ORCA Manual for ab initio, DFT and semiempirical SCF-MO package

489 Pages·2016·16.2 MB·English

by  Neese F.

- An ab initio, DFT and semiempirical SCF-MO package -

Version 2.8-20 September 2010

Design
 andScientific
 Directorship:

Frank Neese
Technical
 Directorship:

Frank Wennmohs
Lehrstuhl
 für
 Theoretische
 Chemie

Wegelerstr.
 12D-­‐53115
 Bonn,
 Germany

[email protected]­‐bonn.de

With
 contributions
 from:

Ute Becker, Dmitry Ganyushin, Andreas Hansen, Dimitrios G. Liakos, Christian Kollmar,
Simone Kossmann, Taras Petrenko, Christoph Reimann, Christoph Riplinger,
Kantharuban Sivalingam, Edward Valeev, Boris Wezisla

Input
 Description
TABLE
 OF
 CONTENTS

1
  GENERAL INFORMATION........................................................................................11

1.1
  PROGRAM COMPONENTS.............................................................................................11

1.2
  UNITS AND CONVERSION FACTORS.............................................................................12

2
  PUBLICATIONS RELATED TO ORCA....................................................................13

3
  CALLING THE PROGRAM (SERIAL AND PARALLEL).....................................23

3.1
  CALLING THE PROGRAM..............................................................................................23

3.2
  HINTS ON THE USE OF PARALLEL ORCA.....................................................................26

4
  GENERAL STRUCTURE OF THE INPUT FILE.....................................................29

4.1
  INPUT BLOCKS............................................................................................................29

4.2
  KEYWORD LINES........................................................................................................31

4.3
  ORCA AND SYMMETRY.............................................................................................42

4.4
  USE OF EFFECTIVE CORE POTENTIALS........................................................................43

4.5
  JOBS WITH MULTIPLE STEPS......................................................................................50

5
  INPUT OF COORDINATES........................................................................................51

6
  RUNNING TYPICAL CALCULATIONS...................................................................54

6.1
  SINGLE POINT ENERGIES AND GRADIENTS....................................................................54

6.1.1
  Hartree-Fock......................................................................................................54

6.1.1.1
  Standard single points.........................................................................................................................54

6.1.1.2
  Basis Set Options................................................................................................................................55

6.1.1.3
  SCF and Symmetry.............................................................................................................................56

6.1.2
  MP2....................................................................................................................59

6.1.2.1
  MP2 and RI-MP2 Energies.................................................................................................................59

6.1.2.2
  Orbital Optimized MP2 methods........................................................................................................60

6.1.2.3
  MP2 and RI-MP2 Gradients...............................................................................................................61

6.1.2.4
  Frozen core options............................................................................................................................63

6.1.2.5
  MP2 Densities and Natural Orbitals...................................................................................................63

6.1.3
  Coupled Cluster and Coupled Pair Methods.....................................................64

6.1.3.1
  Basics..................................................................................................................................................64

6.1.3.2
  Static versus Dynamic Correlation.....................................................................................................68

6.1.3.3
  Basis Sets for Correlated Calculations. The case of ANOs................................................................72

6.1.3.4
  Automatic extrapolation to the basis set limit....................................................................................75
Orca Version 2 - Input Description 3

6.1.3.5
  Local Coupled Pair and Coupled Cluster Calculations......................................................................79

6.1.4
  Density Functional.............................................................................................82

6.1.4.1
  Standard Density Functional Calculations.........................................................................................82

6.1.4.2
  DFT Calculations with RI...................................................................................................................83

6.1.4.3
  Hartree-Fock and Hybrid DFT Calculations with RIJCOSX.............................................................85

6.1.4.4
  Hartree-Fock and Hybrid DFT Calculations with RI-JK...................................................................86

6.1.4.5
  DFT Calculations with Second Order Perturbative Correction (double hybrid functionals).............87

6.1.4.6
  DFT Calculations with Empirical Van der Waals Correction............................................................88

6.1.5
  Quadratic Convergence......................................................................................89

6.1.6
  Counterpoise Correction....................................................................................91

6.1.7
  Complete Active Space Self-Consistent Field.....................................................93

6.1.7.1
  Introduction........................................................................................................................................93

