1.3.4 New Features in Q-Chem 5.4

Changes to default behavior:

• –

  Made default SCF convergence criterion for supersystem and fragment jobs in EDA and BSSE calculations consistent (Yuezhi Mao)

General features and improvements:

• –

  Enabled mixed basis for AUTOSAD guess (Kevin Carter-Fenk, Yuezhi Mao, John Herbert)

• –

  Enabled compatibility with the NBO7 program (John Herbert)

• –

  Implementation of intrinsic bond orbital (IBO) analysis (Alexander Zech, Christopher Stein, Abdulrahman Aldossary, Martin Head-Gordon)

• –

  Resolved issues with:

  • *

    frequency job failure when number of threads is thrice larger than number of atoms

  • *

    frequency job failure when CPSCF segments are equal to number of atoms

  • *

    incorrect alpha density generated when using new plots section format

Density functional theory and self-consistent field:

• –

  Enabled analytic Hessian for TPPS/TM/SCAN TDDFT calculations

• –

  Added printing of information about memory requirements for TDDFT (John Herbert)

• –

  Added an experimental implementation of the X2C method for relativistic quantum chemistry (Diptarka Hait, Leonardo Cunha, Richard Kang, Martin Head-Gordon)

• –

  Improved CIS/TDA/RPA guess to avoid missing roots

• –

  Implementation of projection-based embedding with complex basis functions (Valentina Parravicini, Thomas Jagau)

• –

  Improved performance of the GOSTSHYP method through integral screening (Felix Zeller, Tim Neudecker, Eric Berquist)

• –

  Resolved issues with:

  • *

    AIFDEM crash when a larger fragment is listed first

  • *

    NAN in SCF energies using VV10 functionals

  • *

    unrestricted RPA TDDFT analytic Hessian for singlet excited state

  • *

    failure to compute non-adiabatic couplings (NACs) using pure TDDFT

  • *

    incorrect TDDFT energies with FAST_XAS using multiple threads

  • *

    incorrect results from projection-based embedding using LRC-DFT as the low-level theory (Yuezhi Mao)

  • *

    incompletely converged energies in RPA calculations

  • *

    failure to evaluate spin-orbit integrals in TDDFT SOC calculations

  • *

    GPU acceleration of unrestricted pure DFT gradient when using BrianQC

  • *

    incorrect ROHF gradient when using BrianQC

Correlated methods:

• –

  Implementation of CCSD damped polarizability and first hyperpolarizability (Kaushik Nanda)

• –

  Resolved issues with:

  • *

    wrongfully activated ECD properties with EOM-IP-CCSD (Josefine Andersen, Sonia Coriani)

  • *

    convergence issues in EOM-DIP and EOM-DEA methods

  • *

    symmetry check for v2RDM (Rain Li, Eugene DePrince)

  • *

    failure to write ASCI energy to checkpoint files

Molecular dynamics:

• –

  Enabled the use of new SCF drivers (GEN_SCFMAN=TRUE) in path integral MD

• –

  Resolved issues with:

  • *

    missing energy-component file for AIMD when GEN_SCFMAN=TRUE

Fragment and energy decomposition analysis:

• –

  When EDA2_MOM is used with EDA_BSSE, apply IMOM to BSSE calculations with ghost atoms to prevent collapsing to the lower-energy states (Yuezhi Mao)

• –

  Allowed SCFMI_MOM and EDA2_MOM to preserve the electronic configuration of the frozen state (Yuezhi Mao)

• –

  Multiple stability improvements in ALMO-EDA (Yuezhi Mao)

• –

  Implemented non-perturbative CT analysis for ALMO-EDA (Hengyuan Shen, Srimukh Prasad, Martin Head-Gordon)

• –

  Resolved issues with:

  • *

    final print of the one-side CT energy in VFB CT analysis incorrectly contained the contribution from SMD’s CDS (non-electrostatic) term, when using the SMD solvent model (Yuezhi Mao)

  • *

    double-counting of environment frozen core orbitals with default N_FROZEN_CORE setting for projection-based embedding (Yuezhi Mao)

  • *

    display of preparation energy for ALMO-EDA (Yuezhi Mao)

  • *

    many-body expansion (MBE) geometry optimization (John Herbert)

  • *

    convergence of linear solvers for orthogonal frozen decomposition (Yuezhi Mao)

  • *

    the dispersion term in classic frozen decomposition in non-aufbau ALMO-EDA (Yuezhi Mao)

Miscellaneous:

• –

  Disabled analytic force calculation with projection-based embedding (Yuezhi Mao)

• –

  Disabled complex SCF for fragment jobs (Yuezhi Mao)

• –

  Resolved issue with NAN printing efield file for in QM/MM calculations when external charges are set to zero

• –

  Added warning that CDFT does not support algorithms other than DIIS and RCA (Yuezhi Mao)

• –

  Added warning when 3c methods are used without recommended basis sets (John Herbert)

• –

  Added NBO version number in output (John Herbert)

• –

  Fixed minor spelling errors in the printing of TDDFT (Bushra Alam, John Herbert)

Changes to default behavior:

• –

  Renamed Onsanger SOLVENT_METHOD to Kirkwood (John Herbert)

• –

  Updated the SM8 solvation model to use Cartesian Gaussians (PURECART 2222) (John Herbert)

• –

  Renamed spin-specific keywords to EA_ALPHA, EA_BETA, IP_ALPHA and IP_BETA (Wojtek Skomorowski)

General features and improvements:

• –

  Added Intrinsic Atomic Orbitals (IAO) and Intrinsic Bond Orbitals (IBO) (Abdulrahman Aldossary, Alexander Zech, Christopher Stein)

• –

  Added a new localization method, Oxidation State Localized Orbitals (OSLO) (Abdulrahman Aldossary, Alexander Zech, Christopher Stein)

• –

  Included installation of Romberg utilities

Density functional theory and self-consistent field:

• –

  Implemented hybrid functionals for TAO-DFT (Shaozhi Li, Jeng-Da Chai)

• –

  Improved efficiency of range-separated DFT frequency calculations when run in parallel with shared memory and multithreading

• –

  Added option to turn off ground-state PCM calculations for TDDFT (John Herbert)

• –

  Added option to enforce level shifting in every SCF cycle for state-targeted energy projection (STEP) (Kevin Carter-Fenk)

• –

  Implemented projection-based embedding for unrestricted calculations (Yuezhi Mao)

• –

  Added printing of more digits for the TDDFT transition strength

• –

  Improved SCF guess for optimization jobs using BASIS2

• –

  Resolved issues with:

  • *

    segmentation fault in CIS frequency calculations when using libqints

  • *

    index out of bounds error with TDKS sample in manual (Hung-Yi Tsai, Jeng-Da Chai)

  • *

    errors in unrestricted TDDFT Hessian calculations

  • *

    small error in RPA excitation energies

  • *

    incorrect SCF energy with libqints-based SRC-DFT

  • *

    crash when computing numerical derivatives with BASIS=GEN

  • *

    crash while running large frequency jobs due to insufficient memory in CPSCF

  • *

    incorrect evaluation of iterative Hirshfeld charges (Abdulrahman Aldossary)

Correlated methods:

• –

  Added options for custom scaling in complex basis function calculations (Florian Matz, Thomas Jagau)

• –

  Improved projected CAP-EOM-CC (James Gayvert)

• –

  Implemented EOM-DEA-CCSD two-photon absorption (Kaushik Nanda, Sahil Gulania, Anna Krylov)

• –

  Implemented complex-valued CC2 and RI-CCSD (Cansu Utku, Garrette Pauley Paran, Thomas Jagau)

• –

  Implemented effective nuclear charge approximation for SOCs using EOM (Saikiran Kotaru, Anna Krylov)

• –

  Resolved issues with:

  • *

    freezing string method (FSM) reading SCF energy instead of correlated energy value

  • *

    missing triples corrections for EOM calculations in ccman2 (Pavel Pokhilko)

  • *

    using frozen core and virtual orbitals in projector-based embedding calculations (Yuezhi Mao)

Large systems, QM/MM, and solvation:

• –

  Implemented user-defined permittivity grid for Poisson equation solver (PEqS) (Suranjan Kumar Paul)

• –

  Enabled SCRF for GEN_SCFMAN-based ROHF/ROKS calculations (Yuezhi Mao)

• –

  Implemented state-specific PCM/TDDFT (SS-PCM/TDDFT) method based on the constrained equilibrium theory (Haisheng Ren, Fan Wang, Xiangyuan Li, Yingli Su)

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  Improved GROMACS QM/MM interface (Vale Cofer-Shabica)

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  Improved gradient performance of the SM8 solvation model (John Herbert)

• –

  Improved memory usage of the SM8 solvation model (John Herbert)

• –

  Added TDDFT_LR_PCM to control linear-response solvent correction (John Herbert)

Fragment and energy decomposition analysis:

• –

  Enabled the linearized approximation in projection-based embedding (Yuezhi Mao)

• –

  Implemented POD2L and POD2GS for projection operator diabatization (POD) (Yuezhi Mao)

• –

  Enabled calculation of couplings between multiple pairs of diabatic orbitals for POD (Yuezhi Mao)

