Software Focus

The ORCA program system

Frank Neese∗

ORCA is a general-purpose quantum chemistry program package that features

virtually all modern electronic structure methods (density functional theory,
many-body perturbation and coupled cluster theories, and multireference and
semiempirical methods). It is designed with the aim of generality, extendibility,
efficiency, and user friendliness. Its main field of application is larger molecules,
transition metal complexes, and their spectroscopic properties. ORCA uses stan-
dard Gaussian basis functions and is fully parallelized. The article provides an
overview of its current possibilities and documents its efficiency. C 2011 John Wiley
& Sons Ltd.

How to cite this article:

WIREs Comput Mol Sci 2012, 2: 73–78 doi: 10.1002/wcms.81

PROGRAM DESIGN for individual atoms. Effective core potentials (ECPs)

O RCA is a flexible electronic structure project
that was initiated in 1999. Executables (but not
source code) can be obtained free of charge (for aca-
demics) from http://www.thch.uni-bonn.de/tc/orca/.
Highlights of the program are user friendliness, flexi-
bility, and efficiency. It has been written from scratch
in a straightforward way (simplicity and readability
being given preference over elegance in programming)
using C++ and is completely parallelized using the
message passing interface (MPI). Platform or third-
party library dependence was carefully avoided. The
only exceptions are the basic linear algebra subrou-
tines (BLAS), the Message Passing Interface (MPI),
and a very small amount of the Linear Algebra PAck-
age (LAPACK). ORCA compiles out of the box on
any platform with a standard C++ compiler.
SELF-CONSISTENT FIELD METHODS
ORCA uses contracted Gaussian basis functions in
conventional, semidirect, and direct integral handling
models. It is most efficient with segmented contracted
bases, where it is probably comparable in speed to the
most efficient alternative programs. A special integral
branch exists for dealing with generally contracted
atomic natural orbital basis sets. Basis sets are in-
ternally stored in a fairly comprehensive library but
can be read from a file, changed for atom types or
∗
Correspondence to: neese@thch.uni-bonn.de
Lehrstuhl für Theoretische Chemie, Universität Bonn, Institut für
Physikalische und Theoretische Chemie, Bonn, Germany
DOI: 10.1002/wcms.81
and associated basis sets are available for all of the
periodic table.
Closed-shell (RHF), spin-unrestricted (UHF),
and restricted open-shell (ROHF) self-consistent field
(SCF) calculations on the basis of various density
functional theory (DFT) methods as well as Hartree–
Fock (HF) theory are available. The program recog-
nizes and optionally maintains molecular symmetry
(D2h and subgroups) but so far makes little use of it
in speeding up calculations.
Available DFT functionals include Generalized
Gradient Approximation (GGA), meta-GGA, hybrid
DFT (HDFT), and double-hybrid DFT (DHDFT)
functionals (Table 1). Grimme’s semiempirical Van
der Waals corrections to DFT are implemented.
Semiempirical methods in ORCA include Zerner’s In-
termediate Neglect of Differential Overlap (ZINDO),
Modified Neglect of Differential Overlap (MNDO),
AM1, and PM3.
Initial guesses are flexible and include transfer-
ring wavefunctions from one geometry to another
or from one basis set to another. Broken-symmetry
SCF solutions can be searched for with specialized
techniques. A variety of options exist for speeding
up convergence including a quadratically convergent
Newton–Raphson procedure.
Population analysis according to the Löwdin,
Mulliken, and Mayer procedures is available through-
out ORCA. An interface to the natural bond order
(GENNBO) program is provided (http://www.chem.
wisc.edu/∼nbo5/). Electrostatic-potential-derived
charges [CHarges from Electrostatic Potentials using
a Grid based method (CHELPG)] can be generated as
well.

Volume 2, January/February 2012 

c 2011 John Wiley & Sons, Ltd. 73
Software Focus
T A B L E 1 Exchange and Correlation Functionals Built Into ORCA.
Exchange
Correlation
For functionals with no HF exchange, the
resolution-of-the-identity (RI) approximation is ex-
ploited and greatly speeds up the calculation of the
Coulomb term (RI-J). Exchange-correlation terms
are handled by numerical integration using standard
techniques.
