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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 Primitive set definition
11.7 Contracted set definitions
11.8 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
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 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
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 The DIIS directive
24.6 Examples
24.7 Saving the density matrix
24.8 Natural orbitals
24.9 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 SMILES
28.1 INTERNAL BASIS SETS
28.2 EXTERNAL BASIS SETS
29 LOCAL CORRELATION TREATMENTS
29.1 Introduction
29.2 Getting started
29.3 Summary of options
29.4 Summary of directives
29.5 General Options
29.6 Options for selection of domains
29.7 Options for selection of pair classes
29.8 Directives
29.9 Doing it right
29.10 Density-fitted LMP2 (DF-LMP2) and coupled cluster (DF-LCCSD(T0))
30 EXPLICITLY CORRELATED METHODS
30.1 Reference functions
30.2 Wave function Ansätze
30.3 RI Approximations
30.4 Basis sets
30.5 Symmetry
30.6 Options
30.7 Choosing the ansatz and the level of approximation
30.8 CABS Singles correction
30.9 CCSD(T)-F12
30.10 DF-LMP2-F12 calculations with local approximations
30.11 Variables set by the F12 programs
31 THE FULL CI PROGRAM
31.1 Defining the orbitals
31.2 Occupied orbitals
31.3 Frozen-core orbitals
31.4 Defining the state symmetry
31.5 Printing options
31.6 Interface to other programs
31.7 Example
32 SYMMETRY-ADAPTED INTERMOLECULAR PERTURBATION THEORY
32.1 Introduction
32.2 First example
32.3 DFT-SAPT
32.4 High order terms
32.5 Density fitting
32.6 Examples
32.7 Options
33 PROPERTIES AND EXPECTATION VALUES
33.1 The property program
33.2 Distributed multipole analysis
33.3 Mulliken population analysis
33.4 Natural Bond Orbital Analysis
33.5 Finite field calculations
33.6 Relativistic corrections
33.7 CUBE -- dump density or orbital values
33.8 GOPENMOL -- calculate grids for visualization in gOpenMol
34 RELATIVISTIC CORRECTIONS
34.1 Using the Douglas-Kroll-Hess Hamiltonian
34.2 Example for computing relativistic corrections
35 DIABATIC ORBITALS
36 NON ADIABATIC COUPLING MATRIX ELEMENTS
36.1 The DDR procedure
37 QUASI-DIABATIZATION
38 THE VB PROGRAM CASVB
38.1 Structure of the input
38.2 Defining the CASSCF wavefunction
38.3 Other wavefunction directives
38.4 Defining the valence bond wavefunction
38.5 Recovering CASSCF CI vector and VB wavefunction
38.6 Saving the VB wavefunction
38.7 Specifying a guess
38.8 Permuting orbitals
38.9 Optimization control
38.10 Point group symmetry and constraints
38.11 Wavefunction analysis
38.12 Controlling the amount of output
38.13 Further facilities
38.14 Service mode
38.15 Examples
39 SPIN-ORBIT-COUPLING
39.1 Introduction
39.2 Calculation of SO integrals
39.3 Calculation of individual SO matrix elements
39.4 Approximations used in calculating spin-orbit integrals and matrix elements
39.5 Calculation and diagonalization of the entire SO-matrix
39.6 Modifying the unperturbed energies
39.7 Examples
40 ENERGY GRADIENTS
40.1 Analytical energy gradients
40.2 Numerical gradients
40.3 Saving the gradient in a variables
41 GEOMETRY OPTIMIZATION (OPTG)
41.1 Options
41.2 Directives for OPTG
41.3 Using the SLAPAF program for geometry optimization
41.4 Examples
42 VIBRATIONAL FREQUENCIES (FREQUENCIES)
42.1 Options
42.2 Printing options (PRINT)
42.3 Saving the hessian and other information (SAVE)
