Detailed change log

Changes ORCA 6.0.1

Fixed

DFT

  • Crash when XCFun functional was overwritten with LibXC.

  • Hessian fixed for DFT GGA, NoRI, RKS.

  • VV10 Hessian is blocked even if invoked with CALC_HESS=TRUE and similar.

  • Wrong orbitals for non-self-consistent DFT-NL calculations (wB97M-V, wB97X-V, B97M-V).

  • X_WR2SCAN:

    • Exchange can now be specified individually in the %method block.

    • Fixed crashes when second derivatives are requested.

    • TRAH is now disabled per default when using X_WR2SCAN.

    • If second derivatives are requested, will now automatically switch to numerical second derivatives.

    • Added appropriate warnings for the above changes.

  • Fixed PBEh-3c gCP parameters for Krypton and Lithium to be consistent with Grimme’s stand-alone.

  • gCP is now fixed (and extended) for r2SCAN-3c up to Z=103.

  • Remove restriction to COSX for wB97X-3c .

TD-DFT

  • Ground state gradient for TDDFT calculations with sgradlist was wrong.

  • DCORR 2/3 with DoSCS giving wrong results in parallel.

  • (D)-Correction not available for full TDDFT.

  • Fix for memory estimates for Hessian/TDDFT when running without COSX.

  • FollowIRoot was not supposed to do anything if the overlap was to small, was still updating.

  • Fixed interface to BHP22 solver in CIS.

MP2

  • Crash in conventional U-MP2.

  • Parallel crash in RI-MP2 density.

  • Crash in (RI-)MP2 gradient with SMD.

  • Crash in (RI-)MP2 density with PGC and RIJK.

  • MP2+CPCM gradient was wrong.

  • Crash in NearIR + B2PLYP.

  • Bug with MP2 gradient in property file.

MDCI

  • SemiCore was not applied correctly if ECP is present.

  • ECP-related crashes.

  • Fixed redundant integral generation for specific problems.

  • Restored old CITrafos to address reported performance issues.

  • Added missing 4th-order doubles term in (T) for RKS reference (already present in UKS-(T), RKS-DLPNO-(T), and UKS-DLPNO-(T) and zero for RHF/UHF reference).

  • UHF CIS/STEOM calculation with UseCISUpdate is set to false.

  • RHF STEOM: TD-DFT initial guess.

AutoCI

  • Fixed large stack allocation, e.g., in MRCC.

  • Fixed runtime behavior for !Moread Noiter (falsely reporting “not converged”).

  • Fixed !UseSym falsely aborting.

  • AutoCI gradients: abort at start of a calculation when RI is requested instead of after coupled cluster iterations.

CASSCF/NEVPT2/QD-NEVPT2

  • Issue running LR over SA-CASSCF solution.

  • Incorrect setting of gauge origin in CASSCF QDPT led to misleading output and in some cases complained about not being able to find densities for the origin evaluation.

  • Canonicalize the inactive and virtual spaces of AVAS guesses, to avoid spurious warnings about core orbitals in the following CASSCF calculation.

  • AVAS: fixed wrong number of occupied orbitals in case no occupied orbitals should have been selected.

  • TRAH-CASSCF: compute generalized Fock matrix which is needed for the CASSCF nuclear gradient.

  • Fixed redundant generation of coupling coefficients in the CI guess.

  • Fixed ABS/CD spectra in calculation with !UseSym and QD-NEVPT2: The wrong densities were picked for the CASSCF transition moments.

  • Fixed ABS/CD when the NEVPT/QD-NEVPT2 ground state differs from CASSCF. Respecitve transition were missing.

  • Fixed MCD spectra not using transition densities from QD-NEVPT2 for the flag DoFullSemiclassical=true.

  • Updated manual: Reported D4TPre are updated to the new default value 1e-12. ORCA 5 used D4TPre=1e-10.

  • Fixed closed-shell case, e.g. CAS(6,3), crashing in NEVPT2.