The nonlocal HF exchange term can be approx-
imated in an efficient way (asymptotically linear scal-
ing Chain Of Spheres (COSX) algorithm; similar to
pseudospectral techniques) and combined with RI-J
to give the popular RIJCOSX approximation.1
RELATIVISTIC OPTIONS
Scalar-relativistic all-electron calculations are avail-
able. The latter can be done using the zeroth-order
regular approximation (ZORA) [or the infinite-order
regular approximation (IORA)]. Alternatively, the
second-order Douglas–Kroll–Hess (DKH) Hamilto-
nian is available in the standard implementation.
Two-component methods are not supported. Analytic
derivatives are available for all of these methods; ge-
ometry optimizations using scalar-relativistic Hamil-
tonians use the one-center approximation.
A set of segmented-all-electron relativistically
contracted (SARC) basis sets were developed for
third-row transition metals, lanthanides and actinides
in ZORA and DKH2 versions. For the remaining el-
ements, the all-electron basis sets of Weigend et al.
were recontracted. All-electron and small-core ECP
calculations are usually of comparable efficiency.
Note a comprehensive study of the performance of
scalar relativistic and ECP-based DFT for transition
metal geometries.2
EXCITED STATE CALCULATIONS
Excited states can be calculated with all multirefer-
ence methods described below. For large molecules,
it is more convenient to resort to easier albeit much
less general methods. Such methods are implemented
in the orca cis program.
Configuration interaction (CI) with single exci-
tations (CIS) relative to an RHF or UHF reference
determinant and the associated time-dependent DFT
(TD-DFT) methods are available. CIS is known to
have major deficiencies and rarely (if ever) provides
balanced predictions for electronic spectra. In cases,
where it is reasonable starting point, a double correc-
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Slater, B88, G96, LB94, PBE, RPBE, PW91, mPW, TPSS, revTPSS, OPTX, B97,
VWN3, VWN5, PWLDA, P86, PW91, PBE, OP, TPSS, revTPSS, B97
tion improves results (CIS(D) method). The RIJCOSX
approximation leads to dramatic speedups at no loss
of accuracy. For HDFT, the Tamm–Dancoff approx-
imation (TDA) is presently obligatory. In conjunction
with the (D) correction, excited states can be calcu-
lated for DHDFs.3
Intensities for electronic transitions are com-
puted within the dipole length and dipole velocity
formalisms. Quadrupole and magnetic dipole intensi-
ties are optionally available. The latter become impor-
tant for the computation of X-ray absorption spectra
for which orca cis is widely used.4–6
Analytic gradients are available for CIS and
TD-DFT/TDA and form the basis for the efficient
calculation of resonance Raman spectra, and absorp-
tion and fluorescence bandshapes, all of which are
available (orca asa module).7
MANY-BODY PERTURBATION
THEORY AND DHDFT
ORCA features an efficient implementation of
second-order Möller–Plesset perturbation theory
(MP2) and its spin-component-scaled variant (SCS-
MP2) for energies and analytic gradients on the basis
of RHF, UHF, or ROHF wavefunctions. Whereas the
canonical MP2 implementation is fairly efficient, most
calculations are done within the RI-MP2 approxima-
tion. Analytic gradients for DHDFs in RI and non-RI
variants are implemented.8
Despite the unfavorable O(N5 ) scaling, the RI-
MP2 step is usually much faster than the preced-
ing SCF calculation, even for systems with more
than 2000 basis functions. The combination of RI-
MP2 with the RIJCOSX approximation is partic-
ularly powerful. This is also available for analytic
gradients.9 The orbital-optimized MP2 is available
and improves results for open-shell molecues.10 It
has been argued to be similar to the popular CC2
method.10
COUPLED PAIR AND COUPLED
CLUSTER METHODS
Canonical Methods
ORCA features an efficient and parallel module to cal-
culate closed-shell and spin-unrestricted coupled clus-
ter energies including single and double excitations
(CCSD), as well as perturbative triple excitations
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 WIREs Computational Molecular Science
(CCSD(T)). The closely related quadratic CI (QCI)
method is available. A comprehensive set of the
recently revived coupled-electron pair (CEPA) meth-
ods is implemented.11,12 For all methods, implemen-
tations exist that involve either a full four-index trans-
formation or only a partial transformation involving
integrals with up to two external labels, whereas the
remaining terms are directly formed in the atomic-
orbital basis. If triples are computed, all integrals with
up to three external labels must be stored on disk,
which limits the applicability. Orbital optimization,
natural orbital iterations, and generation of Brückner
orbitals are supported. Spin-component-scaled third-
order perturbation theory (SCS-MP3) can be per-
formed. Analytic gradients and use of symmetry has
not been implemented. Arbitrary-order coupled clus-
ter energies (but not gradients or densities) can be
obtained via an interface to Mihail Kally’s MRCC
program (http://tc03.fkt.bme.hu/).
