CRYSTAL17

1 CRYSTAL17 User s ManualApril 20, 2018R. Dovesi, Saunders,1C. Roetti,1R. Orlando,1C. M. Zicovich-Wilson,2F. Pascale,3B. Civalleri,1K. Doll, Harrison,5, Bush,7Ph. D Arco,8M. Llunel,l9M. Caus`a,10Y. No el,8L. Maschio,1A. Erba,1M. R erat,11S. Casassa11 Theoretical Chemistry Group - University of TurinDipartimento di Chimica IFMVia Giuria 5 - I 10125 Torino - Italy2 Centro de Investigaci on en Ciencias, Universidad Aut onoma del Estado de Morelos,Av. Universidad 1001, Col. Chamilpa, 62209 Cuernavaca (Morelos) Mexico3 Facult e des Sciences et Technologies, Universit e de LorraineBP 70239, Boulevard des Aiguillettes 54506 Vandoeuvre-l es-Nancy Cedex, France4 Institut f ur Elektrochemie, Universit at UlmAlbert-Einstein-Allee 47, 89081 Ulm, Germany5 Computational Science & Engineering Department - STFC DaresburyDaresbury, Warrington, Cheshire, UK WA4 4AD6 Department of Chemistry, Imperial CollegeSouth Kensington Campus, London, e-Research Centre, University of Oxford, 7 Keble Road, OX1 3QG, Oxford, UK8 Institut des Sciences de la Terre de Paris (UMR 7193 UPMC-CNRS)

2 ,UPMC, Sorbonne Universit es, 4 Place Jussieu, 75232 Paris CEDEX 05, France9 Departament de Qu mica F sica, Universitat de BarcelonaDiagonal 647, Barcelona, Spain10 Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione industriale,Universit`a di Napoli Federico I Via Cintia (Complesso di Monte S. Angelo) 21, Napoli - Italy11 Equipe de Chimie Physique, IPREM UMR5254,Universit e de Pau et des Pays de l Adour, 64000 Pau, France12 Contents1 Introductory Introduction .. CRYSTAL17 Program Features ..10 Typographical Conventions ..15 Acknowledgments ..16 Getting Started - Installation and testing ..162 Wave-function Calculation:Basic Input Geometry and symmetry information ..17 Geometry input for crystalline compounds.

3 18 Geometry input for molecules, polymers and slabs ..18 Geometry input for polymers with roto translational symmetry ..19 Geometry input from external geometry editor ..19 Comments on geometry input .. Basis set .. route .. set input by keywords .. Computational parameters, hamiltonian,SCF control ..293 Wave-function Calculation - Advanced Input Geometry editing .. Basis set input ..72 Effective core pseudo-potentials ..75 Pseudopotential libraries .. Computational parameters, Hamiltonian,SCF control..794 Density Functional Choice of the exchange-correlation functional .. Dispersion correction to DFT (DFT-D) .. Integration grid and numerical accuracy control.

4 Atomic parameters .. 1315 Semi-classical corrections for HF and London dispersion correction .. Geometrical counterpoise correction .. Minimal basis HF composite method .. Small basis DFT composite method .. London dispersion correction .. Geometrical counterpoise correction .. Minimal basis HF composite method .. Small basis DFT composite method .. 15336 Geometry Geometry optimization strategy .. Default setting .. of optimization .. criteria .. Hessian guess .. updating technique .. convergence and guess .. files .. General sub-keywords .. of optimization .. Hessian .. atomic radii .. updating technique.

5 Convergence criteria .. control .. system related options .. procedure control .. first derivatives .. Printing options .. Notes on geometry optimization .. the integrals classification during a geometry optimization .. of flat surfaces .. optimization .. Searching a transition state .. 177 Searching a transition state .. state control keywords .. keywords .. 1797 Lattice Dynamics - Vibration Calculation of Harmonic Vibration Frequencies .. exploitation .. Geometry .. settings .. files .. keywords .. Restart a calculation .. IR Intensities .. intensities through Berry phase [default] .. intensities through Wannier functions.

6 Intensities through CPHF/CPKS .. Raman Intensities .. contribution to SHG and dc-Pockels tensors .. Scanning of geometry along selected normal modes .. 1 - Methane molecule .. 2 - PbCO3.. Calculation of the infrared spectrum .. Calculation of the Raman spectra .. Phonon dispersion .. Anisotropic Displacement Parameters (ADP) .. Phonon Density-of-State (and Inelastic Neutron Scattering Spectra) .. Anharmonic calculation of frequencies of X-H (X-D) bond stretching .. 20648 Harmonic and Quasi-Harmonic A Few Theoretical Remarks .. Dispersion .. Lattice Dynamics .. Quantities .. uneisen Simplified Model .. The Automated Algorithm: Some Computational Parameters.

7 Keywords .. QHA: A Guided Tour of the Output .. Equation-of-State .. Modes Continuity on Volume .. uneisen Model .. Results: Thermal Properties from Helmholtz Free Energy .. Pressure: The P-V-T Equation-of-State .. 2229 Dielectric Properties up to Fourth Order via the Coupled Perturbed Response to an Electric Field - Theoretical Framework of the Coupled-PerturbedTreatment .. Coupled-Perturbed HF/KS Calculation of Dielectric Properties up to SecondOrder .. for tuning convergence and accuracy in the Coupled-Perturbediterations .. (Frequency-dependent) CPHF/KS.. first hyperpolarizability .. first hyperpolarizability tensors - Pockels and Second-Harmonic Generation.

8 Fourth-Order CPHF/KS second hyperpolarizability calculation .. and control of the CPHF2 iterative procedure .. Restart of first or second order CPHF .. 23010 Tools for Studying Solid Counting and Enumerating Configurations .. Uniform Random Sampling of Symmetry Independent Configurations .. Calculations on Predefined Configurations .. Exploring the Neighborhood of a Configuration .. 23611 Equations of A few theoretical remarks .. Keywords, options and defaults .. Output Information .. 24012 Calculation of Elastic, Piezoelectric and Photoelastic A few theoretical remarks .. The algorithm .. Second-order Elastic Constants .. Elastic Tensor under Pressure.

9 Nuclear-relaxation Term from Internal-strain Tensor .. First-order Piezoelectric Constants .. Piezoelectricity through CPHF/KS Approach .. Elastic and Piezoelectric Constants .. Photoelastic Constants .. 255513 One-electron Properties and Wave-function Preliminary calculations .. Properties keywords .. Electronic Band Structure .. Compton Profiles - fromB(r) Function .. Transport Properties .. Electronic Density-of-State .. Crystal Orbital Overlap/Hamiltonian Populations .. 3D Electron Charge Density .. 2D Electron Charge Density .. Momentum Density .. Crystalline Orbitals - Wannier Functions .. plotting of crystalline (molecular) orbitals.

10 Matrix of Non-interacting Atoms .. Electrostatic Potential .. Electrostatic Potential .. Population Analysis .. Structure Factors and XRD Spectra .. Spontaneous polarization .. M ossbauer Spectroscopy .. Topological analysis .. 31814 Running CRYSTAL in RunningPcrystalandPproperties.. RunningMPPcrystal.. 32015 Input Standard geometry input .. 322 CRYSTAL .. 322 SLAB .. 326 POLYMER .. 328 MOLECULE .. Basis set input .. 329 ECP - Valence only basis set input .. SCF options .. Geometry optimization .. 33416 Basis Molecular BSs performance in periodic systems .. Core functions .. Valence functions .. 344 Molecular crystals.