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recent_changes [2026/01/27 16:14] – dollrecent_changes [2026/05/14 14:32] (current) – [Douglas-Kroll-Hess calculations] werner
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 +===== New features of MOLPRO2026.1 =====
 +
 +==== Fitting basis sets ====
 +
 +If density fitting (DF) basis sets or resolution of the identity (RI) basis sets for F12 calculations are defined in a basis set block, and the set names correspond to the contexts, these sets are now used automatically in the programs where needed. This concerns sets named JFIT, JKFIT, MP2FIT, CCSDFIT,  OPTRI, and CABS.
 +
 +
 +==== Basis set library ====
 +
 +For the elements Ga-Kr, cc-pVDZ-JKFIT and aug-cc-pVDZ-JKFIT have been removed.
 +cc-pVTZ-JKFIT and aug-cc-pVTZ-JKFIT are now used instead, when cc-pVDZ and aug-cc-pVDZ orbital basis sets are chosen and JK fitting is done.
 +
 +def2-SVP-JKFIT basis sets are now the same ones as in Turbomole. In earlier Molpro versions, the highest angular momentum had been omitted, but this could lead to large errors. def2-ASVP-JKFIT (def2-SVP-JKFIT as in Turbomole plus a diffuse exponent for each angular momentum) has been adjusted analogously.
 +
 +Some basis sets for the atomic density guess in HF/KS have been improved.
 +==== Douglas-Kroll-Hess calculations ====
 +
 +DK is now activated automatically if a -DK, -DK3, or -X2C basis set is given. In this case the same basis type must be used for all atoms, otherwise an error occurs. By default, DKHO=2 is set for -DK basis sets, DKHO=3 for -DK3 basis sets, and DKHO=101 for -X2C basis sets. These settings can be overwritten by setting variable DKHO, which then has preference. The DK Hamiltonian can be disabled by setting variable DKOLL=0.
 +==== Intermolecular interactions ====
 +
 +The input for the monomers in the INTERACT program has been generalised. It is now possible to define the monomers manually.
 ===== New features of MOLPRO2025.4 ===== ===== New features of MOLPRO2025.4 =====
  
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 Frequently asked question: 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?+Q: An optimisation (or frequency calculation) is performed, but the icon to open the optimisation (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). 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).
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 ==== CORE directive ==== ==== CORE directive ====
-With ''CORE,MIXED'' correlation of the 2s and 2p electrons for the second-row elements Al - Ar is now excluded.+With ''CORE,MIXED'' correlation of the 2s and 2p electrons for the third-row elements Al - Ar is now excluded.
 Global ''CORE'' command is now supported. Global ''CORE'' command is now supported.
 See [[general_program_structure#defining_orbital_subspaces_occ_closed_core_frozen | defining orbital subspaces]] for details. See [[general_program_structure#defining_orbital_subspaces_occ_closed_core_frozen | defining orbital subspaces]] for details.
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 ==== Time-dependent density-functional (TDDFT) program ==== ==== 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 $C_6$, $C_8$  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,quadrupole,otocpole) polarisabilities.+and $C_{10}$ dispersion coefficients can be computed along with the calculation of frequency dependent (dipole,quadrupole,octopole) polarisabilities.
  
  
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 ==== Electronic - vibrational spectra ==== ==== 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. +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 implementations are provided, the contracted invariant Krylov subspace (CIKS) approach and a Raman wavefunction (RWF) formalism. 
  
 ===== New features of MOLPRO2019.2 ===== ===== New features of MOLPRO2019.2 =====
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 ==== Projection-based wavefunction-in-DFT embedding ==== ==== Projection-based wavefunction-in-DFT embedding ====
  
-The WF-in-DFT impementation in Molpro [F. R. Manby et al., [[https://dx.doi.org/10.1021/ct300544e|J. Chem. Theory Comput.]] **8**, 2564 (2012)] permits embedding of almost any ground-state wavefunction method in Molpro in an environment described by DFT.+The WF-in-DFT implementation in Molpro [F. R. Manby et al., [[https://dx.doi.org/10.1021/ct300544e|J. Chem. Theory Comput.]] **8**, 2564 (2012)] permits embedding of almost any ground-state wavefunction method in Molpro in an environment described by DFT.
  
 ==== Intrinsic bond-orbital analysis and orbital localization (IBO). ==== ==== Intrinsic bond-orbital analysis and orbital localization (IBO). ====
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 ==== Anharmonic Franck-Condon factors: FCON ==== ==== 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 ''SURFTRANS'' [P. Meier and G. Rauhut, J. Chem. Phys. (2015)].+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 allows for the accurate calculation of photoelectron spectra (absorption and fluorescence) relies on the newly developed transformation program ''SURFTRANS'' [P. Meier and G. Rauhut, J. Chem. Phys. (2015)].
  