Local Correlation Methods
The local-pair natural orbital (LPNO) approach has
been recently developed.13,14 The LPNO–CEPA and
LPNO–CCSD methods have been shown to faith-
fully (within a few tenth of a kilocalorie per mole)
reproduce the results of canonical CCSD and CEPA
calculations while leading to speedups of up to and
exceeding three orders of magnitude. The LPNO ap-
proximation is particularly effective in conjunction
with large basis sets. Calculations involving 1000–
2000 basis functions can be routinely done with
the code in an entirely black-box fashion. Typically,
the correlation calculation takes only two to four
times longer than the preceding SCF step. Thus, these
methods are well suited for large-scale computational
chemistry.15,16
MULTIREFERENCE METHODS
Complete Active Space SCF
A flexible and efficient program for the generation of
complete active space SCF (CASSCF) wavefunctions
is part ORCA. The program allows for the averaging
of an arbitrary number of roots of varying spatial
symmetry and multiplicity. The program generally
cycles between CI and orbital optimization steps.
A variety of first- and second-order convergence
accelerating methods is available. Use of the RI ap-
proximation can be made in the integral transfor-
mation steps. The calculation of Fock-like matrices
supports the RIJCOSX and RI-JK approximations.
Large orbital (up to ∼2000 basis functions) and ac-
tive spaces (∼14–16 active orbitals) can be treated.
Analytic gradients are available.
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The ORCA program system
Multireference Perturbation Theory
A highly efficient way to obtain second-order pertur-
bation energies even for large orbital and active spaces
is provided by N-electron valence perturbation theory
(NEVPT2) that is available in a particularly efficient
implementation. NEVPT2 is similar in scope to the
popular CASPT2 method, but in our opinion, fea-
tures a number of advantages: (1) it is intruder state
free due to the choice of the zeroth-order Hamilto-
nian (Dyall Hamiltonian), (2) it is diagonal such that
no linear equation systems need to be solved and no
large sets of coefficients need to be stored, and (3) it
is strongly contracted such that no linear dependen-
cies and nonorthogonal configuration state functions
(CSFs) are ever generated. The challenging steps in an
NEVPT2 calculation are the integral transformation
with integrals up to two external labels and the gen-
eration of the up to fourth-order density matrix. Effi-
cient approximations for both steps are available, and
in general, the calculation of the second-order pertur-
bation energies for all roots involved in the CASSCF
is usually much faster than the CASSCF step itself.
Multireference CI and Related Methods
A flexible module for the generation of multirefer-
ence CI (MR-CI) and related wavefunctions is avail-
able. It is using spin- and space-symmetry-adapted
single-configuration CSFs to expand the wavefunc-
tion and is hence limited to reasonably small reference
spaces. Any set of reference CSFs can be employed
and an arbitrary number of blocks of varying spin
symmetry and space symmetry can be treated at the
same time. Individual selection and reference space
selection is (optionally) performed. Four-index inte-
grals can be generated on the fly from RI-generated
three-index integrals. The program also features MR-
Average Coupled Pair Functional (ACPF) and MR-
Average Quadratic Coupled Cluster (AQCC), as well
as a variety of difference dedicated CI methods that
can be extended to larger molecules (∼50 atoms or
1000 basis functions). The spectroscopy-oriented CI
method17 is original to ORCA.
