7. Detailed Documentation

• 7.1. The SHARK Integral Package and Task Driver
  • 7.1.1. Preface
  • 7.1.2. The SHARK integral algorithm
  • 7.1.3. SHARK and libint
  • 7.1.4. Basis set types
  • 7.1.5. Task drivers
  • 7.1.6. SHARK User Interface
• 7.2. More on Coordinate Input
  • 7.2.1. Fragment Specification
  • 7.2.2. Defining Geometry Parameters and Scanning Potential Energy Surfaces
  • 7.2.3. Mixing internal and Cartesian coordinates
  • 7.2.4. Inclusion of Point Charges
• 7.3. Details on the numerical integration grids
  • 7.3.1. The angular grid scheme
  • 7.3.2. The radial grid scheme
  • 7.3.3. The DEFGRIDs
  • 7.3.4. Other details and options
  • 7.3.5. SCF grid keyword list
  • 7.3.6. Changing TD-DFT, CP-SCF and Hessian grids
  • 7.3.7. When should I change from the default grids?
• 7.4. Choice of Computational Model
  • 7.4.1. Features Common to All Calculations
  • 7.4.2. Density Functional Calculations
    • 7.4.2.1. Choice of Functional
    • 7.4.2.2. LibXC Functionals
      • 7.4.2.2.1. Screening Thresholds
      • 7.4.2.2.2. Modifying LibXC Functional Parameters
      • 7.4.2.2.3. Simple Input of LibXC Functionals
    • 7.4.2.3. Using the RI-J Approximation to the Coulomb Part
    • 7.4.2.4. The Split-RI-J Coulomb Approximation
    • 7.4.2.5. Using the RI Approximation for Hartree-Fock and Hybrid DFT (RIJONX)
    • 7.4.2.6. Using the RI Approximation for Hartree-Fock and Hybrid DFT (RIJCOSX)
      • 7.4.2.6.1. The RIJCOSX gradient
      • 7.4.2.6.2. Working with the COSX Numerical Grids
      • 7.4.2.6.3. Some SFitting Parameters
      • 7.4.2.6.4. Use of Partial Contraction Scheme
      • 7.4.2.6.5. Restoring Full Symmetry
    • 7.4.2.7. COSX Grid and Convergence Issues
    • 7.4.2.8. Treatment of Dispersion Interactions with DFT-D3
      • 7.4.2.8.1. Introduction
      • 7.4.2.8.2. Damping Functions
      • 7.4.2.8.3. Three-body term
      • 7.4.2.8.4. Options
      • 7.4.2.8.5. Example input files
    • 7.4.2.9. DFT Calculations with the Non-Local, Density Dependent Dispersion Correction (VV10): DFT-NL
      • 7.4.2.9.1. The B97-V Family
      • 7.4.2.9.2. Changing the \(b\), \(C\) and Scaling Parameters
      • 7.4.2.9.3. Self-consistent Computations with the DFT-NL Dispersion Correction
    • 7.4.2.10. DFT and HF Calculations with the Geometrical Counterpoise Correction: gCP
    • 7.4.2.11. HF-3c: Hartree-Fock with three corrections
    • 7.4.2.12. PBEh-3c: A PBE hybrid density functional with small AO basis set and two corrections
    • 7.4.2.13. \(r^2\)SCAN-3c: A robust “Swiss army knife” composite electronic-structure method
    • 7.4.2.14. \(\omega\)B97X-3c: A composite range-separated hybrid DFT method with a molecule-optimized polarized valence double-\(\zeta\) basis set
  • 7.4.3. Semiempirical Methods
    • 7.4.3.1. Semi-empirical tight-binding methods: Grimme’s GFN0-xTB, GFN-xTB and GFN2-xTB
      • 7.4.3.1.1. Solvation
      • 7.4.3.1.2. Keywords for XTB
• 7.5. Choice of Basis Set
  • 7.5.1. Built-in Basis Sets
  • 7.5.2. Automatic generation of auxiliary basis sets
  • 7.5.3. Assigning or Adding Basis Functions to an Element
  • 7.5.4. Assigning or Adding Basis Functions to Individual Atoms
  • 7.5.5. Assigning Basis Sets and ECPs to Fragments
  • 7.5.6. Reading Orbital and Auxiliary Basis Sets from a File
  • 7.5.7. Advanced Specification of Effective Core Potentials
    • 7.5.7.1. Library ECPs and Basis Sets
    • 7.5.7.2. Manual Input of ECP Parameters
    • 7.5.7.3. ECPs and ghost atoms
  • 7.5.8. Embedding Potentials
  • 7.5.9. Linear Dependence
    • 7.5.9.1. Automatic Adjustments for Near Linear-Dependent Cases