6.1.7.2
  A simple example...............................................................................................................................94

6.1.7.3
  Starting Orbitals..................................................................................................................................96

6.1.7.4
  CASSCF and Symmetry...................................................................................................................101

6.1.7.5
  RI and RIJCOSX approximations for CASSCF...............................................................................105

6.1.7.6
  Breaking Chemical Bonds................................................................................................................106

6.1.7.7
  Excited States...................................................................................................................................111

6.1.7.8
  CASSCF Natural Orbitals as input for Coupled Cluster Calculations.............................................113

6.1.8
  N-Electron Valence State Perturbation Theory (NEVPT2)..............................118

6.1.8.1
  Introduction......................................................................................................................................118

6.1.8.2
  A simple example.............................................................................................................................119

6.1.8.3
  RI Approximation.............................................................................................................................120

6.1.8.4
  Parametric surface scans...................................................................................................................120

6.1.8.5
  Approximations for large active CASSCF space.............................................................................121

6.1.8.6
  State-averaged NEVPT2...................................................................................................................122

6.1.9
  Scalar Relativistic SCF.....................................................................................123

6.1.9.1
  Douglas-Kroll-Hess..........................................................................................................................123

6.1.9.2
  ZORA and IORA..............................................................................................................................124

6.1.10
  How to do efficient calculations with atomic natural orbitals?.......................125

6.2
  GEOMETRY OPTIMIZATIONS, SURFACE SCANS, TRANSITION STATES, MECPS..........127

6.2.1
  Geometry Optimizations..................................................................................127

6.2.2
  Numerical Gradients........................................................................................128

6.2.3
  Some Notes and Tricks.....................................................................................128

6.2.4
  Initial Hessian for minimization.......................................................................129

6.2.5
  Coordinate systems for Optimizations..............................................................130

6.2.6
  Constrained Optimizations...............................................................................131

6.2.7
  Constrained Optimizations for Molecular Clusters (Fragment Optimization).133
Orca Version 2 - Input Description 4

6.2.8
  Relaxed Surface Scans......................................................................................135

6.2.9
  Multiple XYZ file scans.....................................................................................138

6.2.10
  Transition States...............................................................................................138

6.2.10.1
  Introduction to Transition State Searches....................................................................................138

6.2.10.2
  Hessians for Transition State Calculations..................................................................................141

6.2.10.3
  Special Coordinates for Transition State Optimizations..............................................................143

6.2.11
  MECP optimization..........................................................................................143

6.2.12
  Using the Gaussian optimizer..........................................................................145

6.2.13
  ORCA as external optimizer............................................................................146

6.3
  VIBRATIONAL FREQUENCIES.....................................................................................146

6.4
  REACTION ENERGIES FROM COMPOUND JOBS...........................................................148

6.5
  EXCITED STATES WITH CIS, CIS(D) AND TD-DFT..................................................150

6.5.1
  General Use......................................................................................................151

6.5.2
  Use of TD-DFT for the calculation of X-ray absorption spectra.....................151

6.5.3
  Excited state Geometry optimization................................................................155

6.5.4
  Doubles correction...........................................................................................155

6.6
  MULTIREFERENCE CONFIGURATION INTERACTION AND PERTURBATION THEORY.....156

6.6.1
  Introductory Remarks.......................................................................................156

6.6.1.1
  Introduction......................................................................................................................................156

6.6.1.2
  RI-approximation..............................................................................................................................156

6.6.1.3
  Individual Selection..........................................................................................................................157

6.6.1.4
  Single excitations..............................................................................................................................157

6.6.1.5
  Reference Spaces..............................................................................................................................157

6.6.1.6
  Size Consistency...............................................................................................................................158

6.6.1.7
  Performance......................................................................................................................................158

6.6.1.8
  Symmetry..........................................................................................................................................159

6.6.2
  A Tutorial Type Example of a MR Calculation................................................160

6.6.3
  Excitation Energies between different multiplicities........................................175

6.6.4
  Correlation Energies........................................................................................176

6.6.5
  Thresholds........................................................................................................177

