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, efciency, and user friendliness. Its main eld of application is larger molecules, transition metal complexes, and their spectroscopic properties. ORCA uses standard Gaussian basis functions and is fully parallelized. The article provides an overview of its current possibilities and documents its efciency. C 2011 John Wiley
& Sons Ltd.

How to cite this article:

WIREs Comput Mol Sci 2012, 2: 7378 doi: 10.1002/wcms.81

PROGRAM DESIGN
RCA is a exible electronic structure project that was initiated in 1999. Executables (but not source code) can be obtained free of charge (for academics) from http://www.thch.uni-bonn.de/tc/orca/. Highlights of the program are user friendliness, exibility, and efciency. 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 thirdparty library dependence was carefully avoided. The only exceptions are the basic linear algebra subroutines (BLAS), the Message Passing Interface (MPI), and a very small amount of the Linear Algebra PAckage (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 efcient with segmented contracted bases, where it is probably comparable in speed to the most efcient alternative programs. A special integral branch exists for dealing with generally contracted atomic natural orbital basis sets. Basis sets are internally stored in a fairly comprehensive library but can be read from a le, changed for atom types or

Correspondence to: neese@thch.uni-bonn.de

Lehrstuhl fur Theoretische Chemie, Universitat Bonn, Institut fur Physikalische und Theoretische Chemie, Bonn, Germany DOI: 10.1002/wcms.81

for individual atoms. Effective core potentials (ECPs) 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 eld (SCF) calculations on the basis of various density functional theory (DFT) methods as well as Hartree Fock (HF) theory are available. The program recognizes 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). Grimmes semiempirical Van der Waals corrections to DFT are implemented. Semiempirical methods in ORCA include Zerners Intermediate Neglect of Differential Overlap (ZINDO), Modied Neglect of Differential Overlap (MNDO), AM1, and PM3. Initial guesses are exible and include transferring 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 NewtonRaphson procedure. Population analysis according to the Lowdin, Mulliken, and Mayer procedures is available throughout 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.
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T A B L E 1 Exchange and Correlation Functionals Built Into ORCA.

Exchange Correlation Slater, B88, G96, LB94, PBE, RPBE, PW91, mPW, TPSS, revTPSS, OPTX, B97, VWN3, VWN5, PWLDA, P86, PW91, PBE, OP, TPSS, revTPSS, B97

For functionals with no HF exchange, the resolution-of-the-identity (RI) approximation is exploited 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 approximated in an efcient way (asymptotically linear scaling 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 available. The latter can be done using the zeroth-order regular approximation (ZORA) [or the innite-order regular approximation (IORA)]. Alternatively, the second-order DouglasKrollHess (DKH) Hamiltonian is available in the standