# Differences

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 recent_changes [2021/06/02 07:57] – [Recent changes] werner recent_changes [2022/08/16 14:15] (current) – external edit 127.0.0.1 Line 2: Line 2: Several well parallelized new methods have been implemented in Molpro. A review of recent developments in Molpro can be found in [[https://doi.org/10.1063/5.0005081|J. Chem. Phys.]] 152, 144107 (2020). Several well parallelized new methods have been implemented in Molpro. A review of recent developments in Molpro can be found in [[https://doi.org/10.1063/5.0005081|J. Chem. Phys.]] 152, 144107 (2020). + + 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 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#options_for_f12_calculations|F12 projector option]] is added to the PNO-LCCSD program. + Different F12 geminal exponents for valence, core-valence, and core-core pairs are now supported. + See [[explicitly_correlated_methods#options|GEM_BETA]] for details. + + 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 2.0.0 ==== + + 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 + '' $HOME/.molpro/token '' . Alternatively (useful for group licences), on Linux, it may be installed in '' /usr/share/gmolpro/molpro/lib/.token '' , and on Mac in '' /Applications/gmolpro.app/Contents/Resources/molpro/lib/.token '' + + ===== 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://doi.org/10.1063/5.0079853 is available for closed-shell systems. + + ==== CORE directive ==== + With ''CORE,MIXED'' correlation of the 2s and 2p electrons for the second-row elements Al - Ar is now excluded. + Global ''CORE'' command is now supported. + See [[general_program_structure#defining_orbital_subspaces_occ_closed_core_frozen | defining orbital subspaces]] for details. + The old behaviour, where these electrons were correlated, can be recovered using ''CORE,MIXED_OLD''. + + ==== SCF program === + * Quadratic optimization or mixed quadratic/first-order SO-SCI optimization is available for closed-shell and open-shell RHF by using ''{RHF,SO;...}'' or ''{RHF,SO-SCI;...}''. + * The CAHF optimization with the quadratic or the SO-SCI optimization is implemented into the CAHF program, and it can be called by ''{CAHF,SO;...}'' or ''{CAHF,SO-SCI;...}''. + * A new variant of the SO-SCI optimization is available for the RHF case. It optimizes all AVAS orbitals quadratically and is called by ''{RHF,SO-SCI-ACTIVE}''. + + The ''SO-SCI'' option significantly improves convergence and is recommended in difficult cases. The cost may even be lower than for standard ROHF or CAHF calculations, since the number of iterations is reduced. Furthermore, the probability of convergence to local minima or saddle points is much reduced. + + See section [[the_scf_program#options_for_the_so-sci_optimization|options for the SO-SCI optimization]] for more details and options. + ==== MCSCF/CASSCF ==== + * The entire export of CI vectors to subsequent Molpro programs has been rewritten. CI vectors can be exported via ''SAVE,CIREC=record'' or ''NATORB,orbrecord,CIREC=record''; more details can be found [[the mcscf program multi#saving the ci vectors|here]]. All exported CI vectors are stored in the CSFs basis. Determinants are automatically transformed into the CSFs basis, which also allows an export with state-averaging over different spins. **Warning**: MULTI based CI records from earlier Molpro versions are not compatible anymore, and the wfu file has to be recalculated with Molpro 2022! + * ''{MULTI,CASCI;...}'' can now be simply called by ''{CASCI;...}'', and the input orbitals are not transformed after the CASCI optimization (also for dont,orbital). + * 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 ''SAVE,CIREC=record'' can now be used in the MRCI and CASPT2 programs as reference vectors using option ''CIREC=record''. + + ==== MCSCF/CASSCF spin-orbit calculations (HLSMAT) ==== + + 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 + + ''HLSMAT,type, record1, record2, record3, …'' + + where ''record1'', ''record2'' etc are records saved with MULTI or MRCI. The new program is used if ''type'' is ''ECPLS'' and if no external excitations are present (so either MCSCF/CASSCF wavefunctions or MRCI ones with NOEXC). + + For more details see section [[spin-orbit-coupling#calculation and diagonalization of the entire SO-matrix]]. + ==== PNO-LCCSD ==== + + The IBO localization convergence threshold has been tightened from$10^{-8}$to$10^{-9}$. + The PAO redundancy threshold ''THRLOC'' has been tightened from$10^{-6}$to$10^{-7}$. + + 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: + + ''local, thrpip=1.d-8, thrloc=1.d-6, loc_method_core=ibo'' + + The corresponding new options are + + ''local, thrpip=1.d-9, thrloc=1.d-7, loc_method_core=ibo(ao)'' + + 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, frequency calculations, or even different molecules within one xml file. Start from the brown window, open the orbital window, and then select and load an orbital set. A corresponding optimisation or vibrational modes may now be displayed. + + When creating an input in guided mode, more properties may be selected by buttons. + ===== New features of MOLPRO2021.2 ===== ===== New features of MOLPRO2021.2 =====