6.6.5.1
  Reference Values for Total Energies................................................................................................177

6.6.5.2
  Convergence of Single Reference Approaches with Respect to T ................................................178

sel
6.6.5.3
  Convergence of Multireference Approaches with Respect to T ...................................................178

pre
6.6.6
  Energy Differences – Bond Breaking...............................................................180

6.6.7
  Energy Differences – Spin Flipping.................................................................182

6.6.8
  Potential Energy Surfaces................................................................................184
Orca Version 2 - Input Description 5

6.6.9
  Multireference Systems – Ozone.......................................................................187

6.6.10
  Size Consistency...............................................................................................189

6.6.11
  Efficient MR-MP2 calculations for larger molecules.......................................190

6.7
  SOLVATION...............................................................................................................191

6.8
  CALCULATION OF PROPERTIES..................................................................................193

6.8.1
  Population Analysis and Related Things..........................................................193

6.8.2
  Absorption and Fluorescence Bandshapes.......................................................197

6.8.3
  IR/Raman spectra, Vibrational Modes and Isotope Shifts...............................202

6.8.3.1
  IR Spectra.........................................................................................................................................202

6.8.3.2
  Raman Spectra..................................................................................................................................204

6.8.3.3
  Resonance Raman Spectra................................................................................................................206

6.8.3.4
  NRVS Spectra...................................................................................................................................206

6.8.3.5
  Animation of Vibrational Modes......................................................................................................207

6.8.3.6
  Isotope Shifts....................................................................................................................................208

6.8.4
  Thermochemistry..............................................................................................210

6.8.5
  Electric Properties............................................................................................213

6.8.6
  NMR Chemical Shifts.......................................................................................214

6.8.7
  Hyperfine and Quadrupole Couplings.............................................................216

6.8.8
  The EPR g-Tensor and the Zero-Field Splitting Tensor..................................219

6.8.9
  ‘Broken-Symmetry’ Wavefunctions and Exchange Couplings.........................221

7
  DETAILED DOCUMENTATION.............................................................................224

7.1
  MORE ON COORDINATE INPUT..................................................................................224

7.1.1
  Fragment Specification....................................................................................224

7.1.2
  Defining Geometry Parameters and Scanning Potential Energy Surfaces......225

7.1.3
  Inclusion of Point Charges...............................................................................227

7.2
  CHOICE OF COMPUTATIONAL MODEL.......................................................................228

7.2.1
  Features Common to All Calculations.............................................................228

7.2.2
  Density functional calculations........................................................................230

7.2.2.1
  Choice of Functional........................................................................................................................230

7.2.2.2
  Choice of Integration Grid................................................................................................................235

7.2.2.3
  Using the RI-J approximation to the Coulomb part.........................................................................241

7.2.2.4
  The Split-RI-J Coulomb Approximation..........................................................................................243

7.2.2.5
  Using the RI Approximation for Hartree-Fock and Hybrid DFT (RIJONX)...................................244

7.2.2.6
  Using the RI Approximation for Hartree-Fock and Hybrid DFT (RIJCOSX).................................245

7.2.2.7
  Improved Analytical Evaluation of the Coulomb term: Split-J........................................................247

7.2.2.8
  The Standard Basis Sets and Computational Levels........................................................................247
Orca Version 2 - Input Description 6

7.2.3
  Second Order Møller-Plesset Perturbation Theory.........................................248

7.2.4
  Semiempirical Methods....................................................................................251

7.3
  CHOICE OF BASIS SET...............................................................................................255

7.3.1
  Built in Basis Sets.............................................................................................255

7.3.2
  Assigning or Adding Basis Functions to an Element.......................................260

7.3.3
  Assigning or Adding Basis Functions to Individual Atoms..............................261

7.3.4
  Reading orbital and auxiliary basis sets from a file.........................................262

7.4
  CHOICE OF INITIAL GUESS AND RESTART OF SCF CALCULATIONS...........................263

7.4.1
  AutoStart feature..............................................................................................263

7.4.2
  One Electron Matrix Guess..............................................................................264

7.4.3
  Basis Set Projection..........................................................................................264

