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Contents
1 Introduction to MOLPRO
2 MOLPRO on the WWW
3 Release Notes
4 References
5 HOW TO READ THIS MANUAL
6 RUNNING MOLPRO
7 DEFINITION OF MOLPRO INPUT LANGUAGE
7.1 Input format
7.2 Commands
7.3 Directives
7.4 Global directives
7.5 Options
7.6 Data
7.7 Expressions
7.8 Intrinsic functions
7.9 Variables
7.10 Procedures
8 GENERAL PROGRAM STRUCTURE
8.1 Input structure
8.2 Files
8.3 Records
8.4 Restart
8.5 Data set manipulation
8.6 Memory allocation
8.7 Multiple passes through the input
8.8 Symmetry
8.9 Defining the wavefunction
8.10 Defining orbital subspaces
8.11 Selecting orbitals and density matrices (ORBITAL, DENSITY)
8.12 Summary of keywords known to the controlling program
8.13 MOLPRO help
9 INTRODUCTORY EXAMPLES
9.1 Using the molpro command
9.2 Simple SCF calculations
9.3 Geometry optimizations
9.4 CCSD(T)
9.5 CASSCF and MRCI
9.6 Tables
9.7 Procedures
9.8 Do loops
10 PROGRAM CONTROL
10.1 Starting a job (***)
10.2 Ending a job (--)
10.3 Restarting a job (RESTART)
10.4 Including secondary input files (INCLUDE)
10.5 Allocating dynamic memory (MEMORY)
10.6 DO loops (DO/ENDDO)
10.7 Branching (IF/ELSEIF/ENDIF)
10.8 Procedures (PROC/ENDPROC)
10.9 Text cards (TEXT)
10.10 Checking the program status (STATUS)
10.11 Global Thresholds (GTHRESH)
10.12 Global Print Options (GPRINT/NOGPRINT)
10.13 One-electron operators and expectation values (GEXPEC)
11 FILE HANDLING
11.1 FILE
11.2 DELETE
11.3 ERASE
11.4 DATA
11.5 Assigning punch files (PUNCH)
11.6 MOLPRO system parameters (GPARAM)
12 VARIABLES
12.1 Setting variables
12.2 Indexed variables
12.3 String variables
12.4 System variables
12.5 Macro definitions using string variables
12.6 Indexed Variables (Vectors)
12.7 Vector operations
12.8 Special variables
12.9 Displaying variables
12.10 Clearing variables
12.11 Reading variables from an external file
13 TABLES AND PLOTTING
13.1 Tables
13.2 Plotting
14 INTEGRAL-DIRECT CALCULATIONS (GDIRECT)
14.1 Example for integral-direct calculations
15 DENSITY FITTING
15.1 Options for density fitting
16 GEOMETRY SPECIFICATION AND INTEGRATION
16.1 Sorted integrals
16.2 Symmetry specification
16.3 Geometry specifications
16.4 Writing Gaussian, XMol or MOLDEN input (PUT)
16.5 Geometry Files
16.6 Lattice of point charges
16.7 Redefining and printing atomic masses
16.8 Dummy centres
17 BASIS INPUT
17.1 Overview: sets and the basis library
17.2 Cartesian and spherical harmonic basis functions
17.3 The basis set library
17.4 Default basis sets
17.5 Default basis sets for individual atoms
17.6 Primitive set definition
17.7 Contracted set definitions
17.8 Examples
18 EFFECTIVE CORE POTENTIALS
18.1 Input from ECP library
18.2 Explicit input for ECPs
18.3 Example for explicit ECP input
18.4 Example for ECP input from library
19 CORE POLARIZATION POTENTIALS
19.1 Input options
19.2 Example for ECP/CPP
20 RELATIVISTIC CORRECTIONS
20.1 Using the Douglas-Kroll-Hess Hamiltonian
20.2 Example for computing relativistic corrections
21 THE SCF PROGRAM
21.1 Options
21.2 Defining the wavefunction
21.3 Saving the final orbitals
21.4 Starting orbitals
21.5 Rotating pairs of orbitals
21.6 Using additional point-group symmetry
21.7 Expectation values
21.8 Polarizabilities
21.9 Miscellaneous directives
22 THE DENSITY FUNCTIONAL PROGRAM
22.1 Options
22.2 Directives
22.3 Numerical integration grid control (GRID)
22.4 Density Functionals
22.5 Examples
23 ORBITAL LOCALIZATION
23.1 Defining the input orbitals (ORBITAL)
23.2 Saving the localized orbitals (SAVE)
23.3 Choosing the localization method (METHOD)
23.4 Delocalization of orbitals (DELOCAL)
23.5 Localizing AOs(LOCAO)
23.6 Selecting the orbital space
23.7 Ordering of localized orbitals