    • 7.5.9.2. Removal of Redundant Basis Functions
• 7.6. Choice of Initial Guess and Restart of SCF Calculations
  • 7.6.1. AutoStart feature
  • 7.6.2. One Electron Matrix Guess
  • 7.6.3. Basis Set Projection
  • 7.6.4. PModel Guess
  • 7.6.5. Hückel and PAtom Guesses
  • 7.6.6. Restarting SCF Calculations
  • 7.6.7. Changing the Order of Initial Guess MOs and Breaking the Initial Guess Symmetry
  • 7.6.8. Automatically Breaking of the Initial Guess Symmetry
  • 7.6.9. Calculating only the energy of an input density
• 7.7. SCF Convergence
  • 7.7.1. Convergence Tolerances
  • 7.7.2. Dynamic and Static Damping
  • 7.7.3. Level Shifting
  • 7.7.4. Direct Inversion in Iterative Subspace (DIIS)
  • 7.7.5. An alternative DIIS algorithm: KDIIS
  • 7.7.6. Approximate Second Order SCF (SOSCF)
  • 7.7.7. Trust-Region Augmented Hessian (TRAH) SCF
  • 7.7.8. Finite Temperature HF/KS-DFT
    • 7.7.8.1. Fractional Occupation Numbers
    • 7.7.8.2. Fractional Occupation Number Weighted Electron Density (FOD)
• 7.8. Choice of Wavefunction and Integral Handling
  • 7.8.1. Choice of Wavefunction Type
  • 7.8.2. ROHF Options
  • 7.8.3. UHF Natural Orbitals
  • 7.8.4. Integral Handling (Conventional and Direct)
• 7.9. DeltaSCF: Converging to Arbitrary Single-Reference Wavefunctions
  • 7.9.1. First Example: HOMO-LUMO Excited State of Formaldehyde
  • 7.9.2. Core-ionized States
  • 7.9.3. Diabatic Couplings
  • 7.9.4. Full keyword list
• 7.10. CP-SCF Options
• 7.11. SCF Stability Analysis
• 7.12. Frozen Core Options
• 7.13. The Second Order Many Body Pertubation Theory Module (MP2)
  • 7.13.1. Standard MP2
  • 7.13.2. RI-MP2
  • 7.13.3. “Double-Hybrid” Density Functional Theory
  • 7.13.4. Orbital Optimized MP2
  • 7.13.5. Regularized MP2 and RI-MP2
  • 7.13.6. RIJCOSX-RI-MP2 Gradients
  • 7.13.7. MP2 and RI-MP2 Second Derivatives
  • 7.13.8. RI-MP2 and Double-Hybrid DFT Response Properties
  • 7.13.9. Local MP2
    • 7.13.9.1. Local MP2 Gradient
    • 7.13.9.2. Local MP2 Response Properties
    • 7.13.9.3. Numerical DLPNO-MP2 derivatives
    • 7.13.9.4. Multi-Level DLPNO-MP2 calculations
• 7.14. The Single Reference Correlation Module
  • 7.14.1. Theory
  • 7.14.2. Closed-Shell Equations
  • 7.14.3. Open-Shell Equations
  • 7.14.4. Local correlation
    • 7.14.4.1. Including (semi)core orbitals in the correlation treatment
    • 7.14.4.2. Multi-Level Calculations
    • 7.14.4.3. Multi-Level Calculations for IP and EA-EOM-DLPNO-CCSD
  • 7.14.5. The singles Fock term
  • 7.14.6. Use of the MDCI Module
• 7.15. The Complete Active Space Self-Consistent Field (CASSCF) Module
  • 7.15.1. General Description
  • 7.15.2. CASSCF Densities
  • 7.15.3. CASSCF Properties
  • 7.15.4. 1- and 2-shell Abinitio Ligand Field Theory
  • 7.15.5. Core excited states with (C/R)ASCI/NEVPT2
  • 7.15.6. CASCI-XES
• 7.16. CASSCF Linear Response
  • 7.16.1. Input Block
  • 7.16.2. Technical Notes
  • 7.16.3. Notes on Printing
  • 7.16.4. Troubleshooting
  • 7.16.5. Minimal Input File
• 7.17. Interface to SINGLE_ANISO module
  • 7.17.1. General description
  • 7.17.2. Running SINGLE_ANISO calculations
  • 7.17.3. Reference list of CASSCF/ANISO keywords
  • 7.17.4. How to cite
• 7.18. Interface to POLY_ANISO module
  • 7.18.1. General description
  • 7.18.2. Files
    • 7.18.2.1. Input files
    • 7.18.2.2. Output files
  • 7.18.3. List of keywords
    • 7.18.3.1. Mandatory keywords defining the calculation
    • 7.18.3.2. Keywords defining the magnetic exchange interactions
    • 7.18.3.3. Optional general keywords to control the input
• 7.19. N-Electron Valence State Pertubation Theory
  • 7.19.1. RI, RIJK and RIJCOSX Approximation