7.4.4
  PModel Guess...................................................................................................264

7.4.5
  Hueckel and PAtom Guesses............................................................................265

7.4.6
  Restarting SCF Calculations............................................................................265

7.4.7
  Changing the Order of Initial Guess MOs and Breaking the Initial Guess Symmetry
266

7.5
  SCF CONVERGENCE.................................................................................................267

7.5.1
  Convergence Tolerances..................................................................................267

7.5.2
  Dynamic and Static Damping...........................................................................269

7.5.3
  Level Shifting....................................................................................................270

7.5.4
  Direct Inversion in Iterative Subspace (DIIS)..................................................270

7.5.5
  An alternative DIIS algorithm: KDIIS..............................................................271

7.5.6
  Approximate Second Order SCF (SOSCF)......................................................271

7.5.7
  Full Second Order SCF (NR)...........................................................................272

7.5.8
  Fractional Occupation Numbers......................................................................275

7.6
  CHOICE OF WAVEFUNCTION AND INTEGRAL HANDLING...........................................276

7.6.1
  Choice of Wavefunction Type...........................................................................276

7.6.2
  UHF Natural Orbitals......................................................................................279

7.6.3
  Integral Handling (Conventional, Direct, SemiDirect)....................................279

7.7
  THE SECOND ORDER MANY BODY PERTURBATION THEORY MODULE (MP2)..........283

7.7.1
  Standard MP2...................................................................................................283

7.7.2
  RI-MP2.............................................................................................................284

7.7.3
  Orbital Optimized MP2....................................................................................292
Orca Version 2 - Input Description 7

7.7.4
  RICOSX-RI-MP2 Gradients.............................................................................296

7.8
  THE SINGLE REFERENCE CORRELATION MODULE....................................................297

7.8.1
  Theory...............................................................................................................297

7.8.2
  Closed shell equations......................................................................................301

7.8.3
  Open shell equations (spin-unrestricted formalism)........................................305

7.8.4
  Use of the MDCI Module.................................................................................305

7.9
  THE COMPLETE ACTIVE SPACE SELF-CONSISTENT FIELD (CASSCF) MODULE........307

7.9.1
  General Description.........................................................................................307

7.9.2
  CASSCF Properties.........................................................................................318

7.10
  N-ELECTRON VALENCE STATE PERTURBATION THEORY......................................319

7.11
  RELATIVISTIC OPTIONS.........................................................................................320

7.12
  GEOMETRY OPTIMIZATION....................................................................................324

7.13
  EXCITED STATES VIA CIS AND TD-DFT................................................................342

7.13.1
  General Features..............................................................................................343

7.13.2
  Semiempirical Methods....................................................................................344

7.13.3
  HF-Wavefunctions............................................................................................347

7.13.4
  Non-Hybrid DFT..............................................................................................347

7.13.5
  Hybrid DFT......................................................................................................349

7.13.6
  Doubles Correction..........................................................................................349

7.13.7
  Computational Aspects.....................................................................................351

7.13.7.1
  RI approximation (AO-basis).......................................................................................................351

7.13.7.2
  RI approximation (MO-basis)......................................................................................................351

7.13.7.3
  Integral Handling.........................................................................................................................352

7.13.7.4
  Valence versus Rydberg states.....................................................................................................352

7.13.7.5
  Asymptotatically Corrected Density Functionals........................................................................353

7.13.7.6
  Potential Energy Surface Scans...................................................................................................356

7.13.7.7
  Potential Energy Surface Scans along Normal Coordinates........................................................357

7.13.7.8
  Normal Mode Scan Calculations Between Different Structures..................................................361

7.14
  THE MULTIREFERENCE CORRELATION MODULE...................................................363

7.14.1
  General Description of the Correlation Module..............................................363

7.14.2
  The SOC Submodule of the MRCI Module....................................................367

7.14.2.1
  Calculation of the Spin-Spin Coupling and Spin-Orbit Coupling and Effects............................367

7.14.2.2
  Magnetic fields in MRCI.............................................................................................................375

7.14.2.3
  g-tensor calculations.....................................................................................................................376