 ==== Transformation of multi-dimensional potential energy surfaces: PESTRANS ==== ==== Transformation of multi-dimensional potential energy surfaces: PESTRANS ====
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 ==== Local coupled-cluster methods with orbital-specific virtual orbitals: OSV-LCCSD(T) ==== ==== 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//, [[https://dx.doi.org/10.1063/1.3696963|J. Chem. Phys.]] **136**, 144105 (2012). The main advantage of this method is that the accuracy of the domain approximation can be controlled by a single parameter. Further developments that also use pair-natural orbitals (PNOs) as descibed in C. Krause and H.-J. Werner, //Perspective: Comparison of explicitly correlated local coupled-cluster methods with various choices of virtual orbitals//, [[https://dx.doi.org/10.1039/C2CP40231A|Phys. Chem. Chem. Phys.]] **14**, 7591-7604 (2012) are in progress. A preliminary parallel PNO-LMP2-F12 method is already available.+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//, [[https://dx.doi.org/10.1063/1.3696963|J. Chem. Phys.]] **136**, 144105 (2012). The main advantage of this method is that the accuracy of the domain approximation can be controlled by a single parameter. Further developments that also use pair-natural orbitals (PNOs) as described in C. Krause and H.-J. Werner, //Perspective: Comparison of explicitly correlated local coupled-cluster methods with various choices of virtual orbitals//, [[https://dx.doi.org/10.1039/C2CP40231A|Phys. Chem. Chem. Phys.]] **14**, 7591-7604 (2012) are in progress. A preliminary parallel PNO-LMP2-F12 method is already available.
  
 ==== Explicitly correlated local MP2 and CC methods: DF-LMP2-F12, DF-LCCSD(T)-F12 ==== ==== Explicitly correlated local MP2 and CC methods: DF-LMP2-F12, DF-LCCSD(T)-F12 ====
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 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/basis set combinations. 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/basis set combinations.
  
-If the wavefunction symmetry is not given in the Hartree-Fock input and not known from a previous calculation, the HF program attempts to determine it automatically from the aufbau pricniple (previously, symmetry 1 was assumed in all cases). For example,+If the wavefunction symmetry is not given in the Hartree-Fock input and not known from a previous calculation, the HF program attempts to determine it automatically from the aufbau principle (previously, symmetry 1 was assumed in all cases). For example,
  
 <code> <code>
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 ''Molpro98'' has the full functionality of ''Molpro96'', but in order to make the code more modular and easier to use and maintain, a number of structural changes have been made. In particular, the number of different records has been significantly reduced. The information for a given wavefunction type, like orbitals, density matrices, fock matrices, occupation numbers and other information, is now stored in a single dump record. Even different orbital types, e.g., canonical, natural, or localized orbitals, are stored in the same record, and the user can subsequently access individual sets by keywords on the ''ORBITAL'' directive. New facilities allow the use of starting orbitals computed with different basis sets and/or different symmetries for SCF or MCSCF calculations. The default starting guess for SCF calculations has been much improved, which is most useful in calculations for large molecules. The use of special procedures for computing non-adiabatic couplings or diabatization of orbitals has been significantly simplified. We hope that these changes make the program easier to use and reduce the probability of input errors. However, in order to use the new facilities efficiently, even experienced Molpro users should read the sections //RECORDS// and //SELECTING ORBITALS AND DENSITY MATRICES// in the manual. It is likely that standard ''Molpro96'' inputs still work, but changes may be required in more special cases involving particular records for orbitals, density matrices, or operators. ''Molpro98'' has the full functionality of ''Molpro96'', but in order to make the code more modular and easier to use and maintain, a number of structural changes have been made. In particular, the number of different records has been significantly reduced. The information for a given wavefunction type, like orbitals, density matrices, fock matrices, occupation numbers and other information, is now stored in a single dump record. Even different orbital types, e.g., canonical, natural, or localized orbitals, are stored in the same record, and the user can subsequently access individual sets by keywords on the ''ORBITAL'' directive. New facilities allow the use of starting orbitals computed with different basis sets and/or different symmetries for SCF or MCSCF calculations. The default starting guess for SCF calculations has been much improved, which is most useful in calculations for large molecules. The use of special procedures for computing non-adiabatic couplings or diabatization of orbitals has been significantly simplified. We hope that these changes make the program easier to use and reduce the probability of input errors. However, in order to use the new facilities efficiently, even experienced Molpro users should read the sections //RECORDS// and //SELECTING ORBITALS AND DENSITY MATRICES// in the manual. It is likely that standard ''Molpro96'' inputs still work, but changes may be required in more special cases involving particular records for orbitals, density matrices, or operators.
  
-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 ''GEXPEC'' directive, or for a specific program using the ''EXPEC'' directive. All operators are computed automatically when needed, and the user does not have to give input for this any more. See section //ONE-ELECTRON OPERATORES AND EXPECTATION VALUES// of the manual for details.+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 ''GEXPEC'' directive, or for a specific program using the ''EXPEC'' directive. All operators are computed automatically when needed, and the user does not have to give input for this any more. See section //ONE-ELECTRON OPERATORS AND EXPECTATION VALUES// of the manual for details.
  
 Due to the changed structure of dump and operator records, the utility program ''MATROP'' has a new input syntax. ''Molpro96'' inputs for ''MATROP'' do not work any more. Due to the changed structure of dump and operator records, the utility program ''MATROP'' has a new input syntax. ''Molpro96'' inputs for ''MATROP'' do not work any more.