer B, matching the remaining | atoms of the molecule. - * - dftpackage.orca - - | orca specific keywords can be added here, where the xml | tag corresponds to the option and the value to the option's | value - * - dftpackage.xtpdft.dft_in_dft.activeatoms - - Indices of atoms in active region - * - dftpackage.xtpdft.dft_in_dft.threshold - 0.4 - | Mulliken population above which orbital is considered | in the active region - * - dftpackage.xtpdft.dft_in_dft.levelshift - 10000.0 - Levelshift energy for the projection operator - * - dftpackage.xtpdft.dft_in_dft.truncate_basis - false - Truncate the basis-set to active atoms only - bool * - dftpackage.xtpdft.dft_in_dft.truncation_threshold - 1e-4 - Threshold to convert an inactive atom to a border atom - float+ * - dftpackage.xtpdft.screening_eps - 1e-9 - screening eps - float+ * - dftpackage.xtpdft.overlap_tolerance - 1e-8 - | Eigenvalues of the AO overlap matrix below this value | are removed from the orthogonalization (near linear dependencies; | the removed directions become zero orbitals at the top | of the spectrum). Raise to 1e-7 to 1e-6 if the log reports | a nearly singular overlap and the SCF is unstable. - float+ * - dftpackage.xtpdft.ri_pair_threshold - 1e-10 - | RI only: basis-function shell pairs whose three-centre | integrals (P|ab) are bounded by less than this (Schwarz | bound) are not stored. Reduces the memory of the stored | RI tensor substantially for large molecules; energies | change at the level of the threshold. 0 stores all pairs. - float+ * - dftpackage.xtpdft.fock_matrix_reset - 5 - how often the fock matrix is reset - int+ * - dftpackage.xtpdft.integration_grid - medium - vxc grid quality - | xcoarse | coarse | medium | fine | xfine * - dftpackage.xtpdft.force_uks_path - false - forcing UKS path - bool * - dftpackage.xtpdft.polarizability - false - | After the SCF, compute the static dipole polarizability | tensor analytically (coupled-perturbed Kohn-Sham with | the three dipole operators; closed-shell states, LDA/GGA/global | hybrids) and store it in the orb (HDF5) file, e.g. as | the target for molpol (qmpackage xtp). - bool * - dftpackage.xtpdft.compute_forces - false - | Compute analytic ground-state DFT nuclear forces (RI, | and hybrid exchange for UKS) and store them in the orb | (HDF5) file. Adds cost to every converged SCF. - bool * - dftpackage.xtpdft.cdft.enabled - false - Enable a CDFT charge constraint on this calculation - bool * - dftpackage.xtpdft.cdft.indices - - | Indices (0-based) of the atoms in the constrained fragment, | in the range syntax of the diabatization fragments, e.g. | '1 3 13:17' - * - dftpackage.xtpdft.cdft.charge - 0.0 - | Target charge of the fragment relative to the neutral | fragment (sum of its nuclear charges): +1.0 removes one | electron, -1.0 adds one. - float * - dftpackage.xtpdft.cdft.initial_lambda - 0.0 - | Initial guess for the Lagrange multiplier lambda, the | centre of the initial bisection bracket - float * - dftpackage.xtpdft.cdft.population_tolerance - 1e-4 - | Convergence criterion of the outer loop: maximum deviation | of the fragment population from the target, in electrons - float+ * - dftpackage.xtpdft.cdft.max_iterations - 50 - | Maximum number of outer (bisection) iterations, each a | full inner SCF - int+ * - dftpackage.xtpdft.cdft.guess_strategy - warmstart - | Start guess of the inner SCF for each bisection trial | after the first. warmstart: the converged MOs of the preceding | trial (usually faster, since consecutive lambdas are close); | fresh: the top-level initial_guess, which can help if | consecutive trials have very different electronic structures. - | warmstart | fresh * - dftpackage.xtpdft.convergence.energy - 1E-7 - DeltaE at which calculation is converged - float+ * - dftpackage.xtpdft.convergence.method - DIIS - Main method to