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Contents

• Introduction to MOLPRO
• MOLPRO on the WWW
• References
• 1 HOW TO READ THIS MANUAL
• 2 RUNNING MOLPRO
  • 2.1 Options
  • 2.2 Running MOLPRO on parallel computers
  
  
• 3 DEFINITION OF MOLPRO INPUT LANGUAGE
  • 3.1 Input format
  • 3.2 Commands
  • 3.3 Directives
  • 3.4 Global directives
  • 3.5 Options
  • 3.6 Data
  • 3.7 Expressions
  • 3.8 Intrinsic functions
  • 3.9 Variables
  • 3.10 Procedures
  
  
• 4 GENERAL PROGRAM STRUCTURE
  • 4.1 Input structure
  • 4.2 Files
  • 4.3 Records
  • 4.4 Restart
  • 4.5 Data set manipulation
  • 4.6 Memory allocation
  • 4.7 Multiple passes through the input
  • 4.8 Symmetry
  • 4.9 Defining the wavefunction
  • 4.10 Defining orbital subspaces
  • 4.11 Selecting orbitals and density matrices (ORBITAL, DENSITY)
  • 4.12 Summary of keywords known to the controlling program
  • 4.13 MOLPRO help
  
  
• 5 INTRODUCTORY EXAMPLES
  • 5.1 Using the molpro command
  • 5.2 Simple SCF calculations
  • 5.3 Geometry optimizations
  • 5.4 CCSD(T)
  • 5.5 CASSCF and MRCI
  • 5.6 Tables
  • 5.7 Procedures
  • 5.8 Do loops
  
  
• 6 PROGRAM CONTROL
  • 6.1 Starting a job (***)
  • 6.2 Ending a job (--)
  • 6.3 Restarting a job (RESTART)
  • 6.4 Including secondary input files (INCLUDE)
  • 6.5 Allocating dynamic memory (MEMORY)
  • 6.6 DO loops (DO/ENDDO)
  • 6.7 Branching (IF/ELSEIF/ENDIF)
  • 6.8 Procedures (PROC/ENDPROC)
  • 6.9 Text cards (TEXT)
  • 6.10 Checking the program status (STATUS)
  • 6.11 Global Thresholds (GTHRESH)
  • 6.12 Global Print Options (GPRINT/NOGPRINT)
  • 6.13 One-electron operators and expectation values (GEXPEC)
  
  
• 7 FILE HANDLING
  • 7.1 FILE
  • 7.2 DELETE
  • 7.3 ERASE
  • 7.4 DATA
  • 7.5 Assigning punch files (PUNCH)
  • 7.6 MOLPRO system parameters (GPARAM)
  
  
• 8 VARIABLES
  • 8.1 Setting variables
  • 8.2 Indexed variables
  • 8.3 String variables
  • 8.4 System variables
  • 8.5 Macro definitions using string variables
  • 8.6 Indexed Variables (Vectors)
  • 8.7 Vector operations
  • 8.8 Special variables
  • 8.9 Displaying variables
  • 8.10 Clearing variables
  • 8.11 Reading variables from an external file
  
  
• 9 TABLES AND PLOTTING
  • 9.1 Tables
  • 9.2 Plotting
  • 9.3 Diatomic potential curve analysis
  
  
• 10 MOLECULAR GEOMETRY
  • 10.1 Geometry specifications
  • 10.2 Symmetry specification
  • 10.3 Writing Gaussian, XMol or MOLDEN input (PUT)
  • 10.4 Geometry Files
  • 10.5 Lattice of point charges
  • 10.6 Redefining and printing atomic masses
  • 10.7 Dummy centres
  
  
• 11 BASIS INPUT
  • 11.1 Overview: sets and the basis library
  • 11.2 Cartesian and spherical harmonic basis functions
  • 11.3 The basis set library
  • 11.4 Default basis sets
  • 11.5 Default basis sets for individual atoms
  • 11.6 Basis blocks
  • 11.7 Auxiliary basis sets for density fitting or resolution of the identity
  • 11.8 Primitive set definition
  • 11.9 Contracted set definitions
  • 11.10 Examples
  