42.4 Restarting a hessian/Frequency calculation (START)
42.5 Coordinates for numerical hessian calculations (COORD)
42.6 Stepsizes for numerical hessian calculations (STEP)
42.7 Numerical hessian using energy variables (VARIABLE)
42.8 Thermodynamical properties (THERMO)
42.9 Examples
43 MINIMIZATION OF FUNCTIONS
43.1 Examples
44 BASIS SET EXTRAPOLATION
44.1 Options
44.2 Extrapolation functionals
44.3 Geometry optimization using extrapolated energies
44.4 Harmonic vibrational frequencies using extrapolated energies
45 POTENTIAL ENERGY SURFACES (SURF)
45.1 Options
45.2 Multi-level calculations
45.3 Restart capabilities
45.4 Linear combinations of normal coordinates
45.5 Scaling of individual coordinates
45.6 Recomendations
45.7 Standard Problems
46 THE VSCF PROGRAM (VSCF)
46.1 Options
46.2 Standard Problems
47 THE VCI PROGRAM (VCI)
47.1 Options
47.2 Recommendations
47.3 Examples
48 THE COSMO MODEL
48.1 BASIC THEORY
49 QM/MM INTERFACES
49.1 Chemshell
50 ORBITAL MERGING
50.1 Defining the input orbitals (ORBITAL)
50.2 Moving orbitals to the output set (MOVE)
50.3 Adding orbitals to the output set (ADD)
50.4 Defining extra symmetries (EXTRA)
50.5 Defining offsets in the output set (OFFSET)
50.6 Projecting orbitals (PROJECT)
50.7 Symmetric orthonormalization (ORTH)
50.8 Schmidt orthonormalization (SCHMIDT)
50.9 Rotating orbitals (ROTATE)
50.10 Initialization of a new output set (INIT)
50.11 Saving the merged orbitals
50.12 Printing options (PRINT)
50.13 Examples
51 MATRIX OPERATIONS
51.1 Calling the matrix facility (MATROP)
51.2 Loading matrices (LOAD)
51.3 Saving matrices (SAVE)
51.4 Adding matrices (ADD)
51.5 Trace of a matrix or the product of two matrices (TRACE)
51.6 Setting variables (SET)
51.7 Multiplying matrices (MULT)
51.8 Transforming operators (TRAN)
51.9 Transforming density matrices into the MO basis (DMO)
51.10 Diagonalizing a matrix DIAG
51.11 Generating natural orbitals (NATORB)
51.12 Forming an outer product of two vectors (OPRD)
51.13 Combining matrix columns (ADDVEC)
51.14 Forming a closed-shell density matrix (DENS)
51.15 Computing a fock matrix (FOCK)
51.16 Computing a coulomb operator (COUL)
51.17 Computing an exchange operator (EXCH)
51.18 Printing matrices (PRINT)
51.19 Printing diagonal elements of a matrix (PRID)
51.20 Printing orbitals (PRIO)
51.21 Assigning matrix elements to a variable (ELEM)
51.22 Reading a matrix from the input file (READ)
51.23 Writing a matrix to an ASCII file (WRITE)
51.24 Examples
51.25 Exercise: SCF program
Bibliography
A. Installation Guide
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 MOLPRO2009.1
B..2 New features of MOLPRO2008.1
B..3 New features of MOLPRO2006.1
B..4 New features of MOLPRO2002.6
B..5 New features of MOLPRO2002
B..6 Features that were new in MOLPRO2000
B..7 Facilities that were new in MOLPRO98
C. Density functional descriptions
C..1 B86: X
C..2 B86MGC: X with Modified Gradient Correction
C..3 B86R: X 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 Approximation
C..22 LYP: Lee, Yang and Parr Correlation Functional
C..23 MK00: Exchange Functional for Accurate Virtual Orbital Energies
C..24 MK00B: Exchange Functional for Accurate Virtual Orbital Energies
C..25 P86:
C..26 PBEC: PBE Correlation Functional
C..27 PBEX: PBE Exchange Functional
C..28 PBEXREV: Revised 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 THGFC:
C..39 THGFCFO:
C..40 THGFCO:
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 2010-03-10
