17590884, 2022, 5, Downloaded from https://wires.onlinelibrary.wiley.com/doi/10.1002/wcms.1606 by National Medical Library The Director, Wiley Online Library on [12/12/2022].

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Received: 17 November 2021 Revised: 1 February 2022 Accepted: 3 February 2022
DOI: 10.1002/wcms.1606

SOFTWARE FOCUS

Software update: The ORCA program system—Version 5.0

Frank Neese

Max Planck Institut für Kohlenforschung,

Mülheim an der Ruhr, Germany
Abstract
Version 5.0 of the ORCA quantum chemistry program suite was released in
Correspondence
July 2021. ORCA 5.0 represents a major improvement over all previous ver-
Frank Neese, Max Planck Institut für
Kohlenforschung, Kaiser-Wilhelm Platz sions of ORCA and features (1) highly improved performance, (2) increased
1, Mülheim an der Ruhr D-45470, numerical robustness, (3) a host of new functionality, and (4) greatly improved
Germany.
user friendliness. The article describes the most salient features of the
Email: neese@kofo.mpg.de
program.
Funding information
Max-Planck-Gesellschaft This article is categorized under:
Electronic Structure Theory > Ab Initio Electronic Structure Methods
Data Science > Computer Algorithms and Programming
Edited by: Peter R. Schreiner, Editor-in-
Chief Software > Quantum Chemistry

KEYWORDS
density functional theory, electron correlation, QM/MM, quantum chemistry, theoretical
spectroscopy

1 | INTRODUCTION

The ORCA project was started in the mid 1990s as an in-house project to understand some features in the spectroscopy
of open-shell transition metal complexes.1 It has since evolved into a general-purpose quantum chemistry program with
more than 40,000 academic users and quickly growing number of commercial users. Citation statistics indicate that
ORCA is presently the second most used quantum chemistry program world-wide with a steep upward slope. ORCA is
free of charge for academic users and distributed commercially to industry via the company FAccTs (www.faccts.de).
ORCA is supported by a very active users forum hosted at https://orcaforum.kofo.mpg.de and is extensively docu-
mented in a >1300 page manual. Additional educational resources include the tutorials site at FAccTs (https://www.
orcasoftware.de/tutorials_orca/index.html), the ORCA input library (https://sites.google.com/site/orcainputlibrary/
home), as well as a number of tutorials, jump-start guides, and video lessons that are available on the ORCA forum.
Highlights of ORCA include (1) State-of-the art performance, (2) comprehensive theoretical methodology, (3) user
friendliness, and (4) platform independence. Taken together, these features allow for computational studies throughout
all domains of chemistry to be performed efficiently and largely without the need to rely on third party software. This
short software update will provide an overview over the functionality added to ORCA since the publication of the origi-
nal 2012 WIRES article,2 the 2017 update for ORCA 4.0.3 The new features in ORCA 5.0 have also been partly described
in the most recent article describing ORCA functionality.4

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2022 The Author. WIREs Computational Molecular Science published by Wiley Periodicals LLC.

WIREs Comput Mol Sci. 2022;12:e1606. wires.wiley.com/compmolsci 1 of 15

https://doi.org/10.1002/wcms.1606
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2 | I N T E G R A L GE N E R A T I O N

