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+ | ====== Recent changes ====== | ||
+ | |||
+ | Several well parallelized new methods have been implemented in Molpro. A review of recent developments in Molpro can be found in [[https:// | ||
+ | |||
+ | We recommend always to use the most recent version, since developments are ongoing and problems reported by users are always fixed as quickly as possible. In particular, before reporting bugs, please check if these still occur in the latest version. | ||
+ | |||
+ | ===== New features of MOLPRO2024.1 ===== | ||
+ | |||
+ | Various bug fixes and improvements of existing methods. | ||
+ | |||
+ | ==== iMolpro ==== | ||
+ | |||
+ | A new graphical user interface called '' | ||
+ | |||
+ | ==== D4 dispersion correction ==== | ||
+ | |||
+ | Unfortunately this has been wrong (usually too small) for pseudo-potential calculations. This bug has been fixed. | ||
+ | |||
+ | |||
+ | |||
+ | ==== DFT functional alias names ==== | ||
+ | |||
+ | Many alias names for functionals computed with libxc have been added. These are compatible with those used in the D4 program. | ||
+ | |||
+ | ==== Density-based basis set correction ==== | ||
+ | |||
+ | This program has been very much speeded up, with and without density fitting. Various functionals can now be used in it. | ||
+ | |||
+ | |||
+ | ==== Internally Contracted Multireference Coupled-Cluster Theory ==== | ||
+ | |||
+ | A CAS(2,2) version of icMRCCSD is now available, as published in [[https:// | ||
+ | ==== PNO-LMP2-F12 / PNO-LCCSD(T)-F12 ==== | ||
+ | |||
+ | New variables EMP2F12_PNO and EMP2F12_OSV are set for MP2-F12 energies computed with PNO or PAO/OSV projector, respectively. This happens in calculations with option projector=PAO or projector=MIXED. | ||
+ | |||
+ | ==== Nuclear-electronic orbital (NEO) methods ==== | ||
+ | |||
+ | A new automated procedure for the optimisation of quantum nuclei positions has been introduced (adaptive-NEO). The latter works by updating the nuclei position (meaning the nuclear basis centers, together with the respective electronic basis functions) to the nuclear orbital centroids during the SCF cycles. See [[nuclear-electronic_orbital_method# | ||
+ | |||
+ | ==== Basis set short names ==== | ||
+ | |||
+ | The short names [awc]vnz-dk (n=d,t,q,5) now refer to the [aug]-cc-p[wC]V(n+d)Z-DK sets for second-row elements Al-Cl. To avoid using the +d sets (not recommended!) use the full basis set name. | ||
+ | ===== GUI gmolpro 2.3.0 ===== | ||
+ | Version 2.3.0 is bundled with Molpro 2024.1 . | ||
+ | |||
+ | There is now a switch " | ||
+ | in the builder and viewer window to deal with those Mac's which have retina screens. | ||
+ | It switches from a normal display (retina factor 1) | ||
+ | to a display with doubled number of pixels in both directions (retina factor 2). | ||
+ | When this factor is changed, then it gets auto-saved in a configuration file $HOME/ | ||
+ | If necessary, this configuration file can be edited and retina factors different from 1 or 2 may be used. | ||
+ | |||
+ | LIBGL_ALWAYS_SOFTWARE is set to be true. This avoids a crash on some Linux distributions, | ||
+ | in the Mesa library. | ||
+ | |||
+ | |||
+ | ===== New features of MOLPRO2023.1 ===== | ||
+ | Molpro 2023.2 is a bug-fix release with the same features as Molpro 2023.1 | ||
+ | ==== Binaries for calculations on multiple nodes ==== | ||
+ | |||
+ | The Linux MPI-PR binary now supports parallel calculations on multiple computer nodes based on UCX (which must be installed on the cluster). Currently, multi-node calculations are restricted to closed-and open-shell DF-HF, DF-KS, and PNO-LCCSD(T). It is generally recommended to use the MPI-PR version for parallel calculations, | ||
+ | |||
+ | ==== Unrestricted coupled cluster ==== | ||
+ | |||
+ | Unrestricted UCCSD(T) and related methods based on UHF orbitals are now available, see section [[Open-shell coupled cluster theories|Open-shell coupled cluster theories]]. | ||
+ | |||
+ | ==== Improved geometry optimization ==== | ||
+ | |||
+ | An improved geometry optimizer using natural internal coordinates is now available and used by default, see section [[Geometry optimization (OPTG)|Geometry optimization (OPTG)]]. New special options for this optimizer are described in section [[Geometry optimization (OPTG)# | ||
+ | |||
+ | ==== DFT Grids ==== | ||
+ | |||
+ | Rotationally invariant DFT grids have been implemented and is used by default. This is achieved by rotating the grid of each atom dependent of its local environment (see section [[the_density_functional_program# | ||
+ | |||
+ | ==== Treatment of core correlation in PNO methods ==== | ||
+ | |||
+ | The algorithm for automatically sorting inner and outer core orbitals has been improved and new a new option '' | ||
+ | |||
+ | ==== Nuclear-electronic orbital (NEO) methods ==== | ||
+ | |||
+ | The multicomponent restricted NEO Hartree-Fock method has been implemented in Molpro. This allows for the quantum mechanical treatment of a selected number of protons concurrent with the electronic SCF. For more information, | ||
+ | |||
+ | ==== Basis set extrapolation based on a DFT model ==== | ||
+ | |||
+ | The basis set incompleteness error correction based on a DFT model by E. Giner and J. Toulouse ([[https:// | ||
+ | |||
+ | ==== σ-functionals and RPA calculations with RIRPA code ==== | ||
+ | The σ-functionals developed by Görling and coworkers ([[https:// | ||
+ | |||
+ | ==== The CISPT2 method ==== | ||
+ | |||
+ | A new variant of multi-reference perturbation theory, denoted cispt2, has been added. This adds a perturbative double correction to a MRCI-singles (MRCIS) calculation. The initial MRCIS relaxes the reference coefficients before generating the internally contracted doubles. | ||
+ | |||
+ | ==== Bug fixes in NEVPT2 ==== | ||
+ | |||
+ | Some problems in NEVPT2 have been fixed, and tighter default integral screening thresholds for DF-NEVPT2 have been set. | ||
+ | |||
+ | ==== GUI gmolpro version 2.2.0 ==== | ||
+ | |||
+ | Version 2.2.0 of the graphical user interface gmolpro is bundled with Molpro2023.2.0 . | ||
+ | When installing gmolpro, then it is installed together with this Molpro version, and uses this version on the local machine. | ||
+ | |||
+ | Due to moving to gtk2.24, the menu bar on Mac is better synchronised. | ||
+ | |||
+ | Important: on some platforms such as openSUSE15.5, | ||
+ | |||
+ | Frequently asked question: | ||
+ | |||
+ | Q: An optimisation (or frequency calculation) is performed, but the icon to open the optimsation (or frequency) window is greyed out, why? | ||
+ | |||
+ | A: The GUI searches for orbitals, and generates a pulldown menu with a set of orbitals found. If there is more than one set of orbitals, then it may be necessary to load a different set of orbitals. If a corresponding optimisation (or frequency) calculation is found, then the icon to open the window will become clickable (and is not greyed out any more). | ||
+ | ===== New features of MOLPRO2022.3 ===== | ||
+ | |||
+ | ==== MPPX option ==== | ||
+ | |||
+ | The '' | ||
+ | |||
+ | ==== Coupled-cluster calculations using KS orbitals ==== | ||
+ | |||
+ | It is now possible to run CCSD or CCSD(T) calculations using orbitals from a previous Kohn-Sham (KS) calculation. New options '' | ||
+ | |||
+ | Option '' | ||
