MOLPRO is a complete system of ab initio programs for
molecular electronic structure calculations, designed and maintained by
H.-J. Werner and P. J. Knowles, and containing contributions from a number
of other authors. As distinct from other commonly used quantum chemistry
packages, the emphasis is on highly accurate computations,
with extensive treatment of the electron correlation problem
through the multiconfiguration-reference CI, coupled cluster and associated
The recently developed explicitly correlated coupled-cluster
methods yield CCSD(T) results with near basis set limit accuracy
already with double or triple basis sets, thus reducing the
computational effort for calculations of this quality by two orders of magnitude.
Using local electron correlation
methods, which significantly reduce the increase of the computational cost with molecular size,
accurate ab initio calculations can be performed for much larger molecules than
with most other programs. These methods have recently been augmented by explicitly
correlated terms, which strongly reduce both the basis set truncation errors and the
errors of the local approximations.
The heart of the program consists of the multiconfiguration SCF,
multireference CI, and coupled-cluster
routines, and these are accompanied by a full set of
supporting features. The package comprises
- Integral generation for generally contracted symmetry adapted gaussian
basis functions (). There are two programs with identical
the preferred code is SEWARD (R. Lindh) which
is the best on most machines;
ARGOS (R. M. Pitzer) is available as an alternative, and in
some cases is optimum for small memory
Also two different gradient integral codes, namely CADPAC (R. Amos) and
ALASKA (R. Lindh) are available. Only the latter allows the use of
generally contracted symmetry adapted gaussian
- Effective Core Potentials (contributions from H. Stoll).
- Many one-electron properties.
- Some two-electron properties, e.g. , , , etc..
- Closed-shell and open-shell (spin restricted and unrestricted) self consistent field.
- Density-functional theory in the Kohn-Sham framework with various gradient
corrected exchange and correlation potentials.
- Multiconfiguration self consistent field. This is the quadratically
convergent MCSCF procedure described in J. Chem. Phys. 82 (1985) 5053. The
program can optimize a weighted energy average of several states, and is
capable of treating both completely general configuration expansions and
also long CASSCF expansions as described in Chem. Phys. Letters 115 (1985)
- Multireference perturbation theory (MRPT2, CASPT2, CASPT3), including (extended)
multi-state methods MS-CASPT2 and XMS-CASPT2 as described in
Mol. Phys. 89, 645 (1996),
J. Chem. Phys. 112, 5546 (2000),
J. Chem. Phys. 135, 081106 (2011).
- Multireference CI. As well as the usual single reference function
approaches (MP2, SDCI, CEPA), this module implements the internally
contracted multireference CI method as described in J. Chem. Phys. 89
(1988) 5803 and Chem. Phys. Lett. 145 (1988) 514. Non variational variants
(e.g. MR-ACPF), as described in Theor. Chim. Acta 78 (1990) 175, are also
available. Electronically excited states can be computed as described in
Theor. Chim. Acta, 84 95 (1992). A new more efficient MRCI implementation
is described in J. Chem. Phys. 135, 054101 (2011).
- Møller-Plesset perturbation theory (MPPT),
Coupled-Cluster (CCSD), Quadratic configuration interaction
(QCISD), and Brueckner Coupled-Cluster (BCCD) for closed shell
systems, as described in
Chem. Phys. Lett. 190 (1992) 1.
Perturbative corrections for triple excitations can also be calculated
(Chem. Phys. Letters 227 (1994) 321).
- Open-shell coupled cluster theories as described in
J. Chem. Phys. 99 (1993) 5219,
Chem. Phys. Letters 227 (1994) 321.
- An interface to the MRCC program of M. Kallay, allowing coupled-cluster calculations
with arbitrary excitation level.
- Full Configuration Interaction. This is the determinant based benchmarking
program described in Comp. Phys. Commun. 54 (1989) 75.
- Analytical energy gradients for SCF, DFT, state-averaged MCSCF/CASSCF, MRPT2/CASPT2,
MP2 and QCISD(T) methods.
- Analytical non-adiabatic coupling matrix elements for MCSCF.
- Valence-Bond analysis of CASSCF wavefunction, and energy-optimized
valence bond wavefunctions as described in
Int. J. Quant. Chem. 65, 439 (1997).
- One-electron transition properties for MCSCF, MRCI, and EOM-CCSD wavefunctions,
CASSCF and MRCI transition properties also between wavefunctions with different orbitals,
as described in Mol. Phys. 105, 1239, (2007).
- Spin-orbit coupling, as described in
Mol. Phys., 98, 1823 (2000). More recently,
a new spin-orbit integral program for generally contracted basis sets has been implemented.
- Douglas-Kroll-Hess Hamiltonian up to arbitrary order and the eXact-2-Component (X2C) Hamiltonian.
- Density-functional theory symmetry-adapted intermolecular perturbation theory (with density fitting),
DFT-SAPT , as described in J. Chem. Phys. 122, 014103 (2005).