23.8 Localization thresholds (THRESH)
23.9 Options for PM localization (PIPEK)
23.10 Printing options (PRINT)
24 THE MCSCF PROGRAM MULTI
24.1 Structure of the input
24.2 Defining the orbital subspaces
24.3 Defining the optimized states
24.4 Defining the configuration space
24.5 Restoring and saving the orbitals and CI vectors
24.6 Selecting the optimization methods
24.7 Calculating expectation values
24.8 Miscellaneous options
24.9 Coupled-perturbed MCSCF
24.10 Optimizing valence bond wavefunctions
24.11 Hints and strategies
24.12 Examples
25 THE CI PROGRAM
25.1 Introduction
25.2 Specifying the wavefunction
25.3 Options
25.4 Miscellaneous thresholds
25.5 Print options
25.6 Examples
26 MULTIREFERENCE RAYLEIGH SCHRÖDINGER PERTURBATION THEORY
26.1 Introduction
26.2 Excited state calculations
26.3 Multi-State CASPT2
26.4 Modified Fock-operators in the zeroth-order Hamiltonian.
26.5 Level shifts
26.6 Integral direct calculations
26.7 CASPT2 gradients
26.8 Coupling MRCI and MRPT2: The CIPT2 method
26.9 Further options for CASPT2 and CASPT3
27 MØLLER PLESSET PERTURBATION THEORY
27.1 Expectation values for MP2
27.2 Density-fitting MP2 (DF-MP2, RI-MP2)
27.3 Spin-component scaled MP2 (SCS-MP2)
28 THE CLOSED SHELL CCSD PROGRAM
28.1 Coupled-cluster, CCSD
28.2 Quadratic configuration interaction, QCI
28.3 Brueckner coupled-cluster calculations, BCCD
28.4 Singles-doubles configuration interaction, CISD
28.5 The DIIS directive
28.6 Examples
28.7 Saving the density matrix
28.8 Natural orbitals
29 EXCITED STATES WITH EQUATION-OF-MOTION CCSD (EOM-CCSD)
29.1 Options for EOM
29.2 Options for EOMPAR card
29.3 Options for EOMPRINT card
29.4 Examples
29.5 Excited states with CIS
30 OPEN-SHELL COUPLED CLUSTER THEORIES
31 The MRCC program of M. Kallay (MRCC)
31.1 Installing MRCC
31.2 Running MRCC
32 LOCAL CORRELATION TREATMENTS
32.1 Introduction
32.2 Getting started
32.3 Summary of options
32.4 Summary of directives
32.5 General Options
32.6 Options for selection of domains
32.7 Options for selection of pair classes
32.8 Directives
32.9 Doing it right
32.10 Density-fitted LMP2 (DF-LMP2) and coupled cluster (DF-LCCSD(T0))
33 EXPLICITLY CORRELATED METHODS
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 Printing options
34.6 Interface to other programs
34.7 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 Options
36 PROPERTIES AND EXPECTATION VALUES
36.1 The property program
36.2 Distributed multipole analysis
36.3 Mulliken population analysis
36.4 Finite field calculations
36.5 Relativistic corrections
36.6 CUBE -- dump density or orbital values
36.7 GOPENMOL -- calculate grids for visualization in gOpenMol
37 DIABATIC ORBITALS
38 NON ADIABATIC COUPLING MATRIX ELEMENTS
38.1 The DDR procedure
39 QUASI-DIABATIZATION
40 THE VB PROGRAM CASVB
40.1 Structure of the input
40.2 Defining the CASSCF wavefunction
40.3 Other wavefunction directives
40.4 Defining the valence bond wavefunction
40.5 Recovering CASSCF CI vector and VB wavefunction
40.6 Saving the VB wavefunction
40.7 Specifying a guess
40.8 Permuting orbitals
40.9 Optimization control
40.10 Point group symmetry and constraints
40.11 Wavefunction analysis
40.12 Controlling the amount of output
40.13 Further facilities
40.14 Service mode
40.15 Examples
41 SPIN-ORBIT-COUPLING
41.1 Introduction
41.2 Calculation of SO integrals
41.3 Calculation of individual SO matrix elements
41.4 Calculation and diagonalization of the entire SO-matrix
41.5 Modifying the unperturbed energies
41.6 Examples
42 ENERGY GRADIENTS
42.1 Analytical energy gradients
42.2 Numerical gradients
42.3 Saving the gradient in a variables
43 GEOMETRY OPTIMIZATION (OPTG)
43.1 Options
43.2 Directives for OPTG
43.3 Using the SLAPAF program for geometry optimization