  • Fixed NEVPT2/FIC-NEVPT2 wrong energies or crashing for the Vija class to wrong addressing.

  • Fixed ICE densities not stored in density container.

ANISO

  • Fixed T and L matrices passed to the single-aniso.

  • Fixed wrong number of non-relativistic states passed to single-aniso.

QDPT

  • Corrected QDPT transition density for excitations beyond “none”.

  • Information added to QDPT AMatrix.

  • Issues in QDPT properties in orca_lft have been addressed.

QM/MM

  • Speed issue for QMMM optimizations.

  • Crystal-QMMM and compound crashed.

  • Removed leftover files from QMMM-IRC amd QMMM-NEB.

Relativity

  • Crash for F12 + X2C/ZORA/DKH.

  • Unnecessary abort in AutoCI gradients with X2C/DKH/ZORA.

  • Disabled X2C+GIAO+FiniteNuc (not yet implemented).

  • 2nd-order PC correction to DKH gDSO now skipped when fpFWtrafo==false due to numerical instability.

Solvation

  • Disabled analytical gradient and Hessian for XTB calculations requesting CPCMX (not implemented).

  • FINAL SINGLE POINT ENERGY for calculations requesting CPCMX was wrong.

  • Crash for calculations requesting Freq + CPCM + dummy atoms.

  • Crash for QM/QM2 calculations with CPCM requesting excited states.

  • Crash for multiple XYZ File Scans for DRACO.

  • Crash with CPCM + NoIter + Pal + open-shell.

  • Fix for GC and CPCM.

Optimization

  • Multi-XYZ optimization crash.

  • Random possible break when using GFN-xTB Hessian.

  • Random crashes for RECALC_HESS=TRUE.

  • COPT was saving wrong Cartesian Hessian under certain conditions, would break.

  • Maximum number of angles that can be included is fixed + better error message.

  • Analytic Hessian as initial Hessian option crashed with IRC.

  • Crash in NEB-TS with subsequent Hessian, caused by change of number of parallel processes for NEB (max 32).

  • NEB parallelization (will - again - automatically start in parallel, if enough processes are available).

GOAT

  • GOAT/DOCKER/SOLVATOR now running on Windows.

  • WorkerRandomStart fixed and working as intended.

  • -REACT and -EXPLORE were (by mistake) not included sqrt(NFrag) to number of opts.

  • Missing timings for GOAT.

DOCKER

  • Abort if all final optimizations fail, was ending normally.

  • Do not switch to COPT if constraints are given.

Stability analysis

  • Stability analysis + closed-shell systems + post-processing (Hirshfeld, NBO, …).

  • SkipSecondSTAB was still checking for energy differences between steps. Now will move on regardless.

orca_2json

  • Exported relativistic integrals were wrong in, HMO and angular momentum were missing.

  • Choice of origin corrected.

  • Empty [] and [""] are no longer crashing but disabling the options.

  • Invalid property JSON syntax in the following cases:

    • multiple geometries (e.g. optimizations);

    • some jobs with multiple properties of the same kind;

    • CIPSI energies;

    • MDCI EOM energies;

    • XTB jobs;

    • energy extrapolation.

orca_mapspc

  • XAS/XES broadening functions satisfy FWHM.

  • Adjusted .stk files normalization to report band integrals.

Compound

  • MORead with same type and number of atoms but different arrangement.

  • Bugs in statistical functions.

Miscellaneous

  • SOMF(1X) parallel bug in semi-numeric Coulomb.

  • Dummy/ghost atoms lead to crash in Hessian (partial fix).

  • Fixed bug of Fermi smearing calculations of two-electron systems.

  • Hangup in leanscf_aftermath when using F12 and ECPs.

  • Issues in RIXSSOC, XESSOC spectra in ROCIS have been addressed.

  • Issues in computing RI-SSC Integrals have been addressed. This property is now turned on in CASSCF, LFT and MRCI modules.

  • Fixed a crash in MD and L-OPT when the input file name was “orca”.

