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recent_changes [2021/06/02 07:56]
werner [Recent changes]
recent_changes [2022/01/27 08:18]
werner [MCSCF/CASSCF spin-orbit calculations (HLSMAT)]
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 ====== Recent changes ====== ====== Recent changes ======
-Several well parallelized new methods have been implemented in Molpro2020/21. 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 MOLPRO2022.1 ===== 
 +==== 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. 
 ===== New features of MOLPRO2021.2 ===== ===== New features of MOLPRO2021.2 =====