Default and keyword changes:
Keywords for MRSF-TDDFT have been updated to align with SF-TDDFT (Arnab Chakraborty, Anna I. Krylov)
MR_SPIN_FLIP and MRSF_DUMP have been removed
SPIN_FLIP = 2 is now used to run an MRSF-TDDFT energy calculation
STS_MOM = TRUE enables state-to-state transition moment calculations
Change CC jobs to use Abelian subgroups by default (USE_ABELIAN_SUBGROUP = TRUE) (Tingting Zhao, Anna Krylov)
Make two-step Cholesky decomposition the default for CC jobs (Tingting Zhao, Anna Krylov)
Set the default of CD_TS_SPAN_FACTOR to (Tingting Zhao, Anna Krylov)
Updated the name of the OPSING keyword to SPIN_PROJ for clarity (John Herbert)
Updated the proton/electron mass ratio in NEO calculations to use the most recent experimental values from NIST CODATA (1836.152673426, rather than 1836.15267389) (Jack Morgenstein, Sharon Hammes-Schiffer)
Make SIMPLE initial Hessian the default for redundant internal coordinates in geometry optimizer (Kuan-Yu Liu)
Change default MAX_SCF_CYCLES to 100 for calculations where SCF_CONVERGENCE>=8 (Kaushik Nanda)
Change default MAX_SCF_CYCLES to 100 for robust SCF workflows (Kaushik Nanda)
Default for SF-1eX2C has been switched from finite-difference to analytic energy (Xiao Liu, Sahand Adibnia, Martin Head-Gordon)
General features and improvements:
Unrestricted VCD (Kaushik Nanda)
MPI improvements (Kaushik Nanda)
wGDD: Print warning that omega is not reset for subsequent TDDFT job (John Herbert)
Added improved SIMPLE initial Hessian to geometry optimizer (Kuan-Yu Liu)
UHF/RHF/ROHF JK, J, K, RS_K, XC contributions to the Fock build with DIIS, GDM, and ROBUST algorithms are now libhpc enabled (Kaushik Nanda)
Density functional theory and self-consistent field:
Extended tight binding DFT (xtb) energy and gradient (Rebecca Tomann, Siyavash Moradi, Lucas de Kam, Christopher Stein, Martin Head-Gordon)
New option for user to choose PT2 engine (MP2, RIMP2, or LMP2) for double hybrid DFT functionals; LMP2 provides scaling comparable to or better than DLPNO for double-hybrid DFT functionals (Yao Shen, Martin Head-Gordon)
Semi-numerical K (Hartree-Fock exchange) for Hartree-Fock, range-separated functionals, and global hybrids (Jesse David DiCenso, Henryk Laqua, Martin Head-Gordon)
Electronic circular dichroism (ECD) calculations for TDDFT (Xunkun Huang, Wan-Zhen Liang)
The following DFT functionals are now available:
COACH (Jiashu Liang, Martin Head-Gordon)
CF22D (Jiashu Liang, Martin Head-Gordon)
wB97M(OS) (Yao Shen, Martin Head-Gordon)
XYG-OS5 (Yao Shen, Martin Head-Gordon)
Density functional theory using complex absorbing potentials, for local density approximations, generalized gradient approximations and derived hybrids. (Charlotte Titeca, Yifan Jiang, Thomas-C. Jagau)
The following complex-variable functionals are now available (Charlotte Titeca, Yifan Jiang, Thomas-C. Jagau)
LDA: Slater X, VWN5 C, VWN1RPA C
GGA: B88 X, PBE X, PBE C, LYP C
Hybrid: all hybrid functionals composed of the above LDAs and GGAs and possibly exact HF exchange. This comprises (among others) PBE0, B3LYP and BH&HLYP.