  
• 12 EFFECTIVE CORE POTENTIALS
  • 12.1 Input from ECP library
  • 12.2 Explicit input for ECPs
  • 12.3 Example for explicit ECP input
  • 12.4 Example for ECP input from library
  
  
• 13 CORE POLARIZATION POTENTIALS
  • 13.1 Input options
  • 13.2 Example for ECP/CPP
  
  
• 14 INTEGRATION
  • 14.1 Sorted integrals
  • 14.2 INTEGRAL-DIRECT CALCULATIONS (GDIRECT)
  
  
• 15 DENSITY FITTING
  • 15.1 Options for density fitting
  
  
• 16 THE SCF PROGRAM
  • 16.1 Options
  • 16.2 Defining the wavefunction
  • 16.3 Saving the final orbitals
  • 16.4 Starting orbitals
  • 16.5 Rotating pairs of orbitals
  • 16.6 Using additional point-group symmetry
  • 16.7 Expectation values
  • 16.8 Polarizabilities
  • 16.9 Miscellaneous directives
  • 16.10 Handling difficult cases: When SCF does not converge
  
  
• 17 THE DENSITY FUNCTIONAL PROGRAM
  • 17.1 Options
  • 17.2 Directives
  • 17.3 Numerical integration grid control (GRID)
  • 17.4 Density Functionals
  • 17.5 Empirical damped dispersion correction
  • 17.6 Time-dependent density functional theory
  • 17.7 Examples
  
  
• 18 ORBITAL LOCALIZATION
  • 18.1 Defining the input orbitals (ORBITAL)
  • 18.2 Saving the localized orbitals (SAVE)
  • 18.3 Choosing the localization method (METHOD)
  • 18.4 Delocalization of orbitals (DELOCAL)
  • 18.5 Localizing AOs(LOCAO)
  • 18.6 Selecting the orbital space
  • 18.7 Ordering of localized orbitals
  • 18.8 Localization thresholds (THRESH)
  • 18.9 Options for PM localization (PIPEK)
  • 18.10 Printing options (PRINT)
  
  
• 19 THE MCSCF PROGRAM MULTI
  • 19.1 Structure of the input
  • 19.2 Defining the orbital subspaces
  • 19.3 Defining the optimized states
  • 19.4 Defining the configuration space
  • 19.5 Restoring and saving the orbitals and CI vectors
  • 19.6 Selecting the optimization methods
  • 19.7 Calculating expectation values
  • 19.8 Miscellaneous options
  • 19.9 Coupled-perturbed MCSCF
  • 19.10 Optimizing valence bond wavefunctions
  • 19.11 Hints and strategies
  • 19.12 Examples
  
  
• 20 THE CI PROGRAM
  • 20.1 Introduction
  • 20.2 Specifying the wavefunction
  • 20.3 Options
  • 20.4 Miscellaneous thresholds
  • 20.5 Print options
  • 20.6 Examples
  • 20.7 Cluster corrections for multi-state MRCI
  
  
• 21 MULTIREFERENCE RAYLEIGH SCHRÖDINGER PERTURBATION THEORY
  • 21.1 Introduction
  • 21.2 Excited state calculations
  • 21.3 Multi-State CASPT2
  • 21.4 Modified Fock-operators in the zeroth-order Hamiltonian.
  • 21.5 Level shifts
  • 21.6 Integral direct calculations
  • 21.7 CASPT2 gradients
  • 21.8 Coupling MRCI and MRPT2: The CIPT2 method
  • 21.9 Further options for CASPT2 and CASPT3
  
  
• 22 NEVPT2 calculations
  • 22.1 General considerations
  • 22.2 Input description
  
  
• 23 MØLLER PLESSET PERTURBATION THEORY
  • 23.1 Expectation values for MP2
  • 23.2 Polarizabilities and second-order properties for MP2
  • 23.3 CPHF for gradients, expectation values and polarizabilities
  • 23.4 Density-fitting MP2 (DF-MP2, RI-MP2)
  • 23.5 Spin-component scaled MP2 (SCS-MP2)
  