• –

  Added printing of separate energy components in the SAPT output (John Herbert)

Changes to default behavior:

• –

  Use of automatically generated superposition of atomic densities SCF guess for custom basis sets (Yuezhi Mao, Kevin Carter-Fenk)

• –

  Use atomic size-corrected Becke weights for CDFT (Kevin Carter-Fenk)

General features and improvements:

• –

  New methods to distort molecules using force and pressure: HCFF, X-HCFF, GOSTSHYP (Tim Stauch, Maximilian Scheurer)

• –

  Overhauled library of standard basis sets for consistency with Basis Set Exchange and extended support through element 118

• –

  Improved stability of ECP fitting and updated definitions of fitted ECPs (CRENBS, CRENBL, HWMB, LACVP, LANL2DZ, SBKJC)

• –

  Evaluation of electric field at nuclei (Yuezhi Mao)

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  Frequency calculations for rigid fixed-atom constraints (Saswata Dasgupta)

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  Save additional calculation output files to unique folder

• –

  Resolved issues with:

  • *

    inconsistent application of quadrupole field to resolve orbital degeneracies

  • *

    definition of jun-cc-pVDZ basis set (John Herbert)

  • *

    some jobs crashing with the FILE_SET_SYM_REP read error

  • *

    cleaning up in PES scan jobs on Windows

  • *

    unnecessary gradient evaluation at every point of frozen PES scan

Features and improvements in density functional theory and self-consistent field:

• –

  TAO-DFT for global hybrid GGAs (Jeng-Da Chai)

• –

  Vibronic and resonance Raman spectroscopy (Xunkun Huang, Huili Ma, WanZhen Liang)

• –

  Integrated DFT-D4 empirical dispersion model (Kuan-Yu Liu, Romit Chakraborty)

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  New implementation of direct propagation of the time-dependent Kohn-Sham equation (real-time TDKS) with support for unrestricted SCF and implicit solvation (Ying Zhu, John Herbert)

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  State-targeted energy projection method (Kevin Carter-Fenk, John Herbert)

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  Multiple improvements to frozen-density embedding methods (Cristina González-Espinoza, Alexander Zech, Tomasz A. Wesolowski)

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  Faster algorithm for $\omega$GDD tuning (John Herbert)

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  Improvements in the IP/EA omega tuning scripts for long range corrected functionals (John Herbert)

• –

  Support for high angular momentum in DFT frequency calculations

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  Superposition of atomic potentials (SAP) guess for SCF (Yu Zhang, Susi Lehtola)

• –

  Expand density functionals available for NMR chemical shift calculations (Jiashu Liang, Khadiza Begam, Barry Dunietz, Yihan Shao)

• –

  Nuclear gradient and analytical 2nd functional derivative of the VV10 functional (Jiashu Liang)

• –

  Performance improvements in the evaluation of DFT-D3 nuclear hessian contribution

• –

  Consistent constrained DFT and SCF convergence criteria (Kevin Carter-Fenk)

• –

  NVIDIA GPU computing improvements via interface with BrianQC:

  • *

    Accelerated force and vibrational frequency computations with range-separated functionals

  • *

    Accelerated Fock derivative computation in DFT vibrational frequency jobs

• –

  Resolved issues with:

  • *

    buffer overflow in a special case of very large DFT jobs

  • *

    a special case of crashing unrestricted CIS derivative coupling calculations

  • *

    evaluation of finite-difference nonlocal correlation orbital Hessian (Yuezhi Mao)

  • *

    use of AO integrals in general response module

  • *

    differences in DFT quadrature between Linux and macOS

  • *

    using ghost atoms in MBD-vdW calculations (Kevin Carter-Fenk, Evgeny Epifanovsky)

  • *

    using arbitrary density functionals for MBD-vdW and TS-vdW

  • *

    crashing large CIS state following calculations

  • *

    SOC constants with unrestricted TDDFT

  • *

    RI-J/RI-K gradient

  • *

    DFT hyperpolarizabilities

Features and improvements in correlated methods:

• –

  Calculation of electronic $g$-tensors with CCSD (Sven Kähler, Anna Krylov);

• –

  Calculation of electronic circular dichroism (ECD) using EOM-CC (Josefine Andersen, Sonia Coriani)

• –

  Evaluation of spin-orbit couplings using CVS-EOM methods, L-edge XAS/XES spectroscopy calculations (Marta Vidal, Pavel Pokhilko, Sonia Coriani)

• –

  Feshbach method with EOM-CC states and Coulomb wave expanded in terms of plane wave Gaussian type orbitals (Wojciech Skomorowski)