  • 7.19.2. Beyond the RI approximation: DLPNO-NEVPT2
  • 7.19.3. Explicitly correlated NEVPT2: NEVPT2-F12 and DLPNO-NEVPT2-F12
  • 7.19.4. Tackling large active CASSCF spaces
  • 7.19.5. Selecting or Specific States for NEVPT2
  • 7.19.6. Unrelaxed Densities and Natural Orbitals
  • 7.19.7. State-averaged NEVPT2
  • 7.19.8. Quasi-Degenerate SC-NEVPT2
• 7.20. Complete Active Space Peturbation Theory : CASPT2 and CASPT2-K
• 7.21. Dynamic Correlation Dressed CAS
  • 7.21.1. Theory of Nonrelativistic DCD-CAS(2)
  • 7.21.2. Treatment of spin-dependent effects
  • 7.21.3. List of keywords
• 7.22. Density Matrix Renormalization Group
  • 7.22.1. Technical capabilities
  • 7.22.2. How to cite
  • 7.22.3. Overview of BLOCK input and calculations
  • 7.22.4. Standard commands
    • 7.22.4.1. Orbital optimization
    • 7.22.4.2. Advanced options
    • 7.22.4.3. Troubleshooting
    • 7.22.4.4. Complete set of BLOCK options
  • 7.22.5. Appendix: Porphine \(\pi\)-active space calculation
• 7.23. Relativistic Options
  • 7.23.1. Approximate Relativistic Hamiltonians
  • 7.23.2. The Regular Approximation
    • 7.23.2.1. The scaled ZORA variant
    • 7.23.2.2. The regular approximation with model potential
  • 7.23.3. The Douglas-Kroll-Hess Method
  • 7.23.4. Picture-Change Effects
  • 7.23.5. Finite Nucleus Model
  • 7.23.6. Exact Two-Component Theory (X2C)
    • 7.23.6.1. DLU approximation
    • 7.23.6.2. X2C derivatives and properties
  • 7.23.7. Basis Sets in Relativistic Calculations
• 7.24. Approximate Full CI Calculations in Subspace: ICE-CI
  • 7.24.1. Introduction
  • 7.24.2. The ICE-CI and CIPSI Algorithms
  • 7.24.3. A Simple Example Calculation
  • 7.24.4. Accuracy
  • 7.24.5. Scaling behavior
  • 7.24.6. Accuracy of the Wavefunction
  • 7.24.7. Potential Energy Surfaces
  • 7.24.8. Excited States
  • 7.24.9. Tips and Tricks
  • 7.24.10. Large-scale approximate CASSCF: ICE-SCF
  • 7.24.11. The entire input block explained
  • 7.24.12. A Technical Note: orcacclib
• 7.25. CI methods using generated code
  • 7.25.1. Introduction
  • 7.25.2. Input
  • 7.25.3. Available Properties
  • 7.25.4. Analytic Nuclear Gradients with AUTOCI
  • 7.25.5. AUTOCI Response Properties via Analytic Derivatives
  • 7.25.6. Fully Internally Contracted MRCI
  • 7.25.7. Fully Internally Contracted MRCC
    • 7.25.7.1. Input Example
• 7.26. Geometry Optimization
  • 7.26.1. Input Options and General Considerations
    • 7.26.1.1. Redundant Internal Coordinates
    • 7.26.1.2. Coordinate steps
    • 7.26.1.3. Constrained Optimization
    • 7.26.1.4. Constrained Fragments Optimization
  • 7.26.2. Transition State Optimization
    • 7.26.2.1. ScanTS option
    • 7.26.2.2. Hybrid Hessian
    • 7.26.2.3. Partial Hessian Vibrational Analysis
  • 7.26.3. Minimum Energy Crossing Points
  • 7.26.4. Conical Intersections
  • 7.26.5. Numerical Gradients
  • 7.26.6. ORCA as External Optimizer
  • 7.26.7. Gaussian as External Optimizer
• 7.27. Frequency calculations - numerical and analytical
  • 7.27.1. Restarting Numerical Frequency calculations
• 7.28. Intrinsic Reaction Coordinate
• 7.29. Nudged Elastic Band Method
  • 7.29.1. Spring forces
  • 7.29.2. Optimization and convergence of the NEB method
  • 7.29.3. Climbing image NEB
  • 7.29.4. Generation of the initial path
  • 7.29.5. Removal of translational and rotational degrees of freedom
  • 7.29.6. Reparametrization of the path
  • 7.29.7. Useful output
  • 7.29.8. Important warning messages
  • 7.29.9. Parallel execution
  • 7.29.10. zoomNEB
  • 7.29.11. NEB-TS
  • 7.29.12. FAST-NEB-TS and LOOSE-NEB-TS
  • 7.29.13. NEB / NEB-TS and TD-DFT
  • 7.29.14. Summary of Keywords