  
• 24 THE CLOSED SHELL CCSD PROGRAM
  • 24.1 Coupled-cluster, CCSD
  • 24.2 Quadratic configuration interaction, QCI
  • 24.3 Brueckner coupled-cluster calculations, BCCD
  • 24.4 Singles-doubles configuration interaction, CISD
  • 24.5 Quasi-variational coupled cluster, QVCCD
  • 24.6 The DIIS directive
  • 24.7 Examples
  • 24.8 Saving the density matrix
  • 24.9 Expectation values
  • 24.10 Natural orbitals
  • 24.11 Dual basis set calculations
  
  
• 25 EXCITED STATES WITH EQUATION-OF-MOTION CCSD (EOM-CCSD)
  • 25.1 Options for EOM
  • 25.2 Options for EOMPAR card
  • 25.3 Options for EOMPRINT card
  • 25.4 Examples
  • 25.5 Excited states with CIS
  • 25.6 First- and second-order properties for CCSD
  
  
• 26 OPEN-SHELL COUPLED CLUSTER THEORIES
• 27 The MRCC program of M. Kallay (MRCC)
  • 27.1 Installing MRCC
  • 27.2 Running MRCC
  
  
• 28 The FCIQMC program (FCIQMC)
  • 28.1 The FCIQMC Method
  • 28.2 Running FCIQMC
  • 28.3 More advanced options
  • 28.4 Restarting FCIQMC jobs
  • 28.5 CHANGEVARS facility
  • 28.6 FCIQMC output
  • 28.7 FCIQMC error analysis
  • 28.8 Examples
  
  
• 29 AB INITIO MULTIPLE SPAWNING DYNAMICS
  • 29.1 Compilation
  • 29.2 Structure of the input
  • 29.3 Running a CASSCF spawning calculation
  • 29.4 Output
  • 29.5 Examples
  
  
• 30 SMILES
  • 30.1 INTERNAL BASIS SETS
  • 30.2 EXTERNAL BASIS SETS
  • 30.3 Example
  
  
• 31 LOCAL CORRELATION TREATMENTS
  • 31.1 Introduction
  • 31.2 Getting started
  • 31.3 Summary of options
  • 31.4 Summary of directives
  • 31.5 General Options
  • 31.6 Options for selection of domains
  • 31.7 Options for selection of pair classes
  • 31.8 Directives
  • 31.9 Doing it right
  • 31.10 Density-fitted LMP2 (DF-LMP2) and coupled cluster (DF-LCCSD(T0))
  
  
• 32 LOCAL METHODS FOR EXCITED STATES
  • 32.1 Local CC2 and ADC(2)
  • 32.2 Options for EOM
  • 32.3 Parameters on LAPLACE card
  • 32.4 Print options
  • 32.5 Examples
  
  
• 33 EXPLICITLY CORRELATED METHODS
  • 33.1 Reference functions
  • 33.2 Wave function Ansätze
  • 33.3 RI Approximations
  • 33.4 Basis sets
  • 33.5 Symmetry
  • 33.6 Options
  • 33.7 Choosing the ansatz and the level of approximation
  • 33.8 CABS Singles correction
  • 33.9 Pair specific geminal exponents
  • 33.10 CCSD(T)-F12
  • 33.11 DF-LMP2-F12 calculations with local approximations
  • 33.12 Variables set by the F12 programs
  
  
• 34 THE FULL CI PROGRAM
  • 34.1 Defining the orbitals
  • 34.2 Occupied orbitals
  • 34.3 Frozen-core orbitals
  • 34.4 Defining the state symmetry
  • 34.5 Density matrix
  • 34.6 Printing options
  • 34.7 Interface to other programs
  • 34.8 Example
  
  
• 35 SYMMETRY-ADAPTED INTERMOLECULAR PERTURBATION THEORY
  • 35.1 Introduction
  • 35.2 First example
  • 35.3 DFT-SAPT
  • 35.4 High order terms
  • 35.5 Density fitting
  • 35.6 SAPT with ECP's
  • 35.7 Examples
  • 35.8 Options
  • 35.9 SAPT(CCSD)
  