Density fitting (RI) improvements:
Several performance improvements for J gradient and Hessian (Xintian Feng)
Improved Fock XC performance via MO-based algorithm (Xintian Feng)
JK gradient performance improvements (Xintian Feng)
New SCF level NMR shielding feature with RI acceleration and MPI+OpenMP parallelization (Xiao Liu, Kaushik Nanda, Martin Head-Gordon)
Analytic spin-free SF-1eX2C implementation for SCF level single point energy (Xiao Liu, Sahand Adibnia, Martin Head-Gordon)
CAP/CBF RI-EA-CC2 implementation (Cansu Utku, Garrette Paran, Thomas Jagau)
Implementation of new Faddeeva Finite Pulse Approximation (FFPA) method for photoionization cross-section calculations (Jason Yi, Martin Head-Gordon, C. William McCurdy)
New FRZ MO guess for OO-DFT calculations (Nicola Bogo, Christopher J. Stein, Zeyi Zhang, Martin Head-Gordon)
Implementation of BWs-ADC (Linus Dittmer, Adrian Dempwolff, Adrian Muller, Jonas Leitner, Andreas Dreuw)
pTAO method for excitation energies within the TAO-DFT framework (Shaozhi Li, Jeng-Da Chai)
Omega effective tuning for range separated hybrid functionals (Aditi Singh, Subrata Jana, Szymon Smiga, Prasanjit Samal)
Print gradients of multiple TDDFT states (Pavel Pokhilko)
Implementation of second moments of orbitals and densities (John Herbert)
Improved HOMO-LUMO swap check in new DeltaSCF driver (Juanes Arias-Martinez)
Add doublet (cation) calculations to DeltaSCF driver (Juanes Arias-Martinez)
Enable different guesses for DeltaSCF driver (Juanes Arias-Martinez)
Improved printing for new DeltaSCF driver (Juanes Arias-Martinez)
Resolved issues with:
Linear dependencies in DeltaSCF calculations (Juanes Arias-Martinez)
Memory-related bug for rs-DFT frequency (Xintian Feng)
Slowdown of DFT-based ROSCF calculations (Xintian Feng)
Performance bug for unrestricted range-separated DFT stability analysis (Xintian Feng)
Frequency calculations requested with MBD failed to do MBD part; they now correctly incorporate MBD using finite-difference (John Herbert)
TDDFT NTO guess for unrestricted mixed state in new DeltaSCF driver (Juanes Arias-Martinez)
Triplet SOMO printing in new DeltaSCF driver (Juanes Arias-Martinez)
Memory-related crash in libfock-based JK routines when the given memory is very limited (Xintian Feng)
Incompatibility of RI with solvent models (Xintian Feng)
Incorrect results for DFT-D4 energy when using ghost atoms (Kuan-Yu Liu)
Bug in printing moments of the excited-state densities (John Herbert)
Job hanging when computing the shell radius with a loose threshold (Xintian Feng)
Correlated methods:
Numerical sparsity-based local MP2 (Zhenling Wang)
Large speedups in RI-CC2 ground state code in libgmbpt (Hrishikesh Ram and Martin Head-Gordon)
RI-CC2 and sRI-CC2 oscillator strengths (Chongxiao Zhao, Ruihao Bi, Qi Ou, Joohno Lee, Chenyang Li, Wenjie Dou)
THC-sRI-CC2 properties (Chongxiao Zhao, Ruihao Bi, Qi Ou, Joohno Lee, Chenyang Li, Wenjie Dou)
THC-sRI-CCSD ground and excited state energies (Chongxiao Zhao, Ruihao Bi, Qi Ou, Joohno Lee, Chenyang Li, Wenjie Dou)
Added excited-state analysis for MRSF-TDDFT, including natural orbitals (NOs), natural transition orbitals (NTOs), natural difference orbitals (NDOs), and related descriptors through the libwfa framework (Arnab Chakraborty, Anna I. Krylov)
Added new excited-state analysis features based on Earth Mover’s Distance: An accurate but more expensive transportation-simplex approach, and a faster but approximate Sinkhorn-distance approach (Zhe Wang, Martin Head-Gordon)
MRSF-TDDFT now supports checkpoint file output for visualization (GUI = 2) and MOLDEN file generation (Arnab Chakraborty, Anna I. Krylov)