+ | |||
+ | Note that the (T) energies are still slightly different in closed-shell CCSD and UCCSD calculations. This is due to missing singles terms in the closed-shell triples program. Work is in progress to fix this problem. | ||
+ | |||
+ | |||
+ | ==== PNO methods: ==== | ||
+ | |||
+ | * The printed LMP2 energies in PNO-LMP2-F12 and PNO-LCCSD-F12 calculations now include the CABS singles correction (if available). The domain-corrected LMP2 energy is stored in a variable EMP2C (alias EMP2_DC), the MP2-F12 energy in variable EMP2F12 (alias EMP2_F12). | ||
+ | |||
+ | * (T) in PNO-LCCSD(T)-F12 calculations can be restarted from a dump file, see [[local_correlation_methods_with_pair_natural_orbitals_pnos# | ||
+ | |||
+ | * A very tight domain option has been added (domopt=vtight), | ||
+ | |||
+ | * New options for computing intermolecular pairs with special domains have been added, see [[local_correlation_methods_with_pair_natural_orbitals_pnos# | ||
+ | |||
+ | * If '' | ||
+ | |||
+ | |||
+ | ==== MRCI restart: ==== | ||
+ | |||
+ | A bug in the MRCI restart with stored reference vectors has been fixed. | ||
+ | |||
+ | ==== NEVPT2: ==== | ||
+ | |||
+ | The maximum number of active orbitals in NEVPT2 has been increased from 14 to 32. | ||
+ | |||
+ | ==== RS2 Gradients ==== | ||
+ | |||
+ | An parallelisation problem occurring with large reference spaces has been fixed. The performance and parallelisation of some parts of the gradient program have been improved. | ||
+ | |||
+ | ==== Rovibrational Spectra: ==== | ||
+ | |||
+ | The existing VCI program has been extended by a new directive (ROVIB), which allows for the automated calculation of high-resolution rotational and rovibrational spectra based on RVCI theory. Rotational and Coriolis coupling can be included up to high accuracy and several rotational bases are provided. As the final line lists can be very long, they are stored in an external file, which can be further processed by the DAT2GR program in order to simulate the corresponding spectra. To allow for maximal flexibility with respect to the vibrational bases, the VIBSTATE program has been significantly extended and controls now for all parts of the VSCF/VCI programs the list of states to be computed - including non-Abelian point groups (see the VSCF manual). | ||
+ | |||
+ | ==== NMR shielding tensors with DFT: ===== | ||
+ | NMR shielding tensors can be computed with LDA, GGA and hybrid GGA functionals using density fitting approximations of two-electron integrals using the new '' | ||
+ | |||
+ | ==== Documentation of default basis sets ==== | ||
+ | |||
+ | The documentation of default basis sets in Molpro has been extended, see section | ||
+ | [[basis_input# | ||
+ | |||
+ | ==== Cartesian basis functions: ==== | ||
+ | |||
+ | The input specifications for cartesian basis functions have been generalised. It is no possible to specify option '' | ||
+ | |||
+ | ==== Python project management === | ||
+ | |||
+ | The pymolpro Python package has been released, and is available via conda-forge. | ||
+ | |||
+ | ===== New features of MOLPRO2022.2 ===== | ||
+ | |||
+ | Various problems concerning the use of cartesian basis functions have been fixed, including the starting guess and AVAS. Density fitting now works for cartesian basis sets up to h-functions. | ||
+ | |||
+ | The default of DFT grid option orient has been change to 1; this makes KS energies rotationally invariant, but may slightly change energies (mostly in the microhartree range. To recover the old behaviour add grid option orient=1. | ||
+ | |||
+ | A new [[local_correlation_methods_with_pair_natural_orbitals_pnos# | ||
+ | Different F12 geminal exponents for valence, core-valence, | ||
+ | See [[explicitly_correlated_methods# | ||
+ | |||
+ | The memory usage and performance of the RS2C expectation value calculations are significantly improved. | ||
+ | The [[multireference_rayleigh_schroedinger_perturbation_theory|NOPROP]] option is added to skip the expectation value calculations. | ||
+ | |||
+ | DFT options for controlling grid accuracy have been added to gmolpro. | ||
+ | |||
+ | OPTG options for choosing optimization methods and coordinates have been added to gmolpro. | ||
+ | |||
+ | ==== GUI gmolpro version 2.1.0 ==== | ||
+ | |||
+ | Version 2.1.0 of the graphical user interface gmolpro is bundled with Molpro2022.2.3 . | ||
+ | When installing gmolpro, then it is installed together with Molpro version 2022.2.3 , and uses this version on the local machine. | ||
+ | |||
+ | The token may be installed in | ||
+ | '' | ||
+ | |||
+ | A slider to change the vibrational amplitudes has been added. As before, the animation speed can be changed with Options/ | ||
+ | |||
+ | The xyz-geometry in the builder window is now displayed in a little extra window. | ||
+ | |||
+ | Various bug fixes: z-matrix containing dummy atoms now properly written by Molpro, so that gmolpro correctly displays it; small window (segment window) in builder: hydrogens + dummies properly displayed etc. | ||
+ | |||
+ | Force-field parameters autodetected when importing xyz. | ||
+ | |||
+ | ==== GUI gmolpro version 2.0.0 ==== | ||
+ | |||
+ | Version 2.0.0 of the graphical user interface gmolpro is bundled with Molpro2022.2.2 . | ||
+ | When installing gmolpro, then it is installed together with Molpro version 2022.2.2 , and uses this version on the local machine. | ||
+ | |||
+ | The token may be installed in | ||
+ | '' | ||
+ | |||
+ | ===== New features of MOLPRO2022.1 ===== | ||
+ | |||
+ | ==== Update 2022.1.2 ==== | ||
+ | |||
+ | A bug affecting KS and TDDFT calculations with cartesian basis functions has been fixed. | ||
+ | |||
+ | ==== Perturbation-Adapted Perturbation Theory (PAPT) ==== | ||
+ | The perturbation-adapted zero-order hamiltonian described in J. Chem. Phys. 156, 011101 (2022); https:// | ||
+ | |||
+ | ==== CORE directive ==== | ||
+ | With '' | ||
+ | Global '' | ||
+ | See [[general_program_structure# | ||
+ | The old behaviour, where these electrons were correlated, can be recovered using '' | ||
+ | |||
+ | ==== SCF program === | ||
+ | * Quadratic optimization or mixed quadratic/ | ||
+ | * The CAHF optimization with the quadratic or the SO-SCI optimization is implemented into the CAHF program, and it can be called by '' | ||
+ | * A new variant of the SO-SCI optimization is available for the RHF case. It optimizes all AVAS orbitals quadratically and is called by '' | ||
+ | |||
+ | The '' | ||
+ | |||
+ | See section [[the_scf_program# | ||
+ | ==== MCSCF/ | ||
+ | * The entire export of CI vectors to subsequent Molpro programs has been rewritten. CI vectors can be exported via '' | ||
+ | * '' | ||
+ | * Gradients of the state-averaged energy are now available. | ||
+ | * The program is now more robust against spin-contamination in determinant based calculations. | ||
+ | |||
+ | ==== MRCI, CASPT2 ==== | ||
+ | The CI vectors stored in multi using the directive '' | ||
+ | |||
+ | ==== MCSCF/ | ||
+ | |||
+ | A new much more efficient algorithm for computing the spin-orbit Hamiltonian using MCSCF wavefunctions and ECP spin-orbit operators. The program to compute and diagonalize spin-orbit matrices can generally be called using | ||
+ | |||
+ | '' | ||
+ | |||
+ | where '' | ||
+ | |||
+ | For more details see section [[spin-orbit-coupling# | ||