ORCA 5.0 is largely driven by a completely new integral engine and task driver that was given the name SHARK.5
SHARK is using some basic ORCA infrastructure, but is a largely autonomous C++ software that was written with a
focus on: (1) featuring the highest possible numerical efficiency, (2) providing a clean and easy-to-use interface for the
programmer, (3) keeping the code as compact and transparent as possible, and (4) providing optimized workflows to
facilitate complex quantum chemical tasks.
The SHARK integral package is based on an original idea of how to calculate two electron integrals in the
McMurchie and Davidson formulation6 efficiently. The resulting algorithm is highly efficient, in particular for low- and
high-angular momentum integrals for which it outperforms traditional algorithms by a factor of up to 5–6 (for l = 4
(g) and higher angular momentum functions). For intermediate angular momenta, FLOP count optimal algorithms like
the Obara-Saika scheme, as implemented in Libint,7 are most advantageous. Efforts were undertaken to select the most
efficient algorithm for a given task and batch of integrals. Consequently, SHARK also features a new interface to the
Libint library with which it is fully integrated. In addition, the already very efficient Split-RI-J algorithm8 has been fur-
ther improved, in particular for high angular momenta.
The result is that almost all integral tasks run faster in ORCA 5.0 than in previous versions. Improvements range
from moderate (e.g., 10%–30% for Hartree–Fock and [hybrid] density functional theory [DFT]) to more than a full order
of magnitude in elapsed time (timings are documented in section 14). Particularly large performance improvements
have been realized in analytic Hessian-, time dependent DFT (TD-DFT)—and response property (magnetic resonance
with Gauge Including Atomic Orbitals [GIAOs]) as well as electron–electron spin–spin9–11 and two-electron spin–orbit
coupling12 calculations all of which perform about a factor of 5–10 faster than with previous ORCA versions and proba-
bly represent the state of the art for the mentioned tasks.
SHARK fully supports segmented (e.g., def2-bases13–16), generally contracted (atomic natural orbital, ANO17) and
partially generally contracted (e.g., correlation consistent, cc-pVnZ18–20 and variations thereof) basis sets and is highly
performant for all three classes. SHARK also features a general implementation of range separation22 throughout all
integral classes as well as supporting a finite nucleus model22 throughout for (scalar) relativistic calculations.23–27
However, SHARK is much more than only an alternative integral generator. Using a number of advanced program-
ming techniques, it is the motor that drives all integral related tasks in ORCA like the calculation of Fock matrices,
response matrices, various residuals, gradients, Hessian contributions, and so on using an interface that is easy to use
or to extend for the programmer and much more fail-safe than traditional approaches. This leads to much more com-
pact code with higher code consistency and integrity. The benefit for the user is greatly enhanced code stability, effi-
ciency as well as shorter development cycles compared to the traditional way of developing quantum chemical
algorithms. Consequently, hundreds of thousands of lines of legacy code could be deleted in the process of designing
ORCA 5.0 and replaced by cleaner and leaner code based on the SHARK concept. Hence, from ORCA 5 onward, the
numerically intensive “nitty-gritty” tasks are handled by SHARK, while the entire workflow is orchestrated by the
ORCA infrastructure.
Additional technicalities include the increased use of shared memory on parallel platforms that helps to eliminate
memory bottlenecks, nearly complete conversion of the code to 64 Bit integers, improved parallelization, and an update
to the latest MPI (OpenMPI 4.128) and BLAS (OpenBLAS; https://github.com/xianyi/OpenBLAS/wiki/faq#publication)
libraries.

3 | INTEGRATION GRIDS AND CHAIN OF SPHERES EXCHANGE

We have realized that the ORCA default grids were no longer meeting the accuracy standards expected by the computa-
tional chemistry community. Since the XC integration is linear scaling and usually does not represent a bottleneck
(except for small molecules), it was decided to reconstruct the grids from scratch and meet more strict accuracy stan-
dards. Hence, all numerical integration grids were re-designed from the bottom up for ORCA 5.0 using machine-
learning techniques.29 In order to keep the number of distinct grids to a reasonable minimum, only three default grids
are available from now on and are called DefGrid1 to DefGrid3 with DefGrid2 being the default. All subsequent grids,
for example, those used in coupled-perturbed self-consistent field (CP-SCF), TD-DFT, Chain-of-spheres exchange
(COSX29–32), and so on calculations are automatically adapted to be consistent with the global accuracy of the underly-
ing chosen DefGrid.
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The new grids can be chosen by the user to be rotationally invariant.33 The grids are self-adapting in the sense that
they will recognize the presence of steep functions, very diffuse functions or core polarization functions and adjust the
numerical integration accuracy in the relevant region accordingly. Consequently, numerical integration is more accu-
rate and numerically robust compared to previous program versions. Typical grid incompleteness errors stemming from
the exchange-correlation integration (COSX numbers in parenthesis) are 0.01 (0.05) kcal/mol in relative energies, 0.1
(0.04) cm 1 in analytic harmonic frequencies and <10 3 eV in excitation energies. DefGrid3 leads to even smaller errors
(about factor 2–5) and hence, is very close to reference grid accuracy. The significantly smaller DefGrid1 still provides
adequate accuracy for survey calculations despite the fact that the errors are larger by 2–5 times relative to DefGrid2.
The new grids are larger than the old default grids by a factor of 2–4. Since the time spent in numerical integration
is directly proportional to the number of grid points, the time spent in the numerical integration part of the increases
by about this factor. However, the numerical integration is linear scaling with respect to system size and scales well
with the number of processors in parallel calculations. Hence, numerical integration only becomes rate limiting under
special circumstances (e.g., Hessian calculations using DFT without exact exchange) for small molecules.
For the COSX implementation, the analytic integrals have been completely redesigned and highly optimized. They
run up to an order of magnitude faster than the previous analytic integrals leading to overall speedups of the COSX part
of the calculation by a factor of 2–5.30

