MOLPRO2022 重磅来袭

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.

(1) 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 defining orbital subspaces for details. The old behaviour, where these electrons were correlated, can be recovered using CORE,MIXED_OLD.

(2) 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}.

(3) 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 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.

(4) 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/CASSCFspin-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 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 arelocal,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 MOLPRO2021.1Hartree-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 “old”, e.g. hf,old.

• Optionally, the hybrid second-order/super-ci method(so-sci)can be used in difficult cases(hf,so-sci). In open-shell cases this converges more robustly than the standard ROHF procedure.

MCSCF/ CASSCF<<<<

• Generalized dynamical weighting, in which the dynamical weighting can be restricted to certain states.

• CAHF optimization with the multi program for the state-averaged optimization including all irreducible representations and spin manifolds. Convergence is more robust than in the equivalent Hartree-Fock optimization, especially for multiple CAHF shells.

• RHF export for multi orbitals.

• State restrictions for one-electron properties.

• Export of the raw orbitals used in the MCSCF optimization. Input orbitals stay untouched in combination with the command dont,orbital.

Analytical energy gradients

Analytical energy gradients are now available for RASPT2(using rs2).

(1)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)

(2)Miscellaneous

• All fundamental constants used in the program have been updated to the most recent CODATA 2018 standard https://physics.nist.gov/cuu/Constants

• 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).

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