  
• 36 PROPERTIES AND EXPECTATION VALUES
  • 36.1 The property program
  • 36.2 Distributed multipole analysis
  • 36.3 Mulliken population analysis
  • 36.4 Natural Bond Orbital Analysis
  • 36.5 Finite field calculations
  • 36.6 Relativistic corrections
  • 36.7 CUBE -- dump density or orbital values
  • 36.8 GOPENMOL -- calculate grids for visualization in gOpenMol
  
  
• 37 RELATIVISTIC CORRECTIONS
  • 37.1 Using the Douglas-Kroll-Hess Hamiltonian
  • 37.2 Example for computing relativistic corrections
  
  
• 38 DIABATIC ORBITALS
• 39 NON ADIABATIC COUPLING MATRIX ELEMENTS
  • 39.1 The DDR procedure
  
  
• 40 QUASI-DIABATIZATION
• 41 THE VB PROGRAM CASVB
  • 41.1 Structure of the input
  • 41.2 Defining the CASSCF wavefunction
  • 41.3 Other wavefunction directives
  • 41.4 Defining the valence bond wavefunction
  • 41.5 Recovering CASSCF CI vector and VB wavefunction
  • 41.6 Saving the VB wavefunction
  • 41.7 Specifying a guess
  • 41.8 Permuting orbitals
  • 41.9 Optimization control
  • 41.10 Point group symmetry and constraints
  • 41.11 Wavefunction analysis
  • 41.12 Controlling the amount of output
  • 41.13 Further facilities
  • 41.14 Service mode
  • 41.15 Examples
  
  
• 42 SPIN-ORBIT-COUPLING
  • 42.1 Introduction
  • 42.2 Calculation of SO integrals
  • 42.3 Calculation of individual SO matrix elements
  • 42.4 Approximations used in calculating spin-orbit integrals and matrix elements
  • 42.5 Calculation and diagonalization of the entire SO-matrix
  • 42.6 Modifying the unperturbed energies
  • 42.7 Examples
  
  
• 43 ENERGY GRADIENTS
  • 43.1 Analytical energy gradients
  • 43.2 Numerical gradients
  • 43.3 Saving the gradient in a variables
  
  
• 44 GEOMETRY OPTIMIZATION (OPTG)
  • 44.1 Options
  • 44.2 Directives for OPTG
  • 44.3 Using the SLAPAF program for geometry optimization
  • 44.4 Examples
  
  
• 45 VIBRATIONAL FREQUENCIES (FREQUENCIES)
  • 45.1 Options
  • 45.2 Printing options (PRINT)
  • 45.3 Saving the hessian and other information (SAVE)
  • 45.4 Restarting a hessian/Frequency calculation (START)
  • 45.5 Coordinates for numerical hessian calculations (COORD)
  • 45.6 Stepsizes for numerical hessian calculations (STEP)
  • 45.7 Numerical hessian using energy variables (VARIABLE)
  • 45.8 Thermodynamical properties (THERMO)
  • 45.9 Examples
  
  
• 46 CHEMICAL SHIELDINGS OF MOLECULES
• 47 MINIMIZATION OF FUNCTIONS
  • 47.1 Examples
  
  
• 48 INSTANTONS
  • 48.1 Thermal reaction rates
  • 48.2 Tunnelling splittings
  • 48.3 Input file
  • 48.4 Procedures
  • 48.5 Options
  • 48.6 Parallelization
  • 48.7 Examples
  
  
• 49 BASIS SET EXTRAPOLATION
  • 49.1 Options
  • 49.2 Extrapolation functionals
  • 49.3 Geometry optimization using extrapolated energies
  • 49.4 Harmonic vibrational frequencies using extrapolated energies
  