7.14.2.4
  Relativistic Picture Change in Douglas Kroll SOC and Zeeman operators.................................377

7.14.2.5
  MCD and Absorption Spectra Calculation and Generation.........................................................378
Orca Version 2 - Input Description 8

7.15
  SIMULATION AND FIT OF VIBRONIC STRUCTURE IN ELECTRONIC SPECTRA, RESONANCE
RAMAN EXCITATION PROFILES AND SPECTRA WITH THE ORCA_ASA PROGRAM...................382

7.15.1
  General Description of the Program................................................................383

7.15.2
  Spectral Simualtion Procedures: Input Structure and Model Parameters.......384

7.15.2.1
  Example: Simple Model...............................................................................................................384

7.15.2.2
  Example: Modelling of Absorption and Fluorescence Spectra within the IMDHO Model........386

7.15.2.3
  Example: Modelling of Absorption and Fluorescence Spectra within the IMDHOFA Model...389

7.15.2.4
  Example: Modelling of Effective Broadening, Effective Stokes Shift and Temperature Effects in
Absorption and Fluorescence Spectra within the IMDHO Model.....................................................................390

7.15.2.5
  Example: Modelling of Absorption and Resonance Raman Spectra for the 1-1A →1-1B Transition in 1,3,5
g u
trans-hexatriene..................................................................................................................................................393

7.15.2.6
  Example: Modelling of Absorption spectrum and Resonance Raman Profiles for the 1-1A →1-1B
g u
Transition in 1,3,5 trans-hexatriene...................................................................................................................397

7.15.3
  Fitting of Experimental Spectra.......................................................................399

7.15.3.1
  Example: Gauss-Fit of Absorption Spectrum..............................................................................399

7.15.3.2
  Example: Fit of Absorption and Resonance Raman Spectra for 1-1A →1-1B transition in 1,3,5 trans-
g u
hexatriene 406

7.15.3.3
  Example: Single-Mode Fit of Absorption and Fluorescence Spectra for 1-1A →1-1B transition in
g 2u
Tetracene 413

7.15.4
  Quantum-Chemically Assisted Simulations and Fits of Optical Bandshapes and
Resonance Raman Intensities.........................................................................................417

7.15.4.1
  Example: Quantum-Chemically Assisted Analysis and Fit of the Absorption and Resonance Raman Spectra
for the 1-1A →1-1B Transition in 1,3,5 trans-hexatriene.................................................................................418

g u
7.15.4.2
  Important Notes about Proper Comparison of Experimental and Quantum Chemically Calculated
Resonance Raman Spectra.................................................................................................................................426

7.15.4.3
  Example: Normal mode scan calculations of model paramters for 1-1A →1-1B transition in 1,3,5 trans-
g u
hexatriene 428

7.16
  THE COSMO SOLVATION MODEL........................................................................430

7.17
  CALCULATION OF PROPERTIES..............................................................................433

7.17.1
  Electric Properties............................................................................................433

7.17.2
  The Spin-Orbit Coupling Operator..................................................................433

7.17.3
  The EPR/NMR Module.....................................................................................436

7.17.3.1
  Hyperfine and Quadrupole Couplings.........................................................................................437

7.17.3.2
  The g-tensor.................................................................................................................................440

7.17.3.3
  Zero-Field-Splitting......................................................................................................................441

GENERAL TREATMENT........................................................................................................443

7.18
  POPULATIONS ANALYSIS AND CONTROL OF OUTPUT.............................................450

7.18.1
  Controlling Output...........................................................................................450
Orca Version 2 - Input Description 9

7.18.2
  Mulliken Population Analysis...........................................................................452

7.18.3
  Löwdin Population Analysis.............................................................................453

7.18.4
  Mayer Population Analysis..............................................................................454

7.18.5
  Natural Population Analysis............................................................................455

7.18.6
  UNO Orbital Printing.......................................................................................460

7.19
  ORBITAL AND DENSITY PLOTS...............................................................................460

7.19.1
  Contour Plots....................................................................................................460

7.19.2
  Surface Plots.....................................................................................................462

7.19.2.1
  General Points..............................................................................................................................462

7.19.2.2
  Interface to gOpenMol.................................................................................................................464