4 | DENSITY FUNCTIONAL THEORY

The DFT capabilities of ORCA include local (LDA), gradient corrected (GGA), meta-GGA, hybrid, double-hybrid, and
range-separated hybrid and double-hybrid functionals. For ORCA 5.0, the meta-GGA analytic Hessian, the DFT-D4 dis-
persion correction34 as well as the analytic gradient of the Vydrov and von Voorhis (VV10) dispersion correction35 were
implemented. In addition, the program was adapted to work with the version 5.1.0 of the LibXC library36 thus giving
access to 588 different density functionals including the SCAN family of functionals37 as well as the low-cost/high accu-
racy versions of the Grimme group (r2SCAN-3C38).

5 | SCF C ON VERG E N CE, G EOM E T R Y O P T I M I Z A T I O N, A ND TR A NSI TIO N

STATES

In ORCA 5.0 a highly robust second-order converger based on the trust-radius augmented Hessian (TRAH) method39
was implemented. TRAH essentially guarantees SCF convergence, even for the most difficult cases. Since for well-
converging standard cases, TRAH is a slightly slower than the default converger (DIIS40 combined with a quasi-Newton
second order (SOSCF)41,42 method), an effort has been made to detect slowly- or nonconvergent cases automatically
and to start the TRAH procedure only in these cases. The result is a highly reliable SCF procedure which is of great ben-
efit to high-throughput computational chemistry studies working with large sets of individual molecules or jobs.
As a consequence of the significantly reduced numerical noise in energies and gradients, the number of SCF and
geometry optimization cycles is significantly reduced, on average by about 30% thus providing further speedups. In par-
ticular, large and floppy molecules profit from the improved numerical accuracy. Further efforts were undertaken to
improve the existing nudge elastic band (NEB) functionality to efficiently find transition states with nothing but the
structures of the reactants and products as input.43

6 | T I M E - D E P E N D E N T D F T AN D O T H E R EX C I T E D S T A T E ME T H O D S

Significant enhancements in TD-DFT have been made in ORCA 5.0 including the variational linear-response conductor
like polarizable continuum model (CPCM) excited state solvation,44 colinear spin-flip TDDFT,45 nonadiabatic couplings
between ground and excited states,46,47 and the doubles correction48,49 for triplet states.50 of course, the “doubles correc-
tion” only applies to double hybrid functionals. It was originally derived from the CIS(D) correction51 and scaled appro-
priately for double hybrid functionals.48 The extension to spin-component scaled variants of CIS(D)52 was also applied
to double hybrid TD-DFT.53 The extension to triplet excited states was recently implemented in ORCA together with
new range-separated double hybrid functionals.54 In addition, ORCA can now determine the irreps for each excited
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state and the <S2> value in unrestricted calculations and perform population analysis using relaxed densities for any
number of states. Finally, a conical intersection optimizer and the NEB transition state finder work with TD-DFT.
One of the highly successful developments in local correlation (vide infra) concerns the domain based local pair nat-
ural orbital (DLPNO) similarity transformed equation of motion (STEOM) coupled-cluster method with single-and dou-
ble excitations (CCSD) method55–61 that provides very accurate results at low computational cost.58,62–67 Together with
an automatic scheme to determine the STEOM active space,57 the calculations run in near linear scaling up to the final
step, where a CIS type diagonalization is done that scales as O(N4). In all benchmark and application studies, this
method has shown excellent performance, even exceeding the accuracy of EOM-CCSD, while being computationally
cheaper than the popular CC2 model.55–61