• 7.30. Excited States via RPA, CIS, TD-DFT and SF-TDA
  • 7.30.1. General Features
  • 7.30.2. Semiempirical Methods
  • 7.30.3. Hartree-Fock Wavefunctions
  • 7.30.4. Non-Hybrid and Hybrid DFT
  • 7.30.5. Collinear Spin-Flip TDA (SF-TD-DFT)
    • 7.30.5.1. First example: methylene and SF-CIS
    • 7.30.5.2. Benzyne and SF-TDA
  • 7.30.6. Including solvation effects via LR-CPCM theory
    • 7.30.6.1. Equilibrium and non-equilibrium conditions
    • 7.30.6.2. Population Analysis of Excited States
  • 7.30.7. Simplified TDA and TD-DFT
    • 7.30.7.1. Theoretical Background
    • 7.30.7.2. Calculation Set-up
  • 7.30.8. Double-hybrid functionals and Doubles Correction
  • 7.30.9. Natural Transition Orbitals
  • 7.30.10. Computational Aspects
    • 7.30.10.1. RI Approximation (AO-Basis)
    • 7.30.10.2. RI Approximation (MO-Basis)
    • 7.30.10.3. Integral Handling
    • 7.30.10.4. Valence versus Rydberg States
    • 7.30.10.5. Restrictions for Range-Separated Density Functionals
    • 7.30.10.6. Potential Energy Surface Scans
    • 7.30.10.7. Potential Energy Surface Scans along Normal Coordinates
    • 7.30.10.8. Normal Mode Scan Calculations Between Different Structures
    • 7.30.10.9. Printing Extra Gradients Sequentially
  • 7.30.11. Keyword List
• 7.31. Excited States via ROCIS and DFT/ROCIS
  • 7.31.1. General Use
  • 7.31.2. Transition Metal L-Edges with ROCIS or DFT/ROCIS
  • 7.31.3. Natural Transition Orbitals/ Natural Difference Orbitals
  • 7.31.4. Resonant Inelastic Scattering Spectroscopy
    • 7.31.4.1. General
    • 7.31.4.2. Processing the spectra with orca_mapspc
    • 7.31.4.3. Generating Cuts
  • 7.31.5. Core PNO-ROCIS, PNO-ROCIS/DFT
  • 7.31.6. ROCIS Magnetic Properties
  • 7.31.7. Keyword List
• 7.32. Excited States via MC-RPA
  • 7.32.1. General Description
  • 7.32.2. Detecting CASSCF Instabilities
  • 7.32.3. Natural Transition Orbitals
  • 7.32.4. Computational Aspects
  • 7.32.5. Keyword List
• 7.33. Excited States via EOM-CCSD
  • 7.33.1. General Description
  • 7.33.2. Memory Management
  • 7.33.3. Initial Guess
  • 7.33.4. Hamiltonian Construction
  • 7.33.5. Solution of the (Nonsymmetric) Eigenproblem
  • 7.33.6. Convergence, Restart, Preconditioning and Subspace Expansion
  • 7.33.7. Properties in the RHF EOM implementation
  • 7.33.8. Some tips and tricks for EOM-CC calculation
• 7.34. Excited States via STEOM-CCSD
  • 7.34.1. General Description
  • 7.34.2. Selection of Active space
  • 7.34.3. Active space selection using TD-DFT densities
  • 7.34.4. The reliability of the calculated excitation energy
  • 7.34.5. Removal of IP and EA states with double excitation character
  • 7.34.6. Transition and difference densities
  • 7.34.7. Properties
  • 7.34.8. Solvation (Experimental)
  • 7.34.9. Spin-Orbit Coupling (Experimental)
  • 7.34.10. Core excitation
  • 7.34.11. Transient absorption
• 7.35. Excited States via IH-FSMR-CCSD
  • 7.35.1. General Description
  • 7.35.2. Properties
  • 7.35.3. Solvation Correction
• 7.36. Excited States using PNO-based coupled cluster
  • 7.36.1. General Description
  • 7.36.2. Reference State Energy
  • 7.36.3. Use of Local Orbitals
  • 7.36.4. Some tips and tricks for bt-PNO calculations
• 7.37. Excited States via DLPNO-STEOM-CCSD
  • 7.37.1. PNO dressing (experimental keyword)
  • 7.37.2. Keywords from STEOM-CCSD
  • 7.37.3. Tips and Tricks
• 7.38. Core-level spectroscopy with coupled cluster methods
  • 7.38.1. Core-ionization
  • 7.38.2. Core-Excitation
• 7.39. The Multireference Correlation Module
  • 7.39.1. General Description
  • 7.39.2. Properties Calculation Using the SOC Submodule