+ | ==== PNO-LCCSD ==== | ||
+ | |||
+ | The IBO localization convergence threshold has been tightened from $10^{-8}$ to $10^{-9}$. | ||
+ | The PAO redundancy threshold '' | ||
+ | |||
+ | The localisation of core orbitals has been improved; it now uses an AO-based algorithm, which minimises | ||
+ | mixings of orbitals of different types (e.g. s, p$_x$, p$_y$, p$_z$). It has been found that this stabilises the F12(PNO) energy contribution if core orbitals are correlated. The new default for core-orbital localization is loc_method_core=IBO(AO). | ||
+ | |||
+ | The previous behaviour of the PNO program can be recovered by putting before the first PNO command: | ||
+ | |||
+ | '' | ||
+ | |||
+ | The corresponding new options are | ||
+ | |||
+ | '' | ||
+ | |||
+ | The options can also be given on the PNO command, lines. | ||
+ | |||
+ | ==== GUI gmolpro ==== | ||
+ | |||
+ | Version 1.4.0 of the graphical user interface gmolpro is compatible with Molpro2022.1 . | ||
+ | |||
+ | Main improvement over earlier versions is the ability to handle output files (xml files) with several optimisations, | ||
+ | |||
+ | When creating an input in guided mode, more properties may be selected by buttons. | ||
+ | |||
+ | |||
+ | ===== New features of MOLPRO2021.2 ===== | ||
+ | |||
+ | ==== Parallel execution ==== | ||
+ | |||
+ | An option has been added to use MPI files instead of large GlobalArrays to avoid potential GA allocation problems. From Molpro2020.2 the disk option ('' | ||
+ | |||
+ | For molpro2020.2 and Linux systems, an additional binary compiled with the GA '' | ||
+ | |||
+ | ==== RS2C/CASPT2 ==== | ||
+ | |||
+ | Multi-state CASPT2 is now available in the rs2c program, see [[multireference_rayleigh_schroedinger_perturbation_theory# | ||
+ | |||
+ | ==== NEVPT2 ==== | ||
+ | |||
+ | NEVPT2 can now be done with density fitting, the command is '' | ||
+ | |||
+ | ==== AVAS ==== | ||
+ | |||
+ | Additional options allow a more flexible definition of the target space. | ||
+ | |||
+ | |||
+ | ===== New features of MOLPRO2021.1 ===== | ||
+ | |||
+ | ==== Hartree-Fock ==== | ||
+ | |||
+ | A new implementation of the HF/KS program is now used by default. In difficult cases this shows more robust convergence. | ||
+ | |||
+ | * The old version can still be used by specifying option " | ||
+ | |||
+ | * Optionally, the hybrid second-order/ | ||
+ | |||
+ | ==== MCSCF/ | ||
+ | |||
+ | * [[the_mcscf_program_multi# | ||
+ | |||
+ | * [[the_mcscf_program_multi# | ||
+ | |||
+ | * [[the_mcscf_program_multi# | ||
+ | |||
+ | * [[the_mcscf_program_multi# | ||
+ | |||
+ | * Export of the [[the_mcscf_program_multi# | ||
+ | |||
+ | |||
+ | ==== Analytical energy gradients ==== | ||
+ | |||
+ | Analytical energy gradients are now available for RASPT2 (using rs2). | ||
+ | |||
+ | |||
+ | ==== TD-DFT ==== | ||
+ | |||
+ | * Rotatory strengths for simulating CD spectra of optically active molecules can be computed for spin-restricted TDDFT excitations | ||
+ | * First-order nonadiabatic coupling matrix elements (NACME) are available for closed and open-shell TDHF and TDDFT (LDA or GGA-type functionals) | ||
+ | |||
+ | |||
+ | ==== Miscellaneous ==== | ||
+ | |||
+ | * All fundamental constants used in the program have been updated to the most recent CODATA 2018 standard [[https:// | ||
+ | * The sparse orbital print has been modified. Now it shows for each printed coefficient the center number, the function type, and the sequence number for this type at the given atom (denoted MU). | ||
+ | |||
+ | |||
+ | ===== New features of MOLPRO2020.2 ===== | ||
+ | |||
+ | ==== Analytical energy gradients ==== | ||
+ | * DF-MCSCF (single state), DF-HF, DF-UHF, DF-KS, and DF-UKS gradients are now available with symmetry. | ||
+ | * TD-DFT gradients for closed-shell singlet excited states are available with and without density fitting. | ||
+ | |||
+ | ==== PNO-LCCSD(T)-F12 ==== | ||
+ | |||
+ | * The core orbitals are no longer excluded from the CCSD-F12 projector by default. The approximation, | ||
+ | * Correlated core orbitals are now localized separately from the valence orbitals by default, which mostly improves the results and convergence in calculations with core orbital correlation. The old default can be recovered by '' | ||
+ | * The '' | ||
+ | * The scaling factor for F12-scaled triples now excludes the contribution from distant pairs, for which F12 energies are neglected. | ||
+ | |||
+ | ==== Linux binaries ==== | ||
+ | |||
+ | The [[installation_guide# | ||
+ | |||
+ | |||
+ | |||
+ | |||
+ | |||
+ | ===== New features of MOLPRO2020.1 ===== | ||
+ | |||
+ | |||
+ | ===== Windows support ===== | ||
+ | A windows beta version of Molpro is now available. | ||
+ | ==== gMolpro: A graphical user interface ==== | ||
+ | |||
+ | A powerful graphical user interface (based on PQSMol) for building and preoptimising molecular structures, preparing and running Molpro inputs, and visualisation of results (will soon be available). gMolpro also supports remote job submission and is available for Linux and Mac. | ||
+ | |||
+ | |||
+ | ==== The MCSCF/ | ||
+ | The CASSCF program multi has been largely rewritten and well parallelized. Improved second-order algorithms as well as first-order methods applicable to large molecules have been implemented. The new program combines robust convergence with excellent efficiency. Details are described in [[https:// | ||
+ | |||
+ | ==== Multi-state PNO-CASPT2 ==== | ||
+ | The PNO-CASPT2 program for large molecules has been extended to allow multi-state MS-CASPT2 calculations. For details see [[https:// | ||
+ | ==== Time-dependent density-functional (TDDFT) program ==== | ||
+ | The time-dependent DFT program has been completely rewritten to support molecular symmetry, open-shell systems (for spin-unrestricted wave functions), various integral modes (including a very fast parallelised density-fitting mode) and standard LDA, GGA, hybrid-GGA and range-separated hybrid GGA functionals and kernels. Calculations using the exact Kohn-Sham exchange (TDEXX) method can be done both by using the adiabatic and non-adiabatic EXX kernel. Linear response properties can be calculated for any one-electron operators available in Molpro. Isotropic and anisotropic $C_6$, $C_8$ | ||
+ | and $C_{10}$ dispersion coefficients can be computed along with the calculation of frequency dependent (dipole, | ||
+ | |||
+ | |||
+ | ==== LibXC density functionals ==== | ||
+ | An interface to the external LibXC library (see [[https:// | ||
+ | be done now also using an efficient density-fitting implementation of the Fock matrix computation. | ||
+ | |||
+ | ==== Van-der-Waals density functionals ==== | ||
+ | An implementation of the nonlocal van-der-Waals DF VV10 by Vydrov & Van Voorhis is available for spin-restriced wave functions to improve the description of long-range correlation interactions of standard DFT methods. | ||
+ | |||
+ | ==== Explicitly correlated local coupled-cluster program for high-spin open-shell molecules ==== | ||
+ | The local coupled-cluster program PNO-LCCSD(T)-F12 has been revised to support open-shell molecules. | ||
+ | The new revision also includes some minor changes in the local approximations and is also used for closed-shell molecules by default. | ||
+ | The closed-shell program in Molpro 2019.2 and earlier can be executed with the option '' | ||