7 | LOCAL C OR RELATION METHODS

Local correlation methods based on pair natural orbitals (PNOs) expanded in large domains (DLPNO) have been a sta-
ple in the ORCA method arsenal since PNO methods were first brought back to life in 2009.68,69 Since then, many
developments have taken place for closed-70–72 and open73–75 -shell systems, multireference methods,76,77 excited state
methods,55–61 F12 implementations,78–81 local energy decomposition,82–89 multilevel/embedding/quantum mechanics-
molecular mechanics (QM-MM) schemes,65,90–95 and molecular properties.96–101 The method is now widely used by the
scientific community as evidenced by a nearly exponentially increasing number of citations and has proven its accuracy
and applicability in a large number of benchmark studies.102–105
In ORCA 5.0, the rigorous formulation and implementation of DLPNO-MP2 and double hybrid DFT analytic second
derivatives for electric and magnetic property calculations have been achieved and allow for highly efficient polarizabil-
ity and NMR chemical shielding tensor calculations on large molecules.98 The F12 methodology has been completed by
an open-shell DLPNO-CCSD(T)-F12 implementation.78 An additional focus of the development were multilevel
schemes96–101 as well as extensions of the local energy decomposition (LED88). Additional developments include an
extrapolation protocol to the complete PNO limit106 and the HF-LD method84 which allows for accurate and cost-
effective calculations of dispersion interactions in large molecular aggregates such as DNA fragments107 or intricate
donor/acceptor interaction in protein/drug interactions.108 Technical improvements include a proximity check that
ensures domain completeness and optimization of the memory handling.

8 | M UL T I -R E F ER E NC E M E T HO D S

Multireference methods have been another focal point of interest in the history of ORCA, primarily with the aim to
properly109 treat magnetic systems. In ORCA 5.0, a variant of the complete active space second order perturbation the-
ory (CASPT2) method has been developed (CASPT2-K)110 that is virtually intruder state free and does not contain any
empirical parameters such as level- or IP/EA shifts. Furthermore, both CASPT2 and NEVPT2 have been reformulated
to eliminate bottlenecks arising from the four-particle density. Speedups for large active spaces (such as CAS,16 S = 0)
are up to two orders of magnitude while maintaining exact results.111 The feasibility of approximating the higher order
densities in NEVPT2 through cumulant and other approximations has been investigated and met with skepticism due
to the occurrence of false intruder states that are introduced by these approximations.112,113 Finally, a linear scaling
DLPNO-NEVPT2-F12 implementation has been completed.
The ab initio ligand field theory (AILFT)114 has now served for almost a decade as a powerful link between theory
and experiment. In ORCA 5.0, it has been extended to treat two shells at the time which open the possibility of fully
parameterizing all elements. This has been taken advantage of in a standalone multiplet program (orca_lft) that can
either be used in a completely autonomous way to calculate the X-ray absorption, optical and magnetic spectra of tran-
sition metal complexes through ligand field theory or in conjunction with a parameter set provided by AILFT.
A number of articles were published reporting multi-reference methods of the perturb-then-diagonalize type which
are designed to treat static and dynamic correlation as well as relativity on equal footing. The resulting methods are
called second-order dynamic correlation dressed complete active space (DCD-CAS3) as well as Hermitian Quasi-
Degenerate NEVPT2 (HQD-NEVPT2).115–118
Major development efforts have been undertaken for the iterative configuration expansion (ICE),119,120 a
selecting CI method based on Malrieu's pioneering CIPSI (configuration interaction by perturbation with
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multiconfigurational zeroth-order wavefunction selected by iterative process)121 method. The method has now
been formulated in terms of three distinct many body expansion functions (MBEF), namely configurations, indi-
vidual configuration state functions (CSFs) and individual determinants.119,120 The advantages and disadvantages
of each approach have been carefully discussed. An extrapolation method for obtaining results close to the exact
result at threshold zero has been devised.119,120 The ICE method allows for approximate Full-CI results to be
obtained on very large active spaces. Depending on the nature of the system, up to about 80 active orbitals have
been treated with it. The CSF based implementation holds particularly exciting prospects for applications to molec-
ular magnetism.
Based on significant progress in the automatic code generation chain (ORCA_AGE122), an improved implemen-
tation of the fully internally contracted multireference coupled cluster method (FIC-MRCCSD) has been accom-
plished as well as part of ORCA 5.0. A perturbative version of the multireference EOM-CCSD (MR-CCSD) has
been successfully tested.123

9 | S OL V A T IO N

For ORCA 5.0, all implicit solvation methods have been updated to feature the Gaussian charge scheme.124,125 Conse-
quently, it is available for SCF, analytic gradient and analytic Hessian calculations together with the CPCM and SMD
(“Solvation Model Density”) models. The Gaussian charge scheme leads to much smoother and numerically robust
optimizations compared to discrete cavities that were in previous versions, in particular for large molecules with com-
plex shapes. Secondly, solvation was incorporated into the coupled cluster module, thus allowing CCSD(T) and
DLPNO-CCSD(T) calculations to be performed in the presence of a continuum solvent.126 The computational overhead
added by the solvation models is very small.

1 0 | MULTI S CALE AN D MU LT I L E V E L M E T HO DS

A strong focus on the development of ORCA 5.0 were multilevel methods that allow for calculation of macromolecules
and extended systems like solids. All this functionality is provided natively in ORCA, thus minimizing efficiency losses
arising from interfaces to external programs.
ORCA 5.0 features a user friendly, native QM/MM implementation that greatly facilitates the workflow for
QM/MM studies on macromolecules (proteins, DNA, …) or explicitly solvated systems. The implementation fea-
tures an automated treatment of the boundary region, including a charge-shift compensation for possible over-
polarization, a dedicated geometry optimizer for thousands of atoms, easy access to existing force fields as well as
availability of popular force fields including CHARMM,127 AMBER,128 and OPENFF (https://openforcefield.org/
force-fields/force-fields/).
ORCA 5.0 also includes a native ONIOM (Our own n-layered Integrated molecular Orbital and Molecular mechan-
ics129) implementation allowing up to three different layers that are treated by different methods that can range from
semi-empirical methods over DFT to high-level wavefunction based methods. The ONIOM methods can be used with
mechanical as well as electronic embedding. Covalent bonds between different regions are handled in a fully automated
way. In particular the two-layer ONIOM method is very user-friendly, only requiring the definition of the high-level
region, and allows for pure QM calculations on systems with thousands of atoms, for example, large solvated catalysts.
Additionally, it can be combined with implicit solvation. The implementation also allows for QM/QM2/MM type of cal-
culations to be set up for large molecules. The ONIOM methods can be further combined with the DLPNO-multilevel
scheme in case more than three layers of accuracy are required.
For the treatment of solids, surfaces, defects or molecular crystals Crystal-QMMM was introduced, an intuitive and
automated method for electrostatic embedding techniques. It is combined with the orca_crystalprep utility, that allows
for the user to prepare a native ORCA input file directly from a .cif or .xyz file that can then be further edited for the
desired type of calculation. Crystal-QMMM features a charge convergence scheme for the embedding point charge to
guarantee a chemically reasonable, overall neutral system. Highly accurate property calculations of adsorption
energetics,93 band gaps,65 NMR chemical shifts,130 absorption, fluorescence, or X-ray absorption spectra131–138 are possi-
ble in conjunction with the accurate high-level methods featured by ORCA.
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1 1 | A B I N I T I O M O L E C U L A R DY N A M I C S

ORCA 5.0 features a Born-Oppenheimer molecular dynamics module that can be used in conjunction with all method
available in ORCA that deliver energies and gradients. This module has been enhanced by a meta-dynamics module
with many options as well as with the Nosé-Hoover Chain (NHC) and Canonical Sampling through Velocity Rescaling
(CSVR) thermostats. Additional important improvements include the implementation of a meta-dynamics139 in addi-
tion as well as umbrella sampling140 functionality.

1 2 | EP R A ND N MR P RO P ERTI ES

From its early days on, ORCA has been a program for molecular spectroscopy. In ORCA 5.0, in particular the capabili-
ties to predict nuclear magnetic resonance (NMR) properties have been greatly improved.98,141,142 Next to the large-
scale DLPNO-RI-MP2 implementation of chemical shieldings mentioned above,98 ORCA 5.0 features significantly
enhanced performance for chemical shieldings (factor >2) and for spin–spin couplings (factor >5), increasing with sys-
tem size. In addition, a local orbital decomposition analysis of chemical shieldings has been added as well as the possi-
bility to perform vibrational averaging via the VPT2 method and the current dependency of meta-GGAs via the Dobson
Ansatz.143
Electron paramagnetic resonance (EPR) calculations massively profit from the enhanced performance of the inte-
grals leading to speedups up to an order of magnitude, in particular for spin-orbit coupling and electron–electron spin–
spin coupling contributions. G-tensor calculations now feature GIAO's by default. In addition, the g-tensor and orbital
contributions to hyperfine couplings have been implemented at the RI-MP2 and double hybrid DFT level.144 Vibra-
tional corrections to hyperfine couplings are available.145 A careful analysis of gauge correction terms has led to resolv-
ing an old puzzle in the theory of paramagnetic NMR spectra.146