    • 7.39.2.1. Zero-Field Splitting
    • 7.39.2.2. Local Zero-Field Splitting
    • 7.39.2.3. Zero-Field Splitting from an excited Multiplet
    • 7.39.2.4. g-Tensor
    • 7.39.2.5. Magnetization and Magnetic Susceptibility
    • 7.39.2.6. MCD and Absorption Spectra
    • 7.39.2.7. Addition of Magnetic Fields
    • 7.39.2.8. Relativistic Picture Change in Douglas-Kroll-Hess SOC and Zeeman Operators
    • 7.39.2.9. X-ray Spectroscopy
• 7.40. Multireference Equation of Motion Coupled-Cluster (MR-EOM-CC) Theory
  • 7.40.1. The Steps Required to Run an MR-EOM Calculation
    • 7.40.1.1. State-Averaged CASSCF Calculation
    • 7.40.1.2. Selection of the States to Include in the MR-EOM Calculation
    • 7.40.1.3. Running the MR-EOM Calculation
  • 7.40.2. Approximate Inclusion of Spin-Orbit Coupling Effects in MR-EOM Calculations
  • 7.40.3. A Projection/Singular PT Scheme to Overcome Convergence Issues in the T Amplitude Iterations
  • 7.40.4. An Orbital Selection Scheme for More Efficient Calculations of Excitation Spectra with MR-EOM
  • 7.40.5. Nearly Size Consistent Results with MR-EOM by Employing an MR-CEPA(0) Shift in the Final Diagonalization Procedure
  • 7.40.6. Perturbative MR-EOM-PT
• 7.41. Simulation and Fit of Vibronic Structure in Electronic Spectra, Resonance Raman Excitation Profiles and Spectra with the orca_asa Program
  • 7.41.1. General Description of the Program
  • 7.41.2. Spectral Simulation Procedures: Input Structure and Model Parameters
    • 7.41.2.1. Example: Simple Mode
    • 7.41.2.2. Example: Modelling of Absorption and Fluorescence Spectra within the IMDHO Model
    • 7.41.2.3. Example: Modelling of Absorption and Fluorescence Spectra within the IMDHOFA Model
    • 7.41.2.4. Example: Modelling of Effective Broadening, Effective Stokes Shift and Temperature Effects in Absorption and Fluorescence Spectra within the IMDHO Model
    • 7.41.2.5. Example: Modelling of Absorption and Resonance Raman Spectra for the 1-\(^1\)A\(_g\) \(\rightarrow\) 1-\(^1\)B\(_u\) Transition in trans-1,3,5-Hexatriene
    • 7.41.2.6. Example: Modelling of Absorption Spectrum and Resonance Raman Profiles for the 1-\(^1\)A\(_g\) \(\rightarrow\) 1-\(^1\)B\(_u\) Transition in trans-1,3,5-Hexatriene
  • 7.41.3. Fitting of Experimental Spectra
    • 7.41.3.1. Example: Gauss-Fit of Absorption Spectrum
    • 7.41.3.2. Example: Fit of Absorption and Resonance Raman Spectra for 1-\(^1\)A\(_g\) \(\rightarrow\) 1-\(^1\)B\(_u\) Transition in trans-1,3,5-Hexatriene
    • 7.41.3.3. Example: Single-Mode Fit of Absorption and Fluorescence Spectra for 1-\(^1\)A\(_g\) \(\rightarrow\) 1-\(^1\)B\(_{2u}\) Transition in Tetracene
  • 7.41.4. Quantum-Chemically Assisted Simulations and Fits of Optical Bandshapes and Resonance Raman Intensities
    • 7.41.4.1. Example: Quantum-Chemically Assisted Analysis and Fit of the Absorption and Resonance Raman Spectra for 1-\(^1\)A\(_g\) \(\rightarrow\) 1-\(^1\)B\(_u\) Transition in trans-1,3,5-Hexatriene
    • 7.41.4.2. Important Notes about Proper Comparison of Experimental and Quantum Chemically Calculated Resonance Raman Spectra
    • 7.41.4.3. Example: Normal Mode Scan Calculations of Model Parameters for 1-\(^1\)A\(_g\) \(\rightarrow\) 1-\(^1\)B\(_u\) Transition in trans-1,3,5-Hexatriene
• 7.42. One Photon Spectroscopy
  • 7.42.1. General Description
  • 7.42.2. Light-matter interaction approaches
  • 7.42.3. Natural electric circular dichroism
  • 7.42.4. SOC and SSC corrected spectrum
  • 7.42.5. OPS Full list of keywords
  • 7.42.6. Notes
• 7.43. Magnetic properties through Quasi Degenerate Perturbation Theory
  • 7.43.1. Quasi Degenerate Perturbation Theory (QDPT) in a nutshell