  • Default COSX algorithm is set to AUTO everywhere, as originally intended.

  • Disable frozen-core approximation when no frozen-core electrons are present.

  • orca_vib was not able to read hess file from AnFreq run.

  • For very small systems restart Hessian could crash.

  • Small deviations between the Guess CI Matrix and the Sigma Vector in GS-ROCIS.

  • DCD-CAS: Removed left-over files.

  • Uncontracted MRCI: Fixed partial general contraction calls in the MRCI integral transformation (crashed before).

  • Crash for geometry optimization followed by a vibrational frequency calculation with fixed point group Ci.

  • Removal of posix_memalign, due to glibc/kernel bug.

  • NBO communication fixed.

  • Fixes a crash in the integral transformation.

  • Crash in orca_vpot due to missing prescreening matrix.

Improvements

Output

  • Print all orbital energies for !PrintMOs and !LargePrint.

  • Removed redundant warning when using gCP for elements Z > 36 (Kr).

  • Added citations for wr2SCAN and DFT-D4 extension.

  • Better printing of the spin coupling situation of the states resulting from GS-ROCIS calculations.

  • Prepended a counter to irrep labels when printing vibrational frequencies.

orca_2json

  • Citations added to json output file.

  • Absolute path in basename possible.

orca_mapspc

  • Added support for VCD, XASSOCV and XESSOCV spectrum processing.

Symmetry

  • Ensured correctness of gradient cleanup, geometry optimizations with fixed point groups and calculations of vibrational frequencies (for point groups with real irreps using pure Hartree-Fock).

  • Ensured correctness of the petite-list algorithm for SCF energy and gradient.

Compound

  • Implemented automatic knowledge of basenames.

  • Added GOAT interface.

Miscellaneous

  • Added ASCII checker to input file.

  • Add the possibility to read multi-XYZ files with no ‘>’.

  • QDPT in CASSCF now uses the magnetic origin as defined in %eprnmr (if not set, defaults to CenterOfNucCharge for backwards compatibility).

  • Reduced disk usage and optimized performance for CASSCF (transition) densities in density container.

  • Keep topology in initial IDPP path generation.

  • Add CIS Gradient in property file.

Changes ORCA 6.0.0

SCF and Infrastructure

  • Significant improvements to the SOSCF solver to make it more robust, preventing huge steps that break the SCF. Overall improvements on the DIIS solvers.

  • Due to the SCF updates, the AutoTRAH is now not so often needed and will start now only from above 50 cycles (AutoTRAHIter).

  • Improvements to the memory handling of TD-DFT, CP-SCF and the Hessian

Basis sets

  • def-TZVP and ma-def-TZVP pseudo-potential basis sets for the actinides (Z = 89, Ac - 103, Lr)

  • Lehtola’s hydrogenic gaussian basis set family (HGBS) including polarized (HGBSP) and augmented (AHGBS, AHGBSP) variants for all elements up to Oganesson (Z = 118)

  • def2-SVPD, def2-TZVPD, def2-TZVPPD, def2-QZVPD, def2-QZVPPD basis sets for lanthanoids

  • vDZP Grimme’s double-zeta valence basis set

  • !MINIX now correctly activates the corresponding ECP

  • Added user-specified L-limit to AutoAux AutoAuxLLimit

  • Fixed segfault in dhf-ECP

  • Fix for DelECP in %coords

  • Added ReadFragBasis keywords read fragment-specific basis sets from a file

Solvation

  • New charge correction / compensation algorithm (corrected charges printed in an additional file)

  • C-PCM/B scheme for QM/MM calculations

  • DDCOSMO and CPCM/X available for XTB calculations and QM/MM calculations

  • Generalization of names within all solvation models (C-PCM/SMD/ALPB/DDCOSMO/CPCM-X)

  • New discretization scheme for the cavity (C-PCM) based on a constant number of charges per unit of area