Incorporation of Relativistic Effects by
Quasi-Degenerate Perturbation Theory
The CASSCF/NEVPT2 and MR-CI modules feature
analogous options, which allow the rediagonalization
of a relativistic Hamiltonian, which includes spin–
orbit coupling (SOC), spin–spin coupling (SSC), and
linear external magnetic fields in a basis of roots of the
Born–Oppenheimer Hamiltonian [quasi-degenerate
perturbation theory (QDPT)]. All magnetic sublevels
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Software Focus
M = S, S − 1, . . . , −S are generated for each root
with total spin S, and the matrix elements over the
relativistic many particle Hamiltonian is calculated
using Wigner–Eckart algebra.18 Any number of mul-
tiplicities and spatial symmetries can be included in
these calculations. In the case of NEVPT2, the matrix
elements are computed over state-averaged CASSCF
wavefunctions, whereas the diagonal energies of the
QDPT matrix carry the dynamic correlation correc-
tion brought in by NEVPT2. A number of spectro-
scopic parameters, including absorption and circular
dichroism (CD) spectra, Magnetic Circular Dichro-
ism (MCD) spectra, g-values, and zero-field splittings
(ZFSs), can be calculated in this way.
COMBINED QUANTUM
MECHANICAL/MOLECULAR
MECHANICAL AND RELATED
METHODS
ORCA can be easily interfaced with existing Com-
bined Quantum Mechanical/Molecular Mechanical
(QM/MM) package and supports the incorporation
of large sets of external point charges into the quan-
tum Hamiltonian as well as the calculation of all nec-
essary analytic gradients. ORCA is successfully used
together with ChemShell. An interface is supported
by Gromacs and pDynamo.
SOLVATION
ORCA supports the conductor-like screening
(COSMO) polarizable continuum model throughout
all its modules and also in all implemented analytic
gradients. The direct COSMO-RS method19 is also
available.
GEOMETRY OPTIMIZATION
Geometry optimization is most conveniently per-
formed using a set of program-generated redundant
internal coordinates. These coordinates can be user
modified. Special provision is made for disjoint molec-
ular fragments. Any number of constraints can be
imposed on the positions of individual atoms, bonds,
angles, or dihedrals. If desired, the program only op-
timizes the positions of hydrogen atoms or can in-
vert all constraints. Relaxed surface scans can be
generated. Constraints do not need to be satisfied
in the starting geometries. The program will auto-
matically reassign coordinates if the set of redundant
internal coordinates becomes invalid, e.g., because an
angle is approaching linearity. Several initial Hessian
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estimates are supported. Calculated Hessians (e.g.,
from a lower level of theory) can be fed into the
program. The popular Broyden–Fletcher–Goldfarb–
Shanno (BFGS) Hessian update is generally used.
Transition states are located using eigenvector
following. The initial Hessian does not need to have a
single negative frequency. The program will use user-
supplied information in order to follow the mode of
interest. A partial Hessian involving only those atoms
that are implicated most strongly in the transition
state vector can be calculated to initiate the search.
This can save large amounts of computer time. The
Bofill update is used by default.
A special application is a method for the loca-
tion of minimum-energy crossing points between two
potential surfaces. It is implemented in ORCA for all
methods that deliver analytic gradients.
FREQUENCIES
ORCA only supports the calculations of numerical
harmonic frequencies from the differentiation of ana-
lytic gradients. Single- or double-sided numerical fre-
quencies can be calculated. This part of the program is
parallelized for many cores using a master/slave strat-
egy. A similar parallel implementation is available for
numerical gradients of methods for which no analytic
gradients have been coded (e.g., CCSD(T)).
SPECTROSCOPIC PROPERTIES
Electron Paramagnetic Resonance and
Nuclear Magnetic Resonance
The spin-Hamiltonian parameters that enter electron
paramagnetic resonance spectra have always been
a focal point in the development of ORCA. Most
commonly, DFT linear-response methods are used.
These methods are available for the g-tensor, the SSC
and SOC contributions to the ZFS tensor, all three
parts of the hyperfine coupling tensor, as well as for
electric field gradient tensors. Scalar-relativistic cor-
rections including picture change effects are avail-
able for all of these parameters using the DKH
and ZORA Hamiltonians. The spin–orbit mean-field
approximation to the SOC operator is used in an effi-
cient implementation.20 In the presence of near orbital
degeneracy, all of these parameters can be computed
on the basis of CASSCF, MR-CI, or NEVPT2 calcu-
lations using QDPT methods, as described above.
Mössbauer Spectroscopy
The calculation of Mössbauer parameters is a minor
addition that can be achieved with the orca eprnmr
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 WIREs Computational Molecular Science
module following a simple calibration procedure.21,22
Such calculations on the basis of DFT have seen many
successful applications.
Infrared and Raman Spectroscopy.
Thermodynamic Properties
Infrared and Raman spectra are computed on the
basis of harmonic frequencies that are presently
computed using HF, DFT, or MP2 wavefunctions.
Likewise, thermodynamic corrections to the calcu-
lated electronic energies are obtained using standard
ideal gas equations. A nonstandard application is the
calculation of nuclear resonance vibrational spectra
for which ORCA contains a specifically advanced
module.23 Vibrational modes can be animated and
conveniently analyzed according to the contributions
of individual bond stretches.
Absorption and CD Spectroscopy
Absorption and CD spectra can be computed on the
basis of CIS, CIS(D), TD-DFT, CASSCF, NEVPT2,
or MR-CI calculations, as described above.
Magnetic CD Spectroscopy
ORCA features a fairly advanced implementation on
the basis of QDPT for MR-CI and NEVPT2 multiref-
erence approaches.24
REFERENCES
1. Neese F, Wennmohs F, Hansen A, Becker U. Efficient,
approximate and parallel Hartree–Fock and hybrid
DFT calculations. A ‘chain-of-spheres’ algorithm for
the Hartree–Fock exchange. Chem Phys 2009, 356:98–
109.
2. Bühl M, Reimann C, Pantazis DA, Bredow T, Neese
F. Geometries of third-row transition-metal complexes
from density-functional theory. J Chem Theo Comp
2008, 4:1449–1459.
3. Grimme S, Neese F. Double hybrid density functional
theory for excited states of molecules. J Chem Phys
2007, 127:154116.
4. DeBeer George S, Petrenko T, Neese F. A simple time-
dependent density functional theory based protocol for
the prediction of X-ray absorption spectra. I. Ligand
K-edges. Inorg Chim Acta 2007, 361:965–972.
5. DeBeer George S, Petrenko T, Neese F. Prediction of
iron-K-edge absorption spectra using time-dependent
density functional theory. J Phys Chem A 2008,
112:12936–11294.
Volume 2, January/February 2012 
c 2011 John Wiley & Sons, Ltd.
The ORCA program system
Absorption and Fluorescence Bandshapes,
and Resonance Raman Spectroscopy
ORCA features a highly efficient implementation
based on analytic gradient techniques in conjunction
with Heller’s time-dependent semiclassical theory.7
The orca asa module that carries out these calcula-
tions can also be operated in a stand-alone mode
that allows for the fitting and analysis of experimental
spectra.
X-Ray Absorption and Emission
Spectroscopy
X-ray absorption spectra can be fairly successfully
calculated on the basis of TD-DFT approaches, as
described above.4–6 X-ray emission spectra are suc-
cessfully predicted with an even simple one-electron
approach.25 Importantly, quadrupole contributions
to the absorption and emission cross sections must
be taken into account for calculations on metal K-
edges.4,5 Standard protocols for the calculation of
these spectra have been proposed.6
CONCLUSION
It has hopefully become plausible that ORCA is a
powerful, efficient, and flexible multipurpose research
tool that can be used for a wide range of computa-
tional chemistry applications. It is user friendly and
free of charge for academic researchers.
6. DeBeer S, Neese F. Calibration of scalar relativistic
density functional theory for the prediction of sulfur K-
edge absorption spectra. Inorg Chem 2010, 49:1849–
1853.