1 3 | C O M P O U N D S C R I PTI N G L A N G U A G E

A major progress in workflow optimization is provided by the compound feature of ORCA. In a nutshell, the compound
feature represents a simple scripting language which is deeply integrated within ORCA. Through a compound script,
complex multi-step tasks can be driven in an automated way, calculation results can be accessed through the ASCII for-
mat ORCA “property file,” some algebra can be performed and a concise summary of the results is printed. Thus, even
very complex workflows can be executed in a reliable and automatic fashion through a single keyword and readily cus-
tomized to each researcher's needs.
The compound facility allows for standardized computational protocols to be defined in an extremely streamlined
fashion (e.g., throughout a given project or research group). For example, a script that is included in the ORCA distribu-
tion performs geometry optimization and analytic frequency calculations. In the event that negative frequencies (within
a specifiable threshold) are detected, the system is displaced along the imaginary mode and the process repeated until a
real minimum with no negative frequencies is found. The compound scripting language knows variables, “if,” “for,”
“while,” and “goto” statements as well as system calls and formatted print statements. Through the compound script
facility, the user has direct access to the ORCA “property” file through which more than 250 distinct properties can be
accessed. Variables in the compound file (e.g., a basis set, the number of electrons in a CASSCF or the basename of the
calculation) can be overwritten in the ORCA input using the statement “with.” Clearly, the deep integration with the
internal ORCA data allows for jobs to be far more flexible, platform independent and reliably defined and executed
than an external scripting language (like Python) could offer. A compound job library is hosted at GitHub (https://
github.com/ORCAQuantumChemistry/CompoundScripts) and provides a platform for ORCA users to exchange com-
pound protocols.

1 4 | REPRE S EN T AT I VE T I MI NGS CO M P A R I SO NS

Actual wall clock times will be very quickly outdated given the very rapid development in computer hardware. They
may also greatly depend on the specific setup and the system load on the employed machines. Nevertheless, a few
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representative timing comparisons between ORCA 5.0 and the previous ORCA 4.2.1 run under identical conditions on
identical hardware are documented below. The molecules used in the benchmark calculations are shown in Figure 1.
Unless otherwise noted, the calculations were done on 32 Core-machines equipped with AMD EPYC 7302 16-Core pro-
cessors and a total amount of RAM of 512 GB.
Table 1 lists timings for all 11–15 Fock matrix builds for the Vancomycin (176 atoms) with a variety of basis sets.
These calculations (and all other calculations in this section) were done in parallel on 16 cores. The observed speedups
relative to a single core were a factor 14–15. For 32 cores, the parallelization efficiency decreases somewhat to a factor
of about 25. Parallel speedups for the other calculations shown below are comparable and they are representative of
ORCA parallelization efficiency.
For the single point calculations in Table 1 that use “pure” DFT (no Hartree–Fock exchange), the original Split-RI-J
algorithm is difficult to outperform and hence the calculation times for nonhybrid functionals are similar between
ORCA 4.2.1. and ORCA 5.0 The slight increase observed for some ORCA 5.0 calculations is due to the larger and more
accurate grids in the numerical integration part. Similarly, there are limited speedups in the integral generation and
digestion in ORCA 5.0 for four center integrals (partially compensated by the numerical integration). However, massive
speedups are coming from the revised RIJCOSX algorithm that is now default in ORCA 5.0 because due to the

FIGURE 1 Structures used in the benchmark calculations documented in Tables 1–6

T A B L E 1 Wall clock times (seconds) for all 11–15 Fock matrix builds required to converge the SCF equations to ORCA “TightSCF”
criteria for Vancomcin (176 atoms) and Penicillin (42 atoms)

