# 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