- Some two-electron transition properties for MCSCF wavefunctions (e.g.,
- Mulliken population analysis and Natural Population Analysis (NPA)
- Orbital localization.
- Natural bond orbitals (NBOs).
- Distributed Multipole Analysis (A. J. Stone).
- Automatic geometry optimization as described in
J. Comp. Chem. 18, (1997), 1473.
Constrained optimization is also possible.
- Automatic calculation of vibrational frequencies, intensities,
and thermodynamic properties.
- Reaction path following, as described in
Theor. Chem. Acc. 100, (1998), 21.
- Efficient facilities to treat large lattices of point charges for QM/MM calculations,
including lattice gradients.
- Various utilities allowing other more general optimizations,
looping and branching (e.g., for automatic generation of complete
potential energy surfaces), general housekeeping operations.
- Geometry output in XYZ,
formats; molecular orbital and frequency output in
- Integral-direct implementation of all Hartree-Fock, DFT and
pair-correlated methods (MP, CCSD, MRCI etc.), as described
in Mol. Phys., 96, (1999), 719. At present, perturbative
triple excitation methods are not implemented.
- Local second-order Møller-Plesset perturbation theory (LMP2) and
local coupled cluster methods, as described in
J. Chem. Phys. 104, 6286 (1996),
Chem. Phys. Lett. 290, 143 (1998),
J. Chem. Phys. 111, 5691 (1999),
J. Chem. Phys. 113, 9443 (2000),
J. Chem. Phys. 113, 9986 (2000),
Chem. Phys. Letters 318, 370 (2000),
J. Chem. Phys. 114, 661 (2001),
Phys. Chem. Chem. Phys. 4, 3941 (2002),
J. Chem. Phys. 116, 8772 (2002).
- Local density fitting methods, as described in
J. Chem. Phys. 118, 8149 (2003),
Phys. Chem. Chem. Phys. 5, 3349 (2003),
Mol. Phys. 102, 2311 (2004).
- Analytical energy gradients for LMP2, DF-LMP2, and LQCISD as described in
J. Chem. Phys. 108, 5185, (1998),
Phys. Chem. Chem. Phys. 3, 4853 (2001),
J. Chem. Phys. 121, 737 (2004).
- Analytical energy gradients for CASSCF, CASPT2, MS-CASPT2, and XMS-CASPT2 as described in
J. Chem. Phys. 119, 5044 (2003).
J. Chem. Phys. 135, 081106 (2011),
J. Chem. Phys., 138, 104104 (2013).
- Explicitly correlated MP2-F12 and CCSD(T)-F12 methods, as described in
J. Chem. Phys. 119, 4607 (2003),
J. Chem. Phys. 121, 4479 (2004),
J. Chem. Phys. 124, 054114 (2006),
J. Chem. Phys. 124, 094103 (2006),
J. Chem. Phys. 127, 221106 (2007),
J. Chem. Phys. 130, 054104 (2009).
- Explicitly correlated local LMP2-F12 and LCCSD(T)-F12 methods, as described in
J. Chem. Phys. 129, 101103 (2009),
J. Chem. Phys. 130, 054106 (2009),
J. Chem. Phys. 130, 241101 (2009),
J. Chem. Phys. 135, 144117 (2011),
Phys. Chem. Chem. Phys. 14, 7591 (2012).
- Explicitly correlated multireference methods (CASPT2-F12, MRCI-F12), as described in
J. Chem. Phys. 133, 141103 (2010),
J. Chem. Phys. 134, 034113 (2011),
J. Chem. Phys. 134, 184104 (2011),
Mol. Phys. 111, 607 (2013).
- Parallel execution on distributed memory machines, as
described in J. Comp. Chem. 19, (1998), 1215.
At present, SCF, DFT, MRCI, MP2, LMP2, CCSD(T), LCCSD(T) energies and SCF, DFT
gradients are parallelized. Most density fitted codes such as
DF-HF, DF-KS, DF-LMP2, DF-LMP2 gradients, DF-LCCSD(T), DF-MP2-F12, DF-DFT-SAPT, and GIAO-DF-HF
NMR shieldings are also parallelized.
- Automatic embarrassingly parallel computation of numerical gradients and
Hessians (mppx Version).
The program is written mostly in standard Fortran-90. Those parts which
are machine dependent are maintained through the use of a supplied
preprocessor, which allows easy interconversion between versions for
different machines. Each release of the program is ported and tested on
a number of systems.
A large library of commonly used orbital basis sets is available, which
can be extended as required. There is a comprehensive users' manual,
which includes installation instructions. The manual is available in PDF
and also in HTML for mounting on a Worldwide Web server.