+ | For more details see [[Local correlation methods with pair natural orbitals (PNOs)]]. | ||
+ | |||
+ | ==== Extended potential energy surface generator ==== | ||
+ | A new program, XSURF, has been implemented for the efficient calculation of potential energy surfaces (PES) as needed for the calculation of anharmonic spectra. In contrast to the " | ||
+ | |||
+ | ==== Acceleration of the POLY and the PESTRANS programs ==== | ||
+ | Due to a complete redesign of the programs for the fitting (POLY) and the transformation of potential energy surfaces (PESTRANS), these programs could be accelerated by several orders of magnitude (only operative in combination of the new XSURF program). | ||
+ | |||
+ | ==== Electronic - vibrational spectra ==== | ||
+ | Similar to the Franck-Condon program, the new EVSPEC program allows for the calculation of anharmonic electronic-vibrational absorption spectra with the inclusion of Duschinsky effects. Two different imlementations are provided, the contracted invariant Krylov subspace (CIKS) approach and a Raman wavefunction (RWF) formalism. | ||
+ | |||
+ | ===== New features of MOLPRO2019.2 ===== | ||
+ | |||
+ | |||
+ | ==== Improved parallel density fitting in Hartree-Fock and DFT ==== | ||
+ | |||
+ | A new parallel density fitted Fock matrix generation has been implemented. For large molecules this scales well across computer nodes (with a fast network such as Infiniband) up to about half as many computing cores as occupied orbitals. | ||
+ | |||
+ | Symmetry can now be used in DF-HF and DF-KS (restricted and unrestricted), | ||
+ | |||
+ | ===== New features of MOLPRO2018.1 ===== | ||
+ | |||
+ | |||
+ | |||
+ | ==== Quasi-variational coupled-cluster (QVCCD) ==== | ||
+ | |||
+ | Improved efficient implementation of quasi-variational coupled-cluster (QVCCD). | ||
+ | |||
+ | ==== Analytical energy gradients for coupled cluster methods ==== | ||
+ | |||
+ | Analytical energy gradients for closed shell DF-MP2-F12, DF-CCSD(T)-F12, | ||
+ | |||
+ | ==== Analytical energy gradients for projection-based WF-in-DFT embedding ==== | ||
+ | |||
+ | Analytical nuclear gradients have been implemented for projection-based wavefunction-in-DFT (WF-in-DFT) embedding with and without atomic orbital (AO) truncation. The current available methods that can be used for the WF method on subsystem A are CCSD(T), CCSD, MP2, and HF. The current available methods that can be used for the low-level SCF method are LDA, LDAX (LDA with any amount of exact exchange) and HF. The support for using GGAs as the low-level method will be coming soon. | ||
+ | |||
+ | ==== Analytical energy gradients for local methods ==== | ||
+ | |||
+ | Analytic energy gradients for local MP2, RMP2, CC2 and ADC(2) (with density fitting) are available. These methods can be used for geometry optimisations and property calculations of larger molecules. | ||
+ | |||
+ | ==== Local coupled cluster linear response method for ionization potentials ==== | ||
+ | |||
+ | A hierarchy of local coupled cluster models for ionization potentials employing LMP2 or LCC2 ground state amplitudes and the Jacobian formally reaching the IP-CCSD level: IP-CCSD$_{\rm CC2}$ is now available. For details see G. Wälz, D. Usvyat, T. Korona, M. Schütz, [[https:// | ||
+ | |||
+ | ==== Local MP2 NMR shielding ==== | ||
+ | |||
+ | Local MP2 NMR shielding, magnetisability, | ||
+ | |||
+ | ==== MR-CCSD(T) ==== | ||
+ | |||
+ | The internally contracted multi-reference program of A. Köhn et al. has been interfaced to Molpro. An embedded Multireference Coupled Cluster method as described in D. J. Coughtrie, R. Giereth, D. Kats, H.-J. Werner, and A. Köhn, [[https:// | ||
+ | |||
+ | ==== Local density fitting Hartree-Fock and Kohn-Sham (LDF-HF, LDF-KS) ==== | ||
+ | |||
+ | A new parallel implementation of Hartree Fock with local density fitting (closed and open-shell), | ||
+ | |||
+ | ==== Local complete active space second-order perturbation theory with pair natural orbitals (PNO-CASPT2) ==== | ||
+ | |||
+ | An accurate and efficient local PNO-CASPT2 for large molecules as described in F. Menezes, D. Kats, H.-J. Werner, [[https:// | ||
+ | |||
+ | ==== PNO-LCCSD(T)-F12 ==== | ||
+ | |||
+ | Explicitly correlated well parallelized PNO methods are now available up to the PNO-LCCSD(T)-F12 level. This program yields results that are very close to the corresponding canonical CCSD(T)-F12 ones. For medium size cases where canonical calculations are still feasible, the PNO-LCCSD(T)-F12 is up to an order of magnitude faster than the canonical CCSD(T)-F12 program, while relative energies typically differ by only 0.2 kcal/mol. The largest applications so far include molecules with up to about 300 atoms and 10000 basis functions. The methods are described in H.-J. Werner, [[https:// | ||
+ | |||
+ | ==== D4 dispersion correction for DFT ==== | ||
+ | |||
+ | The new D4 dispersion model improves the description of atomic dispersion coefficients through charge-dependent local polarisabilities obtained by a self-consistent tight-binding method, see E. Caldeweyher, | ||
+ | |||
+ | ==== Nonlocal DFT method ==== | ||
+ | |||
+ | The nonlocal DFT method (NLDFT) improves the description of long-range correlation interactions of standard DFT functionals through a double-Hirshfeld partitioning of the correlation energy density, see A. Heßelmann, [[https:// | ||
+ | |||
+ | ==== Kohn-Sham RPA methods ==== | ||
+ | |||
+ | Random-phase approximation electron correlation methods based on Kohn-Sham reference determinants, | ||
+ | |||
+ | ==== New features in DFT-SAPT ==== | ||
+ | |||
+ | Several new features have been implemented in the DFT-SAPT program, including: | ||
+ | |||
+ | * Exchange interaction energy contributions without the single-exchange approximation (R. Schäffer and G. Jansen, | ||
+ | * DFT-SAPT employing exact-exchange response kernels (A. Heßelmann, [[https:// | ||
+ | * Regularised SAPT for estimating short-range polarisation interactions (A. J. Misquitta, [[https:// | ||
+ | |||
+ | ==== Automated selection of molecular active space (AVAS) ==== | ||
+ | |||
+ | This method helps to find good starting orbitals for CASSCF calculations. It is based on the work of Knizia et al., [[https:// | ||
+ | |||
+ | ==== Further enhancements ==== | ||
+ | |||
+ | * Improved parallelization of coupled-cluster codes\\ | ||
+ | |||
+ | * Improved DFT quadrature\\ | ||
+ | |||
+ | * New plugin interfaces for other programs, e.g. MR-CCSD(T), DMRG and FCIQMC codes, supporting directed parallel execution\\ | ||
+ | |||
+ | * Implementation of the eXact-2-Component (X2C) scalar relativistic Hamilitonian\\ | ||
+ | |||
+ | * Support for a Gaussian finite nucleus model\\ | ||
+ | |||
+ | * New correlation consistent basis sets for heavy alkali and alkaline earth elements (both relativistic all-electron and with ECPs), as well as all-electron (DK3 and X2C) basis sets for the lanthanide and actinide elements. | ||
+ | * X2C-contracted versions for all the standard correlation consistent basis sets for H, He, B-Ne, and Al-Cl, e.g., cc-pVDZ-X2C | ||
+ | |||
+ | ===== New features of MOLPRO2015.1 ===== | ||
+ | |||
+ | Molpro 2015 contains many improvements, | ||
+ | |||
+ | ==== Projection-based wavefunction-in-DFT embedding ==== | ||
+ | |||