  • 7.43.2. Magnetic properties through the Effective Hamiltonian
  • 7.43.3. Organization of QDPT Magnetic Properties Computation
• 7.44. Simulation of (Magnetic) Circular Dichroism and Absorption Spectra
  • 7.44.1. General description of the program
  • 7.44.2. Running and analyzing MCD calculations in TDDFT module
  • 7.44.3. Running MCD calculations in other modules
  • 7.44.4. List of related keywords
• 7.45. More on the Excited State Dynamics module
  • 7.45.1. Absorption and Emission Rates and Spectrum
    • 7.45.1.1. General Aspects of the Theory
    • 7.45.1.2. Approximations to the excited state PES
    • 7.45.1.3. Mixing methods
    • 7.45.1.4. Removal of frequencies
    • 7.45.1.5. Normal modes coordinate systems
    • 7.45.1.6. Geometry rotation and Duschinsky matrices
    • 7.45.1.7. Derivatives of the transition dipole
    • 7.45.1.8. The Fourier Transform step
    • 7.45.1.9. Spectrum options
    • 7.45.1.10. General
  • 7.45.2. Intersystem crossing rates
    • 7.45.2.1. General Aspects of the Theory
    • 7.45.2.2. Tips and Tricks
  • 7.45.3. Resonant Raman Spectrum
    • 7.45.3.1. General Aspects of the Theory
    • 7.45.3.2. Specific Keywords and Details
  • 7.45.4. Circular Polarized Spectroscopies
    • 7.45.4.1. General Aspects of the Theory
  • 7.45.5. Magnetic Circular Dichroism
    • 7.45.5.1. General Aspects of the Theory
    • 7.45.5.2. Specific Keywords and recommendations
  • 7.45.6. Complete Keyword List for the ESD Module
• 7.46. More details on the ORCA DOCKER
  • 7.46.1. Underlying theory
  • 7.46.2. Looking Deeper into the Output
  • 7.46.3. The final steps
  • 7.46.4. General Tips
  • 7.46.5. Complete Keyword List
• 7.47. More on the ORCA SOLVATOR
  • 7.47.1. The Simpler Stochastic Mode
  • 7.47.2. Adding Explicit Solvents with the Docker
    • 7.47.2.1. The Wall Potential
    • 7.47.2.2. The DOCKER
  • 7.47.3. Controlling True Randomness
  • 7.47.4. Vacuum Search
  • 7.47.5. Complete Keyword List
• 7.48. Ab initio Molecular Dynamics Simulations
  • 7.48.1. Changes in ORCA 5.0
  • 7.48.2. Changes in ORCA 4.2 (Aug 2019)
  • 7.48.3. Changes in ORCA 4.1 (Dec 2018)
  • 7.48.4. Input Format
    • 7.48.4.1. Commands
    • 7.48.4.2. Separating Arguments
    • 7.48.4.3. Physical Units
  • 7.48.5. Discussion of Features
    • 7.48.5.1. Restarting Simulations
    • 7.48.5.2. Regions
    • 7.48.5.3. Metadynamics
  • 7.48.6. Command List
  • 7.48.7. Command Overview
    • 7.48.7.1. Cell
    • 7.48.7.2. Constraint
    • 7.48.7.3. Dump
    • 7.48.7.4. Initvel
    • 7.48.7.5. Manage_Colvar
    • 7.48.7.6. Manage_Region
    • 7.48.7.7. Metadynamics
    • 7.48.7.8. Minimize
    • 7.48.7.9. PrintLevel
    • 7.48.7.10. Randomize
    • 7.48.7.11. Restart
    • 7.48.7.12. Restraint
    • 7.48.7.13. Run
    • 7.48.7.14. SCFLog
    • 7.48.7.15. Screendump
    • 7.48.7.16. Thermostat
    • 7.48.7.17. Timestep
  • 7.48.8. Scientific Background
    • 7.48.8.1. Time Integration and Equations of Motion
    • 7.48.8.2. Velocity Initialization
    • 7.48.8.3. Thermostats
    • 7.48.8.4. Berendsen Thermostat
    • 7.48.8.5. Constraints
• 7.49. Fast Multipole Method
  • 7.49.1. The Octree hierarchy
  • 7.49.2. Approximation of the Far Field interactions
  • 7.49.3. The “Very” Fast Multipole Method (VFMM)
  • 7.49.4. Recommended input
  • 7.49.5. Some examples
• 7.50. Implicit Solvation Models
  • 7.50.1. The Conductor-like Polarizable Continuum Model (C-PCM)
    • 7.50.1.1. Use of the Gaussian Charge Scheme
    • 7.50.1.2. Use of the Point Charge Scheme
    • 7.50.1.3. Calculation of the free energy of solvation within the C-PCM