• –

  Improved performance in small to medium CC/EOM jobs via in-core computations

• –

  Improvements in projected CAP EOM-CC (James Gayvert)

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  IP/EA-ADC methods and intermediate state representation (ISR) properties (Adrian Dempwolff, Matthias Schneider, Alexander Paul)

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  Dramatic speedup of ADC(3) (Adrian Dempwolff)

• –

  Improved fourth-order static self-energy for all ADC variants (PP (EE), IP, EA) (Adrian Dempwolff)

• –

  Subspace-projected CAP-ADC for all ADC variants (PP (EE), IP, EA) (Adrian Dempwolff)

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  Evaluation of spin-orbit couplings using RAS-CI and RAS2-SF methods (Abel Carreras, Anna Krylov, David Casanova, Hanjie Jiang, Pavel Pokhilko, Paul M. Zimmerman)

• –

  Use of resolution-of-the-identity integrals in LibRASSF-based implementation of RAS-SF (Shannon Houck)

• –

  Implementation of the Bloch effective Hamiltonian approach within LibRASSF-based RAS-SF (Shannon Houck)

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  Experimental implementation of the CC2 and RI-CC2 methods (Garrette Paran, Thomas Jagau)

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  Implementation of the Brueckner CC2 method (Adam Rettig)

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  Implementation of direct RPA for the ground state correlation energy (Joonho Lee)

• –

  Cubic storage RI-MP3 and Laplace-transformed RI-MP2 and RI-MP3 (Joonho Lee)

• –

  Added access to $\kappa$-regularized orbital optimized MP2 via METHOD = koomp2

• –

  New implementation of v2RDM and v2RDM-CASSCF solvers (Rain Li, Wayne Mullinax, Eugene DePrince, Marcus Liebenthal)

• –

  Improved defaults in incremental FCI (Alan Rask)

• –

  Experimental implementation of tensor hypercontraction methods (Joonho Lee)

• –

  Resolved issues with:

  • *

    2 GB limit on temporary files in CC/EOM/ADC calculations on Windows

  • *

    evaluation of analytic gradients of $\kappa$-regularized OO-MP2

  • *

    crashing in fragment excitation difference (FED) calculations due to insufficient memory (Aaditya Manjanath)

  • *

    crashing in large RI-MP2 calculations

  • *

    initial guess in EOM-DIP-CCSD calculations

  • *

    crashing in large RI-CCSD calculations

Features and improvements in molecular dynamics:

• –

  New AIMD variable (AIMD_INIT_VELOC_NANO_RANDOM) for better random seeds (Tarek Scheele)

• –

  Resolved issues with:

  • *

    activating vibrational spectra computation in special cases

Features and improvements for large systems, QM/MM, and solvation:

• –

  AIRBED: A simplified density functional theory model for physisorption on surfaces (Nick Besley, Stephen Mason)

• –

  Resolved issues with:

  • *

    SM12 crashes with general basis set (Yuezhi Mao)

  • *

    MM finite difference force calculations

  • *

    printing of EFG principal components

  • *

    SM12 gradient

  • *

    implicit solvation in SCF and DFT response property calculations

  • *

    requiring explicit derivative level to be set for IEF-PCM frequencies (John Herbert)

  • *

    RI-MP2 + PCM jobs

  • *

    out-of-memory error in large SMD jobs

Features and improvements for fragment and energy decomposition analysis methods:

• –

  Enable geometry optimization on POL and VFB-CT surfaces in the presence of solvent (Yuezhi Mao)

• –

  Enable ALMO-EDA for systems with non-Aufbau electronic configurations (Yuezhi Mao)

• –

  Enable the separation of electrostatic and non-electrostatic terms in SMD solvation energy (Yuezhi Mao)

• –

  Improve error message when attempting ROHF-based SCFMI and EDA

• –

  Improve error message when attempting to use unsupported solvent models with SCFMI and EDA

• –

  Control number of subspace vectors and convergence threshold in SAPT CPSCF (Kevin Carter-Fenk)

• –

  Improved SAPT+aiDX and SAPT+MBD keywords (Kevin Carter-Fenk)

• –

  Resolved issues with:

  • *

    crashing during large projection-based embedding calculations (Yuezhi Mao)

  • *

    requiring explicit derivative level to be set for adiabatic EDA geometries and frequencies (Yuezhi Mao)

  • *

    interoperability between SAPT features and various SAPT basis sets (Kevin Carter-Fenk)

  • *

    crashing when using SAPT(KS) + cDFT with fragment-based Hirshfeld populations (Kevin Carter-Fenk)

  • *

    memory usage in XSAPT (Kevin Carter-Fenk, John Herbert)