+ | The WF-in-DFT impementation in Molpro [F. R. Manby et al., [[https:// | ||
+ | |||
+ | ==== Intrinsic bond-orbital analysis and orbital localization (IBO). ==== | ||
+ | |||
+ | IBOs provide a reliable and efficient way to generate localized orbitals and to analyze wavefunctions, | ||
+ | |||
+ | ==== Interface to NBO6 ==== | ||
+ | |||
+ | Molpro 2015 supports NBO6 Natural Bond Orbital Analysis (NBO6) via an interface. NBO6 must be licensed separately. | ||
+ | |||
+ | ==== Beyond LMP2 treatment of intermolecular pairs in local coupled cluster methods ==== | ||
+ | |||
+ | Usually close (and weak) pairs are treated only at the LMP2 level in LCCSD(T) calculations. This not satisfying since LMP2 often treats van der Waals interactions poorly, hence compromising the high accuracy of the actual LCCSD(T) calculation. Fortunately, | ||
+ | |||
+ | O. Masur, D. Usvyat and M. Schütz, [[https:// | ||
+ | M. Schütz, O. Masur and D. Usvyat, [[https:// | ||
+ | |||
+ | ==== Distinguishable cluster Approximation (DCSD and DCSD-F12) ==== | ||
+ | |||
+ | This approximation yields improved results at the cost of CCSD. In particular, DCSD equilibrium structures are as accurate as for CCSD(T), see | ||
+ | |||
+ | D. Kats and F. R. Manby, [[https:// | ||
+ | D. Kats, J. Chem. Phys. **141i**, 061101 (2014);\\ | ||
+ | D. Kats, D. Kreplin, H.-J. Werner, F. R. Manby, [[https:// | ||
+ | |||
+ | ==== Analytical energy gradients ==== | ||
+ | |||
+ | Analytical gradients are now available for DCSD. Analytical gradients for CCSD(T), as well as for MP2-F12, CCSD(T)-F12, | ||
+ | |||
+ | ==== Orbital relaxed properties and analytical nuclear gradients for excited states ==== | ||
+ | |||
+ | Orbital relaxed properties, and analytical nuclear gradients for excited states are now available for local CC2 response and local ADC(2). This allows for geometry optimizations of excited states of large chromophores at these levels of theory. Furthermore, | ||
+ | |||
+ | K. Ledermüller, | ||
+ | K. Ledermüller and M. Schütz, [[https:// | ||
+ | M. Schütz, [[https:// | ||
+ | |||
+ | ==== PNO-LMP2 and PNO-LMP2-F12 ==== | ||
+ | |||
+ | New parallel linear scaling PNO-LMP2 and PNO-LMP2-F12 programs as described in | ||
+ | |||
+ | H.-J. Werner, G. Knizia, C. Krause, and M. Schwilk, [[https:// | ||
+ | Q. Ma and H.-J. Werner, J. Chem. Theory Comput., DOI: 10.1021/ | ||
+ | C. Köppl and H.-J. Werner, [[https:// | ||
+ | |||
+ | are available in version 2015. PNO-LCCSD(T) is currently under development and will be made freely available to licensees of Molpro 2015 at a later stage. | ||
+ | |||
+ | ==== Magnetizability and rotational g-tensor at DF-LMP2 level using GIAOs ==== | ||
+ | |||
+ | The program for NMR chemical shifts has been extended to include also magnetizability and rotational g-tensor. This is described in | ||
+ | |||
+ | S. Loibl and M. Schütz, [[https:// | ||
+ | |||
+ | ==== Faster density fitting integral routines ==== | ||
+ | |||
+ | DFT and F12 methods with density fitting are significantly speeded up using improved integration routines written by G. Knizia. | ||
+ | |||
+ | ==== Vibrational perturbation theory: VPT2 ==== | ||
+ | |||
+ | A VPT2 program based on a semi-quartic force field (QFF) has been implemented, | ||
+ | |||
+ | ==== Vibrational multi-reference methods: VMCSCF, VMRCI ==== | ||
+ | |||
+ | A suite of vibrational multi-reference methods is available now. Modals can be optimized at the VMCSCF level [S. Heislbetz and G. Rauhut, [[https:// | ||
+ | |||
+ | ==== Anharmonic Franck-Condon factors: FCON ==== | ||
+ | |||
+ | A Franck-Condon program based on anharmonic vibrational wavefunctions has been implemented. Franck-Condon factors can either be computed by rotating the vibrational wavefunction or by transforming the potential energy surface in order to account for Duschinsky effects. This program, which allwos for the accurate calculation of photoelectron spectra (absorption and fluorescence) relies on the newly developed transformation program '' | ||
+ | |||
+ | ==== Transformation of multi-dimensional potential energy surfaces: PESTRANS ==== | ||
+ | |||
+ | Multi-dimensional potential energy surfaces spanned in terms of normal coordinates - as computed with the '' | ||
+ | |||
+ | ==== Localized normal coordinates ==== | ||
+ | |||
+ | Within the '' | ||
+ | |||
+ | ==== Calculation of arbitrary vibrational states: VIBSTATE ==== | ||
+ | |||
+ | In the old Molpro release the calculation of vibrational states was limited to fundamentals, | ||
+ | |||
+ | ==== Raman scattering activities ==== | ||
+ | |||
+ | Raman scattering activities can now be computed within all vibrational SCF and vibration correlation programs. As polarizabilities can only be determined at the Hartree-Fock level, the accuracy is currently still limited. | ||
+ | |||
+ | ==== Reaction databases ==== | ||
+ | |||
+ | A facility is provided to store and interrogate sets of molecules, together with information about how they are to be combined in balanced chemical equations. This database can be generated manually, or partially by running appropriate Molpro calculations. Analysis of the database can give a summary of the energy changes associated with each described reaction, and two or more similar databases can be compared reaction by reaction, to give a statistical analysis of the differences between them. Several common databases are included. | ||
+ | |||
+ | ==== New density-fitting DFT-SAPT program ==== | ||
+ | |||
+ | A new DFT-SAPT program has been implemented in Molpro which can be used in conjunction with monomer-centered (MCBS), monomer-centered plus (MC+BS) or dimer-centered (DCBS) basis sets. Even in DCBS mode fairly large complexes with about 800 electrons can be studied with this program, see A. Heßelmann and T. Korona. [[https:// | ||
+ | |||
+ | ===== New features of MOLPRO2012.1 ===== | ||
+ | |||
+ | A summary of the features in Molpro can be found in a recent review: H.-J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, and M. Schütz, //Molpro – a general purpose quantum chemistry program package//, WIRES Comput. Mol. Sci. **2**, 242 (2012), [[https:// | ||
+ | |||
+ | The new features of Molpro version 2012.1 include the following. | ||
+ | |||
+ | ==== Quasi-variational coupled-cluster theory ==== | ||
+ | |||
+ | This modification of standard CCSD is capable of robustly describing chemical bond breaking with a single Hartree-Fock reference determinant (see J. B. Robinson and P. J. Knowles, [[https:// | ||
+ | |||
+ | ==== A new internally contracted MRCI code: MRCIC ==== | ||
+ | |||
+ | A new internally contracted MRCI code [see K. R. Shamasundar, | ||
+ | |||
+ | ==== Explicitly correlated multireference theories: RS2-F12, MRCI-F12 ==== | ||
+ | |||
+ | Explicitly correlated multireference theories (CASPT2-F12, | ||
+ | |||
+ | A review of the explicitly correlated multireference methods can be found in T. Shiozaki and H.-J. Werner, [[https:// | ||
+ | |||
+ | ==== Extended multi-state CASPT2 ==== | ||
+ | |||
+ | Extended multistate CASPT2 (XMS-CASPT2) [see T. Shiozaki, W. Győrffy, P. Celani, and H.-J. Werner, // | ||
+ | |||
+ | ==== Density fitted CASSCF and CASPT2 ==== | ||
+ | |||
+ | CASSCF and CASPT2 as well as the corresponding analytical gradient theories are now available with density fitting ('' | ||
+ | |||
+ | ==== Extensions of explicitly correlated coupled-cluster methods ==== | ||