  • 7.50.2. The Conductor-like Screening Solvation Model (COSMO)
  • 7.50.3. The SMD Solvation Model
  • 7.50.4. Dynamic Radii Adjustment for Continuum Solvation (DRACO)
  • 7.50.5. OpenCOSMO-RS
    • 7.50.5.1. How to Run a ORCA/COSMO-RS Calculation
  • 7.50.6. Implicit Solvation in Coupled-Cluster Methods
    • 7.50.6.1. PTE scheme
    • 7.50.6.2. PTE(S) scheme
    • 7.50.6.3. PTES scheme
• 7.51. Calculation of Properties
  • 7.51.1. Electric Properties
  • 7.51.2. The Spin-Orbit Coupling Operator
    • 7.51.2.1. Exclusion of Atomic Centers
  • 7.51.3. EPR and NMR properties
    • 7.51.3.1. Hyperfine and Quadrupole Couplings
    • 7.51.3.2. The g-Tensor
    • 7.51.3.3. Zero-Field-Splitting
    • 7.51.3.4. General Treatment of ZFS
    • 7.51.3.5. Spin-rotation constants
    • 7.51.3.6. Cartesian Index Conventions for EPR and NMR Tensors
    • 7.51.3.7. MP2 level magnetic properties
    • 7.51.3.8. Nucleus-independent chemical shielding
    • 7.51.3.9. Shielding tensor orbital decomposition
    • 7.51.3.10. Treatment of Tau in Meta-GGA Functionals
  • 7.51.4. Paramagnetic NMR shielding tensors
  • 7.51.5. Calculating properties from existing densities
  • 7.51.6. Local Energy Decomposition
• 7.52. Natural Bond Orbital (NBO) Analysis
  • 7.52.1. NBO Deletions
  • 7.52.2. NBO for Post-HF Densities
  • 7.52.3. Natural Chemical Shielding Analysis (NCS)
• 7.53. Population Analyses and Control of Output
  • 7.53.1. Controlling Output
  • 7.53.2. Mulliken Population Analysis
  • 7.53.3. Löwdin Population Analysis
  • 7.53.4. Mayer Population Analysis
  • 7.53.5. Natural Population Analysis
  • 7.53.6. Local Spin Analysis
  • 7.53.7. UNO Orbital Printing
  • 7.53.8. Hirshfeld Charges
  • 7.53.9. MBIS Charges
• 7.54. Orbital and Density Plots
  • 7.54.1. Contour Plots
  • 7.54.2. Surface Plots
    • 7.54.2.1. General Points
    • 7.54.2.2. FOD plots
    • 7.54.2.3. Interface to gOpenMol
    • 7.54.2.4. Interface to Molekel
• 7.55. Utility Programs
  • 7.55.1. orca_mapspc
  • 7.55.2. orca_chelpg
  • 7.55.3. orca_pltvib
  • 7.55.4. orca_vib
  • 7.55.5. orca_loc
  • 7.55.6. orca_blockf
  • 7.55.7. orca_plot
    • 7.55.7.1. Perform Orbital Plots
    • 7.55.7.2. List of Density Plots
    • 7.55.7.3. Perform Algebraic Operations
    • 7.55.7.4. Additional TIPS regarding Density Plots
  • 7.55.8. orca_2mkl: Old Molekel as well as Molden inputs
  • 7.55.9. orca_2aim
  • 7.55.10. orca_vpot
  • 7.55.11. orca_euler
  • 7.55.12. orca_exportbasis
  • 7.55.13. orca_eca
  • 7.55.14. orca_pnmr
  • 7.55.15. orca_lft
  • 7.55.16. orca_crystalprep
• 7.56. Compound Methods
  • 7.56.1. Commands
    • 7.56.1.1. &
    • 7.56.1.2. Abort
    • 7.56.1.3. Alias
    • 7.56.1.4. Basenames
    • 7.56.1.5. Break
    • 7.56.1.6. CloseFile
    • 7.56.1.7. Continue
    • 7.56.1.8. Dataset
    • 7.56.1.9. D.MakeReferenceFromDir
    • 7.56.1.10. D.Print
    • 7.56.1.11. Diagonalize
    • 7.56.1.12. End
    • 7.56.1.13. EndRun
    • 7.56.1.14. EndFor
    • 7.56.1.15. For
    • 7.56.1.16. Geometry
    • 7.56.1.17. G.BohrToAngs
    • 7.56.1.18. G.CreateBSSE
    • 7.56.1.19. G.FollowNormalMode
    • 7.56.1.20. G.GetAtomicNumbers
    • 7.56.1.21. G.GetBondDistance
    • 7.56.1.22. G.GetCartesians
    • 7.56.1.23. G.GetGhostAtoms
    • 7.56.1.24. G.GetNumOfAtoms
    • 7.56.1.25. G.MoveAtomToCenter
    • 7.56.1.26. G.Read
    • 7.56.1.27. G.RemoveAtoms
    • 7.56.1.28. G.RemoveElements
    • 7.56.1.29. G.WriteXYZFile
    • 7.56.1.30. GOAT
    • 7.56.1.31. Goat.Get_Energy
    • 7.56.1.32. Goat.Get_Num_Of_Geometries
    • 7.56.1.33. Goat.Parse_Ensemble_File
    • 7.56.1.34. Goat.Set_Basename
    • 7.56.1.35. Goat.Print
    • 7.56.1.36. Goat.WriteXYZFile