  
• 50 POTENTIAL ENERGY SURFACES (SURF)
  • 50.1 Options
  • 50.2 Multi-level calculations
  • 50.3 Special options for Intensities
  • 50.4 Error correction schemes
  • 50.5 Restart capabilities
  • 50.6 Linear combinations of normal coordinates
  • 50.7 Scaling of individual coordinates
  • 50.8 Deleting individual surfaces
  • 50.9 Modeling of high-order $n$-body terms
  • 50.10 Quality Check
  • 50.11 Grid Computing
  • 50.12 Recommendations
  • 50.13 Standard Problems
  
  
• 51 POLYNOMIAL REPRESENTATIONS (POLY)
  • 51.1 Options
  
  
• 52 THE VSCF PROGRAM (VSCF)
  • 52.1 Options
  • 52.2 Examples
  
  
• 53 THE VCI PROGRAM (VCI)
  • 53.1 Options
  • 53.2 Examples
  
  
• 54 VIBRATIONAL MP2 (VMP2)
• 55 THE COSMO MODEL
  • 55.1 BASIC THEORY
  
  
• 56 QM/MM INTERFACES
  • 56.1 Chemshell
  
  
• 57 PERIODIC-BOUNDARY CONDITIONS
• 58 MANY-BODY EXPANSION
  • 58.1 Compilation
  • 58.2 Units
  • 58.3 Incremental Monte-Carlo
  • 58.4 EWALD directive
  • 58.5 Examples
  
  
• 59 THE TDHF AND TDKS PROGRAMS
• 60 ORBITAL MERGING
  • 60.1 Defining the input orbitals (ORBITAL)
  • 60.2 Moving orbitals to the output set (MOVE)
  • 60.3 Adding orbitals to the output set (ADD)
  • 60.4 Defining extra symmetries (EXTRA)
  • 60.5 Defining offsets in the output set (OFFSET)
  • 60.6 Projecting orbitals (PROJECT)
  • 60.7 Symmetric orthonormalization (ORTH)
  • 60.8 Schmidt orthonormalization (SCHMIDT)
  • 60.9 Rotating orbitals (ROTATE)
  • 60.10 Initialization of a new output set (INIT)
  • 60.11 Saving the merged orbitals
  • 60.12 Printing options (PRINT)
  • 60.13 Examples
  
  
• 61 MATRIX OPERATIONS
  • 61.1 Calling the matrix facility (MATROP)
  • 61.2 Loading matrices (LOAD)
  • 61.3 Saving matrices (SAVE)
  • 61.4 Adding matrices (ADD)
  • 61.5 Trace of a matrix or the product of two matrices (TRACE)
  • 61.6 Setting variables (SET)
  • 61.7 Multiplying matrices (MULT)
  • 61.8 Transforming operators (TRAN)
  • 61.9 Transforming density matrices into the MO basis (DMO)
  • 61.10 Diagonalizing a matrix DIAG
  • 61.11 Generating natural orbitals (NATORB)
  • 61.12 Forming an outer product of two vectors (OPRD)
  • 61.13 Combining matrix columns (ADDVEC)
  • 61.14 Forming a closed-shell density matrix (DENS)
  • 61.15 Computing a fock matrix (FOCK)
  • 61.16 Computing a coulomb operator (COUL)
  • 61.17 Computing an exchange operator (EXCH)
  • 61.18 Printing matrices (PRINT)
  • 61.19 Printing diagonal elements of a matrix (PRID)
  • 61.20 Printing orbitals (PRIO)
  • 61.21 Printing contraction coefficients (PRIC)
  • 61.22 Assigning matrix elements to a variable (ELEM)
  • 61.23 Reading a matrix from the input file (READ)
  • 61.24 Writing a matrix to an ASCII file (WRITE)
  • 61.25 Examples
  • 61.26 Exercise: SCF program
  
  
• A. Installation Guide
  • A..1 Installation of pre-built binaries
  • A..2 Installation from source files
  
  
• B. Recent Changes
  • B..1 New features of MOLPRO2010.1
  • B..2 New features of MOLPRO2009.1
  • B..3 New features of MOLPRO2008.1
  • B..4 New features of MOLPRO2006.1
  • B..5 New features of MOLPRO2002.6
  • B..6 New features of MOLPRO2002
  • B..7 Features that were new in MOLPRO2000
  • B..8 Facilities that were new in MOLPRO98
  