+ | |||
+ | The (F12*) approximation proposed by Hättig et al. [[https:// | ||
+ | |||
+ | Further basis sets of K. A. Peterson and J.G. Hill for explicitly correlated methods have been included. In particular these include the aug-cc-pVnZ-PP/ | ||
+ | |||
+ | ==== Density fitted local coupled-cluster methods: DF-LCCSD(T), | ||
+ | |||
+ | The local coupled cluster methods have been further improved. See H.-J. Werner and M. Schütz, //An efficient local coupled-cluster method for accurate thermochemistry of large systems//, [[https:// | ||
+ | |||
+ | ==== Local coupled-cluster methods with orbital-specific virtual orbitals: OSV-LCCSD(T) ==== | ||
+ | |||
+ | Local coupled cluster methods can optionally use orbital specific virtual orbitals (OSVs), see J. Yang, G. K. L. Chan, F. R. Manby, M. Schütz, and H.-J. Werner, //The orbital-specific virtual local coupled-cluster singles and doubles method: OSV-LCCSD//, | ||
+ | |||
+ | ==== Explicitly correlated local MP2 and CC methods: DF-LMP2-F12, | ||
+ | |||
+ | The explicitly correlated coupled cluster methods as described in H.-J. Werner, // | ||
+ | |||
+ | ==== Improved DFT with density fitting ==== | ||
+ | |||
+ | The efficiency of density functional theory has been much improved. In particular, the density fitting (DF-RKS, DF-UKS) codes for analytical energy gradients are now very much faster, due to a new integral code (adaptive integral core, AIC) written by G. Knizia. Some benchmarks can be found in H.-J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, and M. Schütz, //Molpro – a general purpose quantum chemistry program package//, WIRES Comput. Mol. Sci. **2**, 242 (2012). | ||
+ | |||
+ | ==== Additional density functionals ==== | ||
+ | |||
+ | A large number of additional density functionals has been added, including PBE0, PBEREV, M05, M05-2X, M06, M06-2X, M06-L, M06-HF, M08-HX, M08-SO, M11-L, SOGGA, SOGGA11, SOGGA11-X. (M11 is currently not available, but will likely be added in the near future). | ||
+ | |||
+ | ==== Additional gradient theories: CCSD, DF-MP2, DF-CASSCF, DF-RS2 ==== | ||
+ | |||
+ | New analytical gradient codes are now available for DF-MP2, DF-CASSCF, DF-RS2 (including MS and XMS options, also without density fitting), and for CCSD. | ||
+ | |||
+ | ==== Local methods for excited states ==== | ||
+ | |||
+ | First-order properties of excited states via time-dependent Local CC2 linear response theory and ADC(2) are now also available for triplet states. This is described in K. Freundorfer, | ||
+ | |||
+ | ==== NMR shielding tensors at DF-LMP2 level using GIAOs ==== | ||
+ | |||
+ | An efficient method for calculating NMR shielding tensors at the local MP2 level has been implemented. Gauge including atomic orbitals (GIAOs) are used to eliminate the gauge origin dependence. Density fitting is employed to factorize the relevant electron repulsion integrals and their derivatives w.r. to the magnetic field. So far, the method has been already applied to systems with more than 2500 contracted basis functions and 300 correlated electrons. Relevant publications are S. Loibl, F. R. Manby, and M. Schütz, //Density fitted, local Hartree-Fock treatment of NMR chemical shifts using London atomic orbitals//, [[https:// | ||
+ | |||
+ | ==== SAPT(CCSD) ==== | ||
+ | |||
+ | Symmetry-adapted perturbation theory of intermolecular interactions with monomers described in the CCSD level. | ||
+ | |||
+ | ==== Improved SCF algorithms for high-spin open-shell systems ==== | ||
+ | |||
+ | For open-shell systems, RHF and RKS now use a two-step diagonalization process by default: Here the beta orbitals are found by a second diagonalization in the subspace of occupied alpha orbitals. This process usually leads to more stable convergence in difficult cases, compared to the standard diagonalization of a single open-shell Fock matrix (the latter behavior is recovered by {rhf, | ||
+ | |||
+ | ==== FCIQMC: Stochastic Full CI ==== | ||
+ | |||
+ | The FCIQMC program exists through an interface to the '' | ||
+ | |||
+ | ==== Ab Initio Multiple Spawning Dynamics ==== | ||
+ | |||
+ | The AIMS module implements the Ab Initio Multiple Spawning method to perform dynamics calculations on multiple electronic states. It can also be used quite generally for first principles molecular dynamics on a single electronic surface, provided that nuclear gradients are available. Currently, non-adiabatic dynamics is limited to CASSCF wavefunctions; | ||
+ | |||
+ | ==== Updated def2 basis sets ==== | ||
+ | |||
+ | The partially augmented Turbomole basis sets def2-SVPD, def2-TZVPD, and def2-QZVPPD (Rappoport, Furche: [[https:// | ||
+ | |||
+ | ==== Parallel builds merged ==== | ||
+ | |||
+ | The MPP and MPPX builds of Molpro have been merged and the decision to run in MPP or MPPX mode made a run-time option. To build parallel Molpro the '' | ||
+ | |||
+ | ==== Auto-build options for parallel configuration ==== | ||
+ | |||
+ | New options for configuring parallel Molpro to run on a single node or workstation have been implemented. These options (see manual) are prefixed with '' | ||
+ | |||
+ | ===== New features of MOLPRO2010.1 ===== | ||
+ | |||
+ | The functionality is essentially the same as in 2009.1, but many bug fixes and small improvements have been added. Please note the following major changes, in particular of the default RI basis sets in explicitly correlated methods as described below. | ||
+ | |||
+ | ==== AIC density fitting integral program ==== | ||
+ | |||
+ | A faster integral program for density fitting, written by Gerald Knizia, has been added. In particular this speeds up the integral evaluation in F12 calculations by up to a factor of about 10 (depending on the basis set). This program is now used by default, but can be disabled by setting | ||
+ | |||
+ | '' | ||
+ | |||
+ | in the beginning of the input. | ||
+ | |||
+ | ==== Pair specific geminal exponents in explicitly correlated methods ==== | ||
+ | |||
+ | Different exponents for the Slater-type geminals can be used for valence-valence, | ||
+ | |||
+ | ==== Change of defaults in explicitly correlated methods ==== | ||
+ | |||
+ | For explicitly correlated F12 calculations that use the VnZ-F12 orbital basis sets (OBS), it is now the default to use the corresponding VnZ-F12/ | ||
+ | |||
+ | '' | ||
+ | |||
+ | For compatibility reasons, it is still the default to use the JKFIT sets as RI basis for the AVnZ orbital basis sets. In order to use the corresponding OPTRI sets (where available) please specify option RI_BASIS=OPTRI. | ||
+ | |||
+ | ==== New basis sets in the Molpro library ==== | ||
+ | |||
+ | A number of new basis sets have been added to the Molpro library since version 2009.1. The references for these sets can be found in the headers of the respective libmol files. | ||
+ | |||
+ | * **Li, Be, Na, Mg:** a) New official versions of the correlation consistent basis sets for these elements have been added, both non-relativistic and those contracted for Douglas-Kroll relativistic calculations. Specifically these are: cc-pVnZ (n=D-5) cc-pwCVnZ (n=D-5) aug-cc-pVnZ (n=D-5) aug-cc-pwCVnZ (n=D-5) and the above with a -DK extension. The older cc-pVnZ basis sets for these elements can still be accessed via the keywords vdz-old, etc. b) New basis sets, including RI and MP2 auxiliary sets, have been added for F12 explicit correlation calculations: | ||