More recent methods and enhancements include:
- Explicitly correlated
MP2-F12 (closed-shell) and RMP2-F12 (open-shell) methods with many many different ansätze, as described in
H.-J. Werner, T. B. Adler, and F. R. Manby, J. Chem. Phys. 126, 164102 (2007) and
G. Knizia and H.-J. Werner, J. Chem. Phys. 128, 154103 (2008).
- Explicitly correlated CCSD(T)-F12 methods as described in
T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys. 127, 221106 (2007) (closed-shell) and
G. Knizia, T. B. Adler, and H.-J. Werner, J. Chem. Phys. 130, 054104 (2009) (open-shell).
- Explicitly correlated LMP2-F12 and LCCSD-F12 methods as described in
H.-J. Werner, J. Chem. Phys. 129, 101103 (2009),
T. B. Adler, H.-J. Werner, and F. R. Manby, J. Chem. Phys. 130, 054106 (2009),
and T. B. Adler and H.-J. Werner, J. Chem. Phys. 130, 241101 (2009).
- Natural localized orbitals, NPA and NBO analysis and improved methods for domain
selection in local correlation calculations as described in
R. A. Mata and H.-J. Werner, Mol. Phys. 105, 2753 (2007);
see also R. A. Mata and H.-J. Werner, J. Chem. Phys. 125, 184110 (2006).
- Correlation regions in local correlation calculations as described in
R. A. Mata, H.-J. Werner and M. Schütz, J. Chem. Phys. 128, 144106 (2008).
- Beyond LMP2 treatment of intermolecular pairs in local coupled cluster methods as described in
O. Masur, D. Usvyat and M. Schütz, J. Chem. Phys., 139, 164116 (2013),
M. Schütz, O. Masur and D. Usvyat, J. Chem. Phys., 140, 244107 (2014).
- Automated calculation of anharmonic vibrational frequencies and zero-point energies
using VCI methods as described in
T. Hrenar, H.-J. Werner, and G. Rauhut, J. Chem. Phys. 126, 134108 (2007) and references therein.
- Dynamical state weighting as described in
M. P. Deskevich and D. J. Nesbitt, and H.-J. Werner, J. Chem. Phys. 120, 7281 (2004).
- Coupling of DFT and coupled cluster methods as described in
E. Goll, T. Leininger, F. R. Manby, A. Mitrushchenkov, H.-J. Werner, and H. Stoll, Phys. Chem. Chem. Phys. 10,
3353 (2008) and references therein.
- NMR chemical shifts, magnetizability, and rotational g-tensor using London atomic orbitals for density-fitted Hartree-Fock, and local MP2, as described in
S. Loibl, F.R. Manby, M. Schütz, Mol. Phys. 108, 1362 (2010),
S. Loibl, M. Schütz, J. Chem. Phys. 137, 084107 (2012), and
S. Loibl and M. Schütz, J. Chem. Phys., 141, 024108 (2014).
- Local response methods (LCC2) for computing excitation energies and transition properties in large molecule as described in
D. Kats, T. Korona, M. Schütz, J. Chem. Phys. 125, 104106 (2006),
D. Kats, T. Korona, M. Schütz, J. Chem. Phys. 127, 064107 (2007),
D. Kats, M. Schütz, J. Chem. Phys. 131, 124117 (2009), and
K. Freundorfer, D. Kats, T. Korona, M. Schütz, J. Chem. Phys. 133, 244110 (2010).
- LCC2 response and LADC(2) orbital relaxed properties and analytical nuclear gradients as described in
K. Ledermüller, D.Kats and M. Schütz, J. Chem. Phys. 139, 084111 (2013),
K. Ledermüller and M. Schütz, J. Chem. Phys. 140, 164113 (2014),
M. Schütz, J. Chem. Phys. 142, 214103 (2015).
- Automatic basis set extrapolation.
- Enhanced connections to other programs, including graphical display of output and 3-dimensional structures.
- Support for Mac OS X
- Ring-polymer instanton methods for rate and tunnelling-splitting calculations, as described in
J. O. Richardson and S. C. Althorpe, J. Chem. Phys. 131, 214106 (2009), and ibid. 134, 054109 (2011).
- Full Configuration Interation Quantum Monte Carlo (FCIQMC) as described in
G. H. Booth, A. J. W. Thom, and A. Alavi, J. Chem. Phys. 131, 054106 (2009),
D. M. Cleland, G. H. Booth, and A. Alavi, J. Chem. Phys. 134, 024112 (2011), and
G. H. Booth, D. M. Cleland, A. J. W. Thom, and A. Alavi, J. Chem. Phys. 135, 084104 (2011).
- DMRG calculations through the BLOCK code of the Chan group.
Future enhancements presently under development include
These features will be included in the base version at later stages.
The above list is for information only, and no representation is made that any of the
above will be available within any particular time.
- Analytical energy gradients for CCSD(T) and CCSD(T)-F12.
- Analytic second derivatives for DFT.
- New, more efficient MRCI methods for larger molecules.