    • 7.56.1.37. GetNumOfInstances
    • 7.56.1.38. GoTo
    • 7.56.1.39. If
    • 7.56.1.40. InvertMatrix
    • 7.56.1.41. Mat_p_Mat
    • 7.56.1.42. Mat_x_Mat
    • 7.56.1.43. Mat_x_Scal
    • 7.56.1.44. New_Geom
      • 7.56.1.44.1. Displace
    • 7.56.1.45. OpenFile
      • 7.56.1.45.1. Remove_Atom
      • 7.56.1.45.2. Remove_Element
    • 7.56.1.46. New_Step
    • 7.56.1.47. Print
    • 7.56.1.48. Read
    • 7.56.1.49. ReadProperty
    • 7.56.1.50. Read_Geom
    • 7.56.1.51. ReadMOs
    • 7.56.1.52. S.GetBasename
    • 7.56.1.53. S.GetChar
    • 7.56.1.54. S.GetSuffix
    • 7.56.1.55. Step_End
    • 7.56.1.56. Sys_cmd
    • 7.56.1.57. Timer
    • 7.56.1.58. T.Last
    • 7.56.1.59. T.Reset
    • 7.56.1.60. T.Start
    • 7.56.1.61. T.Stop
    • 7.56.1.62. T.Total
    • 7.56.1.63. Variables - General
    • 7.56.1.64. Variables - Declaration
    • 7.56.1.65. Variables - Assignment
    • 7.56.1.66. Variables - Functions
    • 7.56.1.67. V.GetBool()
    • 7.56.1.68. V.GetDim1()
    • 7.56.1.69. V.GetDim2()
    • 7.56.1.70. V.GetDouble()
    • 7.56.1.71. V.GetInteger()
    • 7.56.1.72. V.GetSize()
    • 7.56.1.73. V.GetString()
    • 7.56.1.74. V.PrintMatrix()
    • 7.56.1.75. With
    • 7.56.1.76. Write2File
    • 7.56.1.77. Write2String
  • 7.56.2. List of known Properties
  • 7.56.3. List of known Simple input commands
• 7.57. Compound Examples
  • 7.57.1. Introduction
  • 7.57.2. Hello World
  • 7.57.3. New Job
  • 7.57.4. High Accuracy
  • 7.57.5. Scan
  • 7.57.6. Numerical polarizabilities
  • 7.57.7. Iterative optimization
  • 7.57.8. Gradient extrapolation
  • 7.57.9. BSSE Optimization
  • 7.57.10. Umbrella script
  • 7.57.11. Multi reference
  • 7.57.12. GoTo
• 7.58. orca_2json
  • 7.58.1. Export ORCA data
  • 7.58.2. Configuration file
  • 7.58.3. Available information
    • 7.58.3.1. Property File
    • 7.58.3.2. Basic Information
    • 7.58.3.3. Densities
    • 7.58.3.4. Electron Integrals
      • 7.58.3.4.1. 1-electron integrals
      • 7.58.3.4.2. 1-electron property integrals
      • 7.58.3.4.3. 1-electron relativistic integrals
      • 7.58.3.4.4. 1-electron relativistic property integrals
      • 7.58.3.4.5. Origin setting
      • 7.58.3.4.6. 2-electron integrals
        • 7.58.3.4.6.1. 2-electron integrals in AO basis
        • 7.58.3.4.6.2. 2-electron integrals in MO basis
        • 7.58.3.4.6.3. RI 2-electron integrals
        • 7.58.3.4.6.4. Full Integral Transformation
        • 7.58.3.4.6.5. More 2-electron integrals
        • 7.58.3.4.6.6. Orbital Windows, AuxBasisType and Threshold
    • 7.58.3.5. TDDFT amplitude data (CIS/RPA)
    • 7.58.3.6. JSON Format
    • 7.58.3.7. MO Coefficients
  • 7.58.4. Import JSON data into ORCA
    • 7.58.4.1. Basic Information
    • 7.58.4.2. Definition of the real solid harmonic Gaussian orbitals
      • 7.58.4.2.1. Angular momentum \(\boldsymbol{s}\) (\(\boldsymbol{\ell=0}\))
      • 7.58.4.2.2. Angular momentum \(\boldsymbol{p}\) (\(\boldsymbol{\ell=1}\))
      • 7.58.4.2.3. Angular momentum \(\boldsymbol{d}\) (\(\boldsymbol{\ell=2}\))
      • 7.58.4.2.4. Angular momentum \(\boldsymbol{f}\) (\(\boldsymbol{\ell=3}\))
      • 7.58.4.2.5. Angular momentum \(\boldsymbol{g}\) (\(\boldsymbol{\ell=4}\))
      • 7.58.4.2.6. Angular momentum \(\boldsymbol{h}\) (\(\boldsymbol{\ell=5}\))
      • 7.58.4.2.7. Angular momentum \(\boldsymbol{i}\) (\(\boldsymbol{\ell=6}\))
      • 7.58.4.2.8. Angular momentum \(\boldsymbol{j}\) (\(\boldsymbol{\ell=7}\))
      • 7.58.4.2.9. Angular momentum \(\boldsymbol{k}\) (\(\boldsymbol{\ell=8}\))
• 7.59. Property File
  • 7.59.1. txt format
    • 7.59.1.1. Bracket information
  • 7.59.2. JSON format