+ | * **Cu-Zn, Y-Cd, Hf-Hg:** a) While the aug-cc-pVnZ-PP (n=D-5) and cc-pwCVnZ-PP (n=D-5) sets were already available, the combination aug-cc-pwCVnZ-PP was not yet defined. These have now been added for these elements. b) Triple-zeta DK sets have been included now for all of these elements. Unless otherwise noted, these were optimized for 2nd-order DKH. In the cases of Hf-Hg, sets contracted for 3rd-order DKH are also now included: cc-pVTZ-DK cc-pwCVTZ-DK aug-cc-pVTZ-DK aug-cc-pwCVTZ-DK and the above with -DK replaced by -DK3 for DKH3 calculations in the case of Hf-Hg. | ||
+ | * **H-He, B-Ne, Al-Ar, Ga-Kr:** a) A variety of DK contracted basis sets have been added for these elements: aug-cc-pVnZ-DK (n=D-5) cc-pCVnZ-DK (n=D-5) cc-pwCVnZ-DK (n=D-5) aug-cc-pCVnZ-DK (n=D-5) aug-cc-pwCVnZ-DK (n=D-5) b) Official cc-pCV6Z and aug-cc-pCV6Z are now also available for Al-Ar c) For explicitly correlated calculations, | ||
+ | * **Turbomole def2 basis sets:** The complete Turbomole def2 basis set family has been added to the Molpro basis library (for all elements H to Rn, except Lanthanides). The def2-orbital basis sets can now be accessed as SV(P), SVP, TZVP, TZVPP, QZVP and QZVPP. In this nomenclature SVP, TZVPP, and QZVPP correspond to valence double-zeta (VDZ), valence triple-zeta (VTZ) and valence quadruple-zeta (VQZ) basis sets, respectively. Auxiliary density fitting basis sets for all elements are available as well (e.g., TZVPP/JFIT, TZVPP/ | ||
+ | |||
+ | ==== Improved support for MPI implementation of parallelism ==== | ||
+ | |||
+ | The //ppidd// harness that manages interprocess communication has been improved. The performance of the implementation based on pure MPI, as an alternative to use of the Global Arrays toolkit, is considerably improved, through the use of dedicated helper processes that service one-sided remote memory accesses. | ||
+ | |||
+ | ==== Change of the order of states and the defaults for computing the Davidson correction in multi-state MRCI ==== | ||
+ | |||
+ | The previous way to compute the Davidson correction in multi-state MRCI could lead to non-continuous cluster corrected energies. This is now avoided by ordering the MRCI eigenstates according to increasing energy (previously they were ordered according to maximum overlap with the reference wavefunctions). Furthermore, | ||
+ | |||
+ | ==== IPEA shift for CASPT2 ==== | ||
+ | |||
+ | A variant of the IPEA shift of G. Ghigo, B. O. Roos, and P.A. Malmqvist, [[https:// | ||
+ | |||
+ | ==== Karton-Martin extrapolation of HF energies ==== | ||
+ | |||
+ | The two-point formula for extrapolating the HF reference energy, as proposed by A. Karton and J. M. L. Martin, Theor. Chem. Acc. **115**, 330 (2006) has been added: $E_{\rm HF, | ||
+ | |||
+ | ===== New features of MOLPRO2009.1 ===== | ||
+ | |||
+ | ==== Basis set updates ==== | ||
+ | |||
+ | Correlation consistent basis sets for Li, Be, Na, and Mg have been updated to their official versions as reported in Prascher et al., Theor. Chem. Acc. (2010). These now also include core-valence, | ||
+ | |||
+ | ==== Explicitly correlated calculations ==== | ||
+ | |||
+ | Due to new findings, the default behavior of the F12 programs was changed in the following points: | ||
+ | |||
+ | - For open-shell systems the default wave function ansatz for was modified. This affects RMP2-F12 and open-shell CCSD-F12 calculations. The new default generally improves open-shell treatments and leads to more consistent behavior. The previous behavior can be restored by '' | ||
+ | - The procedure for the construction of complementary auxiliary basis sets (CABS) and the thresholds were changed. This affects all non-local F12 calculations. The previous behavior can be restored by '' | ||
+ | - In numeric frequency calculations, | ||
+ | - Pair energies for the explicitly correlated methods can be printed using '' | ||
+ | |||
+ | ==== Improvements to the Hartree-Fock program ==== | ||
+ | |||
+ | The atomic density guess in Hartree-Fock has been improved and extended. Guess basis sets are now available for most atoms and for all pseudopotentials. Most pseudopotentials have been linked to the appropriate basis sets, so that it is sufficient to specify, e.g. | ||
+ | |||
+ | < | ||
+ | basis=vtz-pp | ||
+ | </ | ||
+ | which will select the correlation consistent triple zeta basis sets and the associated (small core) pseudopotential. Similarly, it is mostly sufficient to specify the basis set for other pseudopotential/ | ||
+ | |||
+ | If the wavefunction symmetry is not given in the Hartree-Fock input and not known from a previous calculation, | ||
+ | |||
+ | < | ||
+ | geometry={n}; | ||
+ | {hf; | ||
+ | </ | ||
+ | automatically finds that the wavefunction symmetry is 8. | ||
+ | |||
+ | ==== Changes to geometry input ==== | ||
+ | |||
+ | - Rationalisation of options for molecular geometry. It is now illegal to specify symmetry and orientation options (eg x; | ||
+ | - Simplification of geometry input. The program now detects automatically whether the geometry is specified as a Z-matrix, or using cartesian coordinates, | ||
+ | |||
+ | ==== MPI-2 parallel implementation ==== | ||
+ | |||
+ | The program now can be built from the source files with the Global Arrays toolkit or the MPI-2 library for parallel execution. | ||
+ | |||
+ | ===== New features of MOLPRO2008.1 ===== | ||
+ | |||
+ | The new features of Molpro version 2008.1 include the following. | ||
+ | |||
+ | - Efficient closed-shell and open-shell MP2-F12 and CCSD(T)-F12 methods which dramatically improve the basis set convergence, | ||
+ | - Natural bond order (NBO) and natural population analysis (NPA) as described in [[https:// | ||
+ | - Correlation regions within a localized molecular orbital approach as described in [[https:// | ||
+ | - Automated calculation of anharmonic vibrational frequencies and zero-point energies using VCI methods as described in [[https:// | ||
+ | - Coupling of DFT and coupled cluster methods as described in [[https:// | ||
+ | - Enhanced connections to other programs, including [[https:// | ||
+ | - Support for latest operating systems and compilers, including Mac OS X. | ||
+ | |||
+ | ===== New features of MOLPRO2006.1 ===== | ||
+ | |||
+ | Features and enhancements in Molpro version 2006.1 most notably included efficient density fitting methods, explicitly correlated methods, local coupled cluster methods, and several new gradient programs: following: | ||
+ | |||
+ | - More consistent input language and input pre-checking. | ||
+ | - More flexible basis input, allowing to handle multiple basis sets | ||
+ | - New more efficient density functional implementation, | ||
+ | - Low-order scaling local coupled cluster methods with perturbative treatment of triples excitations (LCCSD(T) and variants like LQCISD(T)) | ||
+ | - Efficient density fitting (DF) programs for Hartree-Fock (DF-HF), Density functional Kohn-Sham theory (DF-KS), Second-order Møller-Plesset perturbation theory (DF-MP2), as well as for all local methods (DF-LMP2, DF-LMP4, DF-LQCISD(T), | ||
+ | - Analytical QCISD(T) gradients | ||
+ | - Analytical MRPT2 (CASPT2) and MS-CASPT2 gradients, using state averaged MCSCF reference functions | ||
+ | - Analytical DF-HF, DF-KS, DF-LMP2, and DF-SCS-LMP2 gradients | ||