One-Center Approximation method to calculate K-shell Auger widths using EOM-CCSD wave functions (Wojtek Skomorowski, Sonia Coriani)
Optimized lambda equations for better performance in RI-CCSD, and RI-EOM-EE/EA/IP-CCSD (Tingting Zhao, Anna Krylov)
Charge-displacement metrics in libwfa (John Herbert)
CC2 and RI-CC2 Dyson orbitals for EA, IP, EE-EA, and EE-IP (3755, Mauro Gascon, Robin Moorby, Simen Camps, Tianyi Gao, Thomas Jagau)
SOC implementation for MRSF-TDDFT (Arnab Chakraborty, Anna I. Krylov)
Dipole and transition dipole moments with EOMEE/SF-CC2 (Simen Camps, Tianyi Gao, Mauro Gascón Navas, Thomas Jagau)
Resolved issues with:
CAS calculations skipping CAS when using old SCF driver (John Herbert)
Error in calculation of nonorthogonal matrix elements in NOCIS/STEX (Rachel Patterson, Martin Head-Gordon)
Error with Cholesky decomposition when using frozen core (Tingting Zhao, Anna Krylov)
Job failure for single precision RI-CC2 calculations in CCMAN2 (Simen Camps, Thomas Jagau)
Incorporation of quantum nuclear effects (NEO suite):
Addition of electronic density fitting (RI-JK) to NEO-SCF for SPEs (Rowan Goudy, Sharon Hammes-Schiffer)
Addition of NEO-AIMD methods for NEO-HF and NEO-DFT, including NEO Born-Oppenheimer MD (NEO-BOMD) and constrained NEO MD (CNEO-MD) (Joseph Dickinson, Sharon Hammes-Schiffer)
Improved convergence for RPA when v_pp is off via updated initial guesses for NEO-TDDFT (Rowan Goudy, Scott M. Garner, Sharon Hammes-Schiffer)
Resolved issues with:
NEO-MRCI/NEO-CASSCF ignored NEO_ISOTOPE set in the input file, leading to incorrect results for deuterium and tritium containing systems (Jack Morgenstein, Sharon Hammes-Schiffer)
Incorrect results for deuterium and tritium containing systems defined with NEO_ISOTOPE (Jack Morgenstein, Sharon Hammes-Schiffer)
Segfaults in some NEO calculations using spherical functions of angular momentum 2 or higher in NEO basis (Rowan Goudy, Eno Paenurk, Sharon Hammes-Schiffer)
Erroneous results for NEO Hessian calculations using the nuclear Hartree product representation when the nuclear basis set had linear dependencies (Eno Paenurk, Sharon Hammes-Schiffer)
Erroneous results for NEO-SCF in certain cases when run with low memory (Rowan Goudy, Jack Morgenstein, Sharon Hammes-Schiffer)
Molecular dynamics, non-adiabatic dynamics, embedding, and solvation improvements:
Implemented pairwise harmonic confiner for optimization in internal coordinates (Chance Brandt, John Herbert)
Added ability to change the non-additive exchange correlation functionals after supersystem SCF in projection-based embedding (Elena Kolodzeiski, Christopher Stein)
Generalized, file-based external embedding interface enables interfacing to external packages like CP2K (Arnelle Fonlon, Kay Carter-Fenk, Dustin R. Broderick, Elena Kolodzeiski, John M. Herbert, Christopher J. Mundy)
Significant speed up and parallelization of one-electron integrals in QM/EFP jobs provides an order of magnitude total speed up for large jobs (Lyudmila Slipchenko)
Improved printout for QM/EFP provides essential information for debugging convergence issues (Lyudmila Slipchenko)
Improved QM/MM functionality, including efficient constraints for QM/MM geometry optimization (Lyudmila Slipchenko)
Resolved issues with harmonic confining jobs not opening properly in IQmol (Yuezhi Mao)
Fragment and energy decomposition analysis:
EDA OVOCV analysis and OODFT OVOCV analysis (Hengyuan Shen, Martin Head-Gordon)
Added revised MBD parameters (MBDrev) for SAPT (Ka Un Lao, Corentin Villot)
New MBD dispersion models for XSAPT+MBD (Keegan Paice, John Herbert)