Vancomycin/PBE Penicilin/B3LYP

#(Basis) ORCA 4.2.1 ORCA 5.0 ORCA 4.2.1 ORCA 5.0 ORCA 5.0a
Def2-SVP 1797 79 (15) 89 (15) 19 (8) 19 (8) 20 (8)
Def2-TZVP 3593 220 (15) 231 (14) 266 (13) 261 (13) 90 (13)
Def2-QZVP 8033 798 (14) 808 (14) 3765 (13) 3686 (13) 334 (13)
cc-pVTZ 4088 269 (14) 243 (14) 379 (13) 348 (13) 97 (13)

Note: In parenthesis, the number of SCF iterations is given.

a
Default with RIJCOSX.
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8 of 15 NEESE

improved accuracy of this approximation there is no numerically significant error introduced. This is why most hybrid
and double hybrid DFT calculations in ORCA 5.0 perform vastly better than in previous ORCA versions. It is
mentioned in passing, that the speedups for ANO bases (not shown), are much more pronounced. Calculations using
such basis sets were barely doable in integral direct mode with older ORCA versions, but proceed efficiently in ORCA
5.0 since SHARK is has been developed to be efficient with either segmented or (partially) generally contracted
basis sets.
The significant improvements in the integral generation and digestion also show up in analytic Hessian calculations
(Table 2). For hybrid functionals, the speedups appear to be particularly dramatic. This is mainly caused by the switch
to using RIJCOSX as default for hybrid functionals in ORCA 5.0 Using RIJCOSX in ORCA 4.2.1 results in timings about
10% slower than ORCA 5.0 Skipping RIJCOSX in both versions, result in ORCA 5.0 being faster than ORCA 4.2.1. but
up to a factor of 2 (for the larger and more accurate basis sets). In comparing these numbers, one should keep in mind
that the much more accurate grids in ORCA 5.0 make the RIJCOSX results almost indistinguishable from the fully ana-
lytic results.
Even larger speedups are realized for TD-DFT calculations and molecular response calculations, where the improve-
ments relative to older ORCA versions exceed an order of magnitude (Tables 3 and 4). This is mostly caused by the
much more efficient integral digestion strategy in ORCA 5.0 that leads to major speedups in cases where many Fock-
like matrices are being built at the same time.
Similarly, large speedups can be observed for the calculation of NMR and EPR properties (Tables 5,6). In this case,
it is the improvement of the intrinsic efficiency of the integral generation that is causing the speedups from ORCA 4.2.1
to ORCA 5.0.

TABLE 2 Wall clock times (seconds) for an analytic Hessian calculation for Penicillin (42 atoms)

Penicilin/PBE Penicilin/B3LYP

ORCA 4.2.1 ORCA 5.0 ORCA 4.2.1a ORCA 5.0a

Def2-SVP 176 125 1180 208
Def2-TZVP 713 376 17,925 1008
Def2-QZVP 3142 1425 326,856 7410
cc-pVTZ 910 440 26,692 1264
a
These are the respective program defaults. ORCA 5.0 defaults to RIJCOSX, 4.2.1 does not.

TABLE 3 Wall clock times for fully converging 25 roots in a TD-DFT calculation on Pheophytin (138 atoms)

Pheophytin A/PBE Pheophytin A/B3LYP

#(Basis) ORCA 4.2.1 ORCA 5.0 ORCA 4.2.1 ORCA 5.0

Def2-SVP 1266 330 94 439 292
Def2-TZVP 2428 1589 312 2788 1239
Def2-QZVP 3950 21,521 2052 57,491 9201
cc-pVTZ 2956 2315 415 4981 1699

TABLE 4 Wall clock times for calculating the static polarizability tensor of Streptogramin A (73 atoms)

Streptogramin A/PBE Streptogramin A/B3LYP

ORCA 4.2.1 ORCA 5.0 ORCA 4.2.1 ORCA 5.0

Def2-SVP 24 11 111 35
Def2-TZVP 83 35 441 114
Def2-QZVP 365 187 7205 1033
cc-pVTZ 108 42 566 144
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T A B L E 5 Wall clock times the calculation of all 555 spin–spin coupling tensors and all chemical shieldings of Amylose 2 (45 atoms)
with the TPSSh functional and the pcJ-2 basis set (1701 basis functions)