+ | - Explicitly correlated methods with density fitting: DF-MP2-R12/ | ||
+ | - Coupling of multi-reference perturbation theory and configuration interaction (CIPT2) | ||
+ | - DFT-SAPT | ||
+ | - Transition moments and transition Hamiltonian between CASSCF and MRCI wavefunctions with different orbitals. | ||
+ | - A new spin-orbit integral program for generally contracted basis sets. | ||
+ | - Douglas-Kroll-Hess Hamiltonian up to arbitrary order. | ||
+ | - Improved procedures for geometry optimization and numerical Hessian calculations, | ||
+ | - Improved facilities to treat large lattices of point charges for QM/MM calculations, | ||
+ | - An interface to the MRCC program of M. Kallay, allowing coupled-cluster calculations with arbitrary excitation level. | ||
+ | - Automatic // | ||
+ | - Additional parallel codes, e.g. DF-HF, DF-KS, DF-LCCSD(T) (partly, including triples). | ||
+ | - Additional output formats for tables ( [[http:// | ||
+ | |||
+ | ===== New features of MOLPRO2002.6 ===== | ||
+ | |||
+ | Relative to version 2002.1, there are the following changes and additions: | ||
+ | |||
+ | - Support for IA-64 Linux systems (HP and NEC) and HP-UX 11.22 for IA-64 (Itanium2). | ||
+ | - Support for NEC-SX systems. | ||
+ | - Support for IBM-power4 systems. | ||
+ | - Modified handling of Molpro system variables. The '' | ||
+ | - The total charge of the molecule can be specified in a variable '' | ||
+ | - Improved numerical geometry optimization using symmetrical displacement coordinates (see sections [[energy gradients# | ||
+ | - Improved numerical frequency calculations using the symmetry ('' | ||
+ | |||
+ | ===== New features of MOLPRO2002 ===== | ||
+ | |||
+ | Relative to version 2000.1, there are the following principal changes and additions: | ||
+ | |||
+ | - Modules direct and local are now included in the base version. This means that integral-direct procedures as described in\\ | ||
+ | M. Schütz, R. Lindh, and H.-J. Werner, [[https:// | ||
+ | linear-scaling local MP2, as described in\\ | ||
+ | G. Hetzer, P. Pulay, and H.-J. Werner, [[https:// | ||
+ | M. Schütz, G. Hetzer, and H.-J. Werner, [[https:// | ||
+ | G. Hetzer, M. Schütz, H. Stoll, and H.-J. Werner, [[https:// | ||
+ | as well as LMP2 gradients as described in\\ | ||
+ | A. El Azhary, G. Rauhut, P. Pulay, and H.-J. Werner, [[https:// | ||
+ | are now available without special license. The linear scaling LCCSD(T) methods as described in\\ | ||
+ | M. Schütz and H.-J. Werner, [[https:// | ||
+ | M. Schütz and H.-J. Werner, [[https:// | ||
+ | M. Schütz, [[https:// | ||
+ | will be made available at a later stage. | ||
+ | - QCISD gradients as described in [[https:// | ||
+ | - Additional and more flexible options for computing numerical gradients and performing geometry optimizations. | ||
+ | - A large number of additional density functionals have been added, together with support for the automated functional implementer described in Comp. Phys. Commun. **136** 310–318 (2001). | ||
+ | - Multipole moments of arbitrary order can be computed. | ||
+ | - Further modules have been parallelized, | ||
+ | - The basis set library has been extended. | ||
+ | - Some subtle changes in the basis set input: it is not possible any more that several one-line basis input cards with definitions for individual atoms follow each other. Each new basis card supercedes previous ones. Either all specifications must be given on //one// '' | ||
+ | - Pseudopotential energy calculations can now be performed with up to $i$-functions, | ||
+ | - Many internal changes have been made to make Molpro more modular and stable. Support has been added for recent operating systems on Compaq, HP, SGI, SUN, and Linux. The patching system has been improved. | ||
+ | |||
+ | ===== Features that were new in MOLPRO2000 ===== | ||
+ | |||
+ | Relative to version 98.1, there are the following principal changes and additions: | ||
+ | |||
+ | - There was a fundamental error in the derivation of the spin-restricted open-shell coupled-cluster equations in J. Chem. Phys. 99, 5129 (1993) that is also reflected in the RCCSD code in '' | ||
+ | - There was a programming error in the transformation of gradients from Cartesian to internal coordinates, | ||
+ | - Vibrational frequencies formerly by default used average atomic masses, rather than those of the most common isotopes, which is now the default behaviour. | ||
+ | - MCSCF second derivatives (author Riccardo Tarroni) added (preliminary version, only without symmetry). Frequency and geometry optimization programs are modified so that they can use the analytic Hessian. | ||
+ | - New internally contracted multi-reference second-order perturbation theory code (author Paolo Celani) through command '' | ||
+ | - EOM-CCSD for excited states (author Tatiana Korona). | ||
+ | - QCISD dipole moments as true analytical energy derivatives (author Guntram Rauhut). | ||
+ | - Linear scaling (CPU and memory) LMP2 as described by G. Hetzer, P. Pulay, and H.-J. Werner, [[https:// | ||
+ | M. Schütz, G. Hetzer, and H.-J. Werner, [[https:// | ||
+ | - Improved handling of basis and geometry records. 98.1 and 99.1 dump files can be restarted, but in case of problems with restarting old files, add '' | ||
+ | - Reorganization and generalization of basis input. Increased basis library. | ||
+ | - Counterpoise geometry optimizations. | ||
+ | - Improved running procedures for MPP machines. Parallel direct scf and scf gradients are working. These features are only available with the MPP module, which is not yet being distributed. | ||
+ | - Important bugfixes for DFT grids, CCSD with paging, finite field calculations without core orbitals, spin-orbit coupling. | ||
+ | - Many other internal changes. | ||
+ | |||
+ | As an additional service to the '' | ||
+ | |||
+ | In order to subscribe to the list, send mail to < | ||
+ | |||
+ | Messages can be sent to the list (< | ||
+ | |||
+ | ===== Facilities that were new in MOLPRO98 ===== | ||
+ | |||
+ | '' | ||
+ | |||
+ | All one-electron operators needed to compute expectation values and transition quantities are now stored in a single record. Operators for which expectation values are requested can be selected globally for all programs of a given run using the global '' | ||
+ | |||
+ | Due to the changed structure of dump and operator records, the utility program '' | ||
+ | |||
+ | In addition to these organizational changes, a number of new programs have been added. Analytic energy gradients can now be evaluated for MP2 and DFT wavefunctions, | ||
+ | |||
+ | An interface to the graphics program MOLDEN has been added, which allows to visualize molecular structures, orbitals, electron densities, or vibrations. | ||
+ | |||
+ | Integral-direct calculations, | ||
+ | |||
+ | //Local// electron correlation methods have been further improved. In combination with the integral-direct modules, which implement efficient prescreening techniques, the scaling of the computational cost with molecular size is dramatically reduced, approaching now quadratic or even linear scaling for MP2 and higher correlation methods. This makes possible to perform correlated calculations for much larger molecules than were previously feasible. However, since these methods are subject of active current research and still under intense development, | ||