43.4 Examples
44 VIBRATIONAL FREQUENCIES (FREQUENCIES)
44.1 Numerical hessian using energy variables (VARIABLE)
44.2 Thermodynamical properties (THERMO)
44.3 Examples
45 THE COSMO MODEL
45.1 BASIC THEORY
46 ORBITAL MERGING
46.1 Defining the input orbitals (ORBITAL)
46.2 Moving orbitals to the output set (MOVE)
46.3 Adding orbitals to the output set (ADD)
46.4 Defining extra symmetries (EXTRA)
46.5 Defining offsets in the output set (OFFSET)
46.6 Projecting orbitals (PROJECT)
46.7 Symmetric orthonormalization (ORTH)
46.8 Schmidt orthonormalization (SCHMIDT)
46.9 Rotating orbitals (ROTATE)
46.10 Initialization of a new output set (INIT)
46.11 Saving the merged orbitals
46.12 Printing options (PRINT)
46.13 Examples
47 MATRIX OPERATIONS
47.1 Calling the matrix facility (MATROP)
47.2 Loading matrices (LOAD)
47.3 Saving matrices (SAVE)
47.4 Adding matrices (ADD)
47.5 Trace of a matrix or the product of two matrices (TRACE)
47.6 Setting variables (SET)
47.7 Multiplying matrices (MULT)
47.8 Transforming operators (TRAN)
47.9 Transforming density matrices into the MO basis (DMO)
47.10 Diagonalizing a matrix DIAG
47.11 Generating natural orbitals (NATORB)
47.12 Forming an outer product of two vectors (OPRD)
47.13 Forming a closed-shell density matrix (DENS)
47.14 Computing a fock matrix (FOCK)
47.15 Computing a coulomb operator (COUL)
47.16 Computing an exchange operator (EXCH)
47.17 Printing matrices (PRINT)
47.18 Printing diagonal elements of a matrix (PRID)
47.19 Printing orbitals (PRIO)
47.20 Assigning matrix elements to a variable (ELEM)
47.21 Reading a matrix from the input file (READ)
47.22 Writing a matrix to an ASCII file (WRITE)
47.23 Examples
47.24 Exercise: SCF program
Bibliography
A. Installation of MOLPRO
A..1 Obtaining the distribution materials
A..2 Installation of pre-built binaries
A..3 Installation from source files
B. Recent Changes
B..1 New features of MOLPRO2006.1
B..2 New features of MOLPRO2002.6
B..3 New features of MOLPRO2002
B..4 Features that were new in MOLPRO2000
B..5 Facilities that were new in MOLPRO98
C. Density functional descriptions
C..1 ALYP: Lee, Yang and Parr Correlation Functional
C..2 B86MGC: X with Modified Gradient Correction
C..3 B86R: X Re-optimised
C..4 B86: X
C..5 B88CMASK:
C..6 B88C: Becke88 Correlation Functional
C..7 B88: Becke88 Exchange Functional
C..8 B95: Becke95 Correlation Functional
C..9 B97R: Density functional part of B97 Re-parameterized by Hamprecht et al
C..10 B97: Density functional part of B97
C..11 BR: Becke-Roussel Exchange Functional
C..12 BRUEG: Becke-Roussel Exchange Functional -- Uniform Electron Gas Limit
C..13 BW: Becke-Wigner Exchange-Correlation Functional
C..14 CS1: Colle-Salvetti correlation functional
C..15 CS2: Colle-Salvetti correlation functional
C..16 DIRAC: Slater-Dirac Exchange Energy
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 Approximation
C..22 LYP: Lee, Yang and Parr Correlation Functional
C..23 MK00B: Exchange Functional for Accurate Virtual Orbital Energies
C..24 MK00: Exchange Functional for Accurate Virtual Orbital Energies
C..25 P86:
C..26 PBEC: PBE Correlation Functional
C..27 PBEXREV: Revised PBE Exchange Functional
C..28 PBEX: PBE Exchange Functional
C..29 PW86:
C..30 PW91C: Perdew-Wang 1991 GGA Correlation Functional
C..31 PW91X: Perdew-Wang 1991 GGA Exchange Functional
C..32 PW92C: Perdew-Wang 1992 GGA Correlation Functional
C..33 STEST: Test for number of electrons
C..34 TH1: Tozer and Handy 1998
C..35 TH2:
C..36 TH3:
C..37 TH4:
C..38 THGFCFO:
C..39 THGFCO:
C..40 THGFC:
C..41 THGFL:
C..42 VSXC:
C..43 VWN3: Vosko-Wilk-Nusair (1980) III local correlation energy
C..44 VWN5: Vosko-Wilk-Nusair (1980) V local correlation energy
Index
molpro@molpro.net
May 12, 2008