ORCA 4.2.1 ORCA 5.0

Spin–spin couplings
SCF 1231 822
DSO 5242 2
PSO 19,836 1068
SD + FC 65,137 11,819
Total (incl. SCF) 92,280 14,057
Chemical shieldings
GIAO-RI-J 146 24
GIAO-COSX 87 59
GIAO-other 104 58
CP-SCF 295 53
Total (incl. SCF) 1352 726

Note: CP-SCF, solution of the coupled-perturbed SCF equations; DSO/PSO, diamagnetic/paramagnetic terms SD + FC = Fermi and spin-dipolar contributions
(including solution of the CP-SCF equations). GIAO-RI-J/GIAO-COSX refers to the times needed for the calculation of the right-hand sides of the CP-SCF
equations, GIAO-other are remaining GIAO integral terms.

T A B L E 6 Wall clock times the calculation of the g-tensor for the chlorophyll A radical (134 atoms) with the B3LYP functional and the
def2-TZVPP basis set (2405 basis functions)

ORCA 4.2.1 ORCA 5.0

g-Tensor
SCF 7140 4851
SOC integrals 1371 1397
GIAO-RI-J 780 119
GIAO-COSX 1020 400
GIAO-other 951 438
Total (incl. SCF) 17,636 7944
Spin–spin tensor
Total (excl. SCF) 3208 366

Note: SOC, spin-orbit coupling. Also shown is the electron–electron spin–spin coupling tensor for the neutral triplet state.

1 5 | C O N C L U S IO N

It hopefully became apparent in brief feature description provided here, that ORCA 5.0 is a major upgrade to the pro-
gram. The changes to the integral generation and handling turned ORCA into one of the most efficient quantum chem-
istry codes available. At the same time, ORCA is also one of the most versatile and user-friendly quantum chemistry
packages available. It features semi-empirical, Hartree-Fock, DFT, single- and multireference (local) correlation
methods, can compute a large array of molecular properties and is a fully integrated system for multilevel calculations
including QM/MM, ONIOM and embedded crystals. The program runs on essentially all contemporary hardware in
either serial or parallel mode. ORCA's user base in the academic community currently amounts to more than 40,000
registered users with a steep upward slope. ORCA is also firmly established in industrial research by now. It is
envisioned that based on the important streamlining of the infrastructure accomplished with ORCA 5.0, future develop-
ments will be greatly facilitated. The entire team is looking forward to providing an even more powerful program to the
scientific community in due course.
 17590884, 2022, 5, Downloaded from https://wires.onlinelibrary.wiley.com/doi/10.1002/wcms.1606 by National Medical Library The Director, Wiley Online Library on [12/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
10 of 15 NEESE

A C K N O WL E D G M E N T S
I gratefully acknowledge the generous financial support of this project by the Max Planck Society. Creating ORCA 5.0
was a true team effort and a tour de force unlike any I have had the pleasure to be involved in over the last three
decades of my scientific career. Throughout the pandemic years 2020 and 2021, the whole development team stood
together as one, motivated, pushed and encouraged each other in a way that is as memorable as it is humbling. I am
deeply indebted to everybody who put their hard work and their enthusiasm into this project. I also thank Ute Becker,
Christoph Riplinger, Frank Wennmohs, Bernardo DeSouza, and Georgi Stoychev for helpful comments on the manu-
script in addition to their outstanding contributions to the ORCA project.

CONFLICT OF INTEREST
The author is co-founder of the company FAccTs (https://www.faccts.de), which is commercially distributing ORCA to
industry (ORCA is and will remain free for academic researchers). The author does not see a scientific conflict of inter-
est in this involvement.

DATA AVAILABILITY STATEMENT

Data sharing is not applicable to this article as no new data were created or analyzed in this study.

ORCID
Frank Neese https://orcid.org/0000-0003-4691-0547

R EL ATE D WIR Es AR TI CL ES
Software update: the ORCA program system, version 4.0
The ORCA Program System

FURTHER READING
For further information, the reader is encouraged to visit https://orcaforum.kofo.mpg.de, https://www.orcasoftware.de/tutorials_orca/index.
html. These sites involve an active discussion forum, step-by-step tutorials as well as video lectures covering many of the subjects dis-
cussed here.

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How to cite this article: Neese F. Software update: The ORCA program system—Version 5.0. WIREs Comput
Mol Sci. 2022;12:e1606. https://doi.org/10.1002/wcms.1606