DFT

  • Allow LibXC functional customization via external parameters

  • Simple input keywords added for some LibXC functionals

  • Added wB97M(2) functional parameters: must be used with wB97M-V orbitals in a two-step job (compound script available)

  • D4 for elements 87 (Fr) - 103 (Lr)

  • r2SCAN-3c extension to elements 87 (Fr) - 103 (Lr)

  • Simple input keyword for functionals with revised D4 parameters by Grimme (wB97X-D4rev, wB97M-D4rev)

  • New hybrid functionals: r2SCANh, r2SCAN0, r2SCAN50, wr2SCAN, wB97X-3c

  • New double-hybrid functionals: Pr2SCAN50, Pr2SCAN69, wPr2SCAN50, kPr2SCAN50

  • Simple input keywords for 2021 variants of revDSD-PBEP86-D4 and revDOD-PBEP86-D4

  • Bugfixes for LibXC combined *_xc_* functionals

  • Fixed crash for D4 + ghost atoms

Excited states

  • Analytical gradient for meta-GGA functionals

  • Small bugfix to spin-adapted triplets and NACMEs.

  • The FolllowIRoot for excited state optimization uses now a much more robust algorithm.

Relativity

  • Enabled NumGrad with relativistic methods

  • Second order DKH picture-change correction of contact density

  • Minor fixes in DKH picture-change corrections of magnetic properties

  • Picture change corrections are activated automatically

Multiscale

  • Reading PDB files for 10k+ atoms with HETATMs now possible

  • Enabled correct FlipSpin behavior with QMMM

  • More efficient MM Module

  • Implemented wall potential

Coupled cluster / DLPNO

  • Implemented energy ordering for PNO generation

  • Added semicore treatment for DLPNO

  • Enable DLPNO-CCSD(T) calculations to run DLPNO-CCSD unrelaxed densities

MP2

  • Corrected memory estimates and batching in response and gradient

  • Removed the slow and limited analytic (RI-)MP2 Hessian code

  • Removed non-default Gamma-in-core option for RI-MP2 response

  • Disabled single-precision calculations

  • Disabled SemiDirect option in AO-MP2

  • Enabled range-separated DHDFT gradients with RIJDX

NEB

  • Improved IDPP initial path

  • More efficient GFN-xTB runs for NEB

COSX

  • Improvements to numerical integration grids, both for DFT and COSX

  • Faster grid step

  • Improved performance and accuracy in COSX, also for the gradient and Hessian

Properties

  • NMR spin-spin coupling:

    • Added SpinSpinElemPairs and SpinSpinAtomPairs keywords to limit which couplings are computed

    • Reduced the number of CP-SCF perturbations necessary via a stochastic selection

    • DSO term was transposed.

    • Off-diagonal PSO elements had the wrong sign

    • Efficiency improvement: solve SD/FC CP-SCF equations in restricted mode for RHF, instead of always using UHF

  • Optimized numeric integration for HFC gauge correction

  • Removed RITRAFO option for CP-SCF

  • Switched to tau=Dobson as default handling of the kinetic energy density in meta-GGA magnetic properties with GIAOs

Hessian

  • Improvements to the Hessian to avoid accumulation on numerical noise and reduce the number of spurious negative frequencies.

Geometry Optimization

  • Several improvements to the geometry optimization, making is much more stable. Complete redesign of the Cartesian optimizer (!COPT), making it quick enough to be used together with faster methods.

  • Fallbacks in the geometry optimization in case something fails, e.g. if the internal coordinates are unacceptable.

  • Arbitrary spherical, ellipsoidal or box-like wall potentials can be added, which will reflect on the energy and gradients and can be used during geometry optimization.

Miscellaneous

  • CHELPG charges that reproduce the ESP together with the molecular dipole moment

  • Fixed issues with constraints in multi-step jobs

  • Molden output: store ECP info in [Pseudo] block, set point charge atomic number to 0, handling of ghost atoms

  • Made the ExtOpt interface easier to use

  • Store energy from NEB and IRC in the XYZ file