use for convergence accelertation - | DIIS | mixing * - dftpackage.xtpdft.convergence.DIIS_start - 0.002 - DIIS error at which DIIS takes over - float+ * - dftpackage.xtpdft.convergence.ADIIS_start - 0.8 - DIIS error at which ADIIS takes over - float+ * - dftpackage.xtpdft.convergence.DIIS_length - 20 - old hamiltonians to keep in history - int+ * - dftpackage.xtpdft.convergence.DIIS_maxout - false - | if true remove the maximum element in the history if DIIS_length | is exceeded.Otherwise, the oldest element is removed. - bool * - dftpackage.xtpdft.convergence.levelshift - 0.0 - levelshift to apply to hamiltonian - float+ * - dftpackage.xtpdft.convergence.levelshift_end - 0.2 - DIIS error at levelshifting is disabled - float+ * - dftpackage.xtpdft.convergence.max_iterations - 100 - max iterations to use - int+ * - dftpackage.xtpdft.convergence.error - 1e-7 - convergence error - float+ * - dftpackage.xtpdft.convergence.mixing - 0.7 - mixing parameter for linear mixing of density matrices - float+ * - dftpackage.xtpdft.convergence.mixing_end - 0.8 - | DIIS error below which linear mixing is switched off. | Independent of ADIIS_start (like ORCA's DampErr), so difficult | systems can keep mixing after (A)DIIS starts; the default | equals that of ADIIS_start. - float+ * - dftpackage.xtpdft.convergence.mixing_max - 0.98 - | Upper limit to which the mixing parameter is raised linearly | with consecutive ADIIS failures (UKS path), like ORCA's | DampMax. - float+ * - dftpackage.xtpdft.convergence.energy_reset - 1.0 - | If the energy rises by more than this above the lowest | energy reached so far, the (A)DIIS history is discarded | and the SCF restarts, damped, from the lowest-energy density. | 0 disables. - float+ * - dftpackage.xtpdft.convergence.second_order - auto - | Second-order (trust-region augmented Hessian, TRAH) SCF | steps. auto: switch to them when (A)DIIS fails repeatedly | or the DIIS error stalls, then use them until convergence; | always: use them from the first iteration; off: never. | Exact analytic orbital Hessian for RKS and UKS (LDA/GGA | and global hybrids; spin-polarized f_xc for UKS); for | UKS with a functional without second derivatives in libxc, | finite differences of the Fock matrix (two Fock builds | per Hessian product). - | auto | always | off * - dftpackage.xtpdft.convergence.davidson_max_iter - 50 - | Maximum number of micro-iterations (Hessian products) | per second-order (TRAH) step. - int+ * - method - analytic - | analytic: coupled-perturbed Kohn-Sham (LDA, GGA, global | hybrids); finite_differences: two SCFs per perturbation - | analytic | finite_differences * - tolerance - 1e-7 - | analytic: relative residual of the coupled-perturbed equations | - float+ * - step - 1e-3 - | finite_differences: strength of each perturbation: Hirshfeld-localized | potential in Hartree, uniform field in Hartree/bohr - float+ * - scf_error - 1e-9 - | Every SCF is converged to at least this DIIS error (and | 1/100 of it in the energy): the ground state for both | methods, and the perturbed SCFs, whose densities are differenced, | for finite_differences - float+ * - inversion - true - | If the geometry has an inversion centre (equivalent atoms | within 1e-4 bohr), perturb only one atom of each pair | and obtain the other response by symmetry - bool * - mpsfile - OPTIONAL - | Template .mps of the molecule with the permanent multipoles | (same atoms in the same order); if given, output.mps is | written with the residual polarizabilities on its P lines, | rotated into the template frame - * - output - OPTIONAL - | Output prefix: output.crm, output.json (the keys of xtp_cr_fit, | readable by xtp_cr_mps) and, with mpsfile, output.mps - .. note:: An *xml* file containing the defaults for the `crfit` calculator can be created via `-p crfit -o FILENAME` command line options `