7.19.2.3
  Interface to Molekel.....................................................................................................................465

7.20
  UTILITY PROGRAMS...............................................................................................466

7.20.1
  orca_mapspc.....................................................................................................466

7.20.2
  orca_chelpg......................................................................................................467

7.20.3
  orca_pltvib........................................................................................................467

7.20.4
  orca_vib............................................................................................................468

7.20.5
  orca_plot...........................................................................................................468

7.20.6
  orca_2mkl: Old Molekel as well as MolDen inputs.........................................468

7.20.7
  orca_vpot..........................................................................................................469

8
  SOME TIPS AND TRICKS (UPDATED DECEMBER 2009)................................469

8.1
  COST VERSUS ACCURACY.........................................................................................469

8.2
  CONVERGING SCF CALCULATIONS...........................................................................473

8.3
  CHOICE OF THEORETICAL METHOD..........................................................................474

9
  LITERATURE..............................................................................................................477

SUMMARY OF REVISIONS............................................................................................480
Orca Version 2 - Input Description 10
Foreword

The
 ORCA
 project
 is
 now
 almost
 10
 years
 old
 and
 it
 is
 probably
 fair
 to
 say
 that
 the
 program
 has
 significantly
 matured
 over
 the
 past
 years.

It
 is
 now
 used
 by
 almost
 4000
 individuals
 or
 research
 groups
 and
 is
 installed
 at
 dozens
 if
 not
 hundreds
 of
 supercomputer
 centers

worldwide.
 We
 feel
 strongly
 encouraged
 by
 this
 fact
 and
 it
 is
 our
 pleasure
 to
 further
 develop
 the
 program
 for
 the
 benefit
 of
 the

computational
 chemistry
 and
 spectroscopy
 communities.

Since
 2006
 when
 the
 group
 moved
 to
 the
 university
 of
 Bonn,
 there
 has
 been
 a
 gradual
 shift
 in
 the
 focus
 of
 the
 development
 from
 special

spectroscopy
 to
 more
 general
 purpose
 quantum
 chemistry.
 This
 was
 made
 possible
 because
 the
 development
 group
 has
 considerably

grown
 and
 highly
 talented
 and
 motivated
 students
 continued
 to
 bring
 in
 new
 features
 in
 and
 greatly
 improved
 existing
 ones.
 The
 areas
 that

are
 perhaps
 most
 active
 in
 future
 developments
 concern
 simplified
 wavefunction
 methods
 or
 the
 single
 reference
 type
 (MP2
 and
 local

coupled
 pair/coupled
 cluster
 methods)
 and
 new
 density
 functionals
 (in
 particular
 double
 hybrid
 functional).
 An
 area
 that
 will
 see
 more

activity
 in
 the
 future
 is
 multireference
 theory.

However,
 with
 all
 developments
 in
 improved
 wavefunctions,
 a
 focus
 of
 the
 program
 will
 remain
 theoretical
 spectroscopy
 and
 we
 plan
 to

further
 enhance

 the
 programs
 capabilities
 in
 this
 area.

Finally,
 performance,
 parallelization
 robustness
 and
 user
 friendliness
 are
 subjects
 that
 are
 high
 on
 our
 priority
 list.

As
 always,
 we
 appreciate
 positive
 as
 well
 as
 negative
 feedback
 from
 our
 growing
 group
 of
 users
 and
 hope
 that
 you
 enjoy
 using
 the
 program

as
 much
 as
 we
 enjoy
 developing
 it.
 As
 ORCA
 is
 strictly
 non-­‐commercial
 you
 can
 count
 on
 the
 fact
 that
 it
 will
 remain
 free
 of
 charge.
 The

best
 way
 to
 show
 your
 appreciation
 of
 our
 efforts
 is
 to
 cite
 our
 original
 research
 and
 development
 papers
 in
 your
 own
 work.
 This
 will

provide
 us
 with
 the
 possibility
 of
 raising
 sufficient
 funding
 for
 continuing
 to
 do
 what
 we
 enjoy
 most
 –
 develop
 quantum
 chemistry!

Frank
 Neese,
 December
 2009