manual   quickstart   instguide   update   basis

Next: MOLPRO on the WWW Up: Users Manual Previous: Users Manual   Contents   Index   PDF

Introduction to MOLPRO

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 methods. The recently developed explicitly correlated coupled-cluster methods yield CCSD(T) results with near basis set limit accuracy already with double$-\zeta$ or triple$-\zeta$ 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

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:

  1. 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).

  2. 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).

  3. 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).

  4. 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).

  5. Correlation regions in local correlation calculations as described in R. A. Mata, H.-J. Werner and M. Schütz, J. Chem. Phys. 128, 144106 (2008).

  6. 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).

  7. 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.

  8. Dynamical state weighting as described in M. P. Deskevich and D. J. Nesbitt, and H.-J. Werner, J. Chem. Phys. 120, 7281 (2004).

  9. 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.

  10. 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).

  11. 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).

  12. 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).

  13. Automatic basis set extrapolation.

  14. Enhanced connections to other programs, including graphical display of output and 3-dimensional structures.

  15. Support for Mac OS X

  16. 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).

  17. 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).

  18. 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.

Next: MOLPRO on the WWW Up: Users Manual Previous: Users Manual   Contents   Index   PDF

manual   quickstart   instguide   update   basis

molpro@molpro.net 2017-09-24