  
• C. Density functional descriptions
  • C..1 B86: X $\alpha\beta\gamma$
  • C..2 B86MGC: X $\alpha\beta\gamma$ with Modified Gradient Correction
  • C..3 B86R: X $\alpha\beta\gamma$ Re-optimised
  • C..4 B88: Becke 1988 Exchange Functional
  • C..5 B88C: Becke 1988 Correlation Functional
  • C..6 B95: Becke 1995 Correlation Functional
  • C..7 B97DF: Density functional part of B97
  • C..8 B97RDF: Density functional part of B97 Re-parameterized by Hamprecht et al
  • C..9 BR: Becke-Roussel Exchange Functional
  • C..10 BRUEG: Becke-Roussel Exchange Functional -- Uniform Electron Gas Limit
  • C..11 BW: Becke-Wigner Exchange-Correlation Functional
  • C..12 CS1: Colle-Salvetti correlation functional
  • C..13 CS2: Colle-Salvetti correlation functional
  • C..14 DIRAC: Slater-Dirac Exchange Energy
  • C..15 ECERF: Short-range LDA correlation functional
  • C..16 EXERF: Short-range LDA correlation functional
  • C..17 G96: Gill's 1996 Gradient Corrected Exchange Functional
  • C..18 HCTH120: Handy least squares fitted functional
  • C..19 HCTH147: Handy least squares fitted functional
  • C..20 HCTH93: Handy least squares fitted functional
  • C..21 LTA: Local $\\ tau$ Approximation
  • C..22 LYP: Lee, Yang and Parr Correlation Functional
  • C..23 M052XC: M05-2X Meta-GGA Correlation Functional
  • C..24 M052XX: M05-2X Meta-GGA Exchange Functional
  • C..25 M05C: M05 Meta-GGA Correlation Functional
  • C..26 M05X: M05 Meta-GGA Exchange Functional
  • C..27 M062XC: M06-2X Meta-GGA Correlation Functional
  • C..28 M062XX: M06-2X Meta-GGA Exchange Functional
  • C..29 M06C: M06 Meta-GGA Correlation Functional
  • C..30 M06HFC: M06-HF Meta-GGA Correlation Functional
  • C..31 M06HFX: M06-HF Meta-GGA Exchange Functional
  • C..32 M06LC: M06-L Meta-GGA Correlation Functional
  • C..33 M06LX: M06-L Meta-GGA Exchange Functional
  • C..34 M06X: M06 Meta-GGA Exchange Functional
  • C..35 MK00: Exchange Functional for Accurate Virtual Orbital Energies
  • C..36 MK00B: Exchange Functional for Accurate Virtual Orbital Energies
  • C..37 P86: .
  • C..38 PBEC: PBE Correlation Functional
  • C..39 PBEX: PBE Exchange Functional
  • C..40 PBEXREV: Revised PBE Exchange Functional
  • C..41 PW86: .
  • C..42 PW91C: Perdew-Wang 1991 GGA Correlation Functional
  • C..43 PW91X: Perdew-Wang 1991 GGA Exchange Functional
  • C..44 PW92C: Perdew-Wang 1992 GGA Correlation Functional
  • C..45 STEST: Test for number of electrons
  • C..46 TFKE: Thomas-Fermi Kinetic Energy
  • C..47 TH1: Tozer and Handy 1998
  • C..48 TH2: .
  • C..49 TH3: .
  • C..50 TH4: .
  • C..51 THGFC: .
  • C..52 THGFCFO: .
  • C..53 THGFCO: .
  • C..54 THGFL: .
  • C..55 VSXC: .
  • C..56 VW: von Weizsacker kinetic energy
  • C..57 VWN3: Vosko-Wilk-Nusair (1980) III local correlation energy
  • C..58 VWN5: Vosko-Wilk-Nusair (1980) V local correlation energy
  
  
• D. License information
  • D..1 BLAS
  • D..2 LAPACK
  • D..3 Boost
  
  
• Index