7. Petrenko T, Neese F. A general efficient quantum chem-
ical method for predicting absorption bandshapes, res-
onance Raman spectra and excitation profiles for larger
molecules. J Chem Phys 2007, 127:164319.
8. Neese F, Schwabe T, Grimme S. Analytic derivatives
for perturbatively corrected ‘double hybrid’ density
functionals. J Chem Phys 2007, 126:124115.
9. Kossmann S, Neese F. Efficient structure optimiza-
tion with second-order many-body perturbation the-
ory. The RJCOSX MP2 method. J Chem Theo Comp
2010, 6:2325–2338.
10. Neese F, Schwabe T, Kossmann S, Schirmer B, Grimme
S. Assessment of orbital optimized, spin-component
scaled second order many body perturbation theory
for thermochemistry and kinetics. J Chem Theo Comp
2009, 5:3060–3073.
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Software Focus
11. Neese F, Wennmohs F, Hansen A, Grimme S. Accurate
theoretical chemistry with coupled electron pair mod-
els. Acc Chem Res. In press. doi:10.1021/ar800241t.
12. Wennmohs F, Neese F. A comparative study of single
reference correlation methods of the coupled-pair type.
Chem Phys 2008, 343:217–230.
13. Neese F, Wennmohs F, Hansen A. Efficient and ac-
curate local approximations to coupled electron pair
approaches. An attempt to revive the pair-natural or-
bital method. J Chem Phys 2009, 130:114108.
14. Neese F, Liakos D, Hansen A. Efficient and accurate
local approximations to the coupled cluster singles and
doubles method using a truncated pair natural orbital
basis. J Chem Phys 2009, 131:064103.
15. Anoop A, Thiel W, Neese F. A local pair natural orbital
coupled cluster study of Rh catalyzed asymmetric olefin
hydrogenation. J Chem Theo Comp 2010, 10:3137–
3144.
16. Liakos DG, Neese F. Weak molecular interactions
studied with parallel implementations of the local pair
natural orbital coupled pair and coupled cluster meth-
ods. J Chem Theo Comp 2010, 6:3137–3144.
17. Neese F. A spectroscopy oriented configuration inter-
action procedure. J Chem Phys 2003, 119:9428–9443.
18. Neese F, Petrenko T, Ganyushin D, Olbrich G. Ad-
vanced aspects of ab initio theoretical spectroscopy
of open-shell transition metal ions. Coord Chem Rev
2007, 251:288–327.
FURTHER READING/RESOURCES
More information on ORCA including an extensive manual can be obtained free of charge under http://www.thch.
uni-bonn.de/tc/orca/
78 
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19. Sinnecker S, Rajendran A, Klamt A, Diedenhofen M,
Neese F. Calculation of solvent shifts on electronic
g-tensors with the conductor-like screening model
(COSMO) and its self-consistent generalization to
real solvents (COSMO-RS). J Phys Chem A 2006,
110:2235–2245.
20. Neese F. Efficient and accurate approximations to the
molecular spin-orbit coupling operator and their use
in molecular g-tensor calculations. J Chem Phys 2005,
122:034107/034101–034113.
21. Römelt M, Ye S, Neese F. Calibration of Mössbauer
isomer shift calculations for modern density functional
theory: meta-GGA and double hybrid functionals.
Inorg Chem 2009, 48:784–785.
22. Neese F. Prediction and interpretation of isomer
shifts in 57 Fe Mössbauer spectra by density func-
tional theory. Inorg Chim Acta 2002, 337C:181–
192.
23. Petrenko T, Sturhahn W, Neese F. First principles
calculation of nuclear resonance vibrational spectra.
Hyperfine Int 2007, 175:165–174.
24. Ganyushin D, Neese F. First principles calculation
of magnetic circular dichroism spectra. J Chem Phys
2008, 128:114117.
25. Lee N, Petrenko T, Bergmann U, Neese F, DeBeer
S. Probing valence orbital composition with iron Kβ
X-ray emission spectroscopy. J Am Chem Soc 2010,
132:9715–9727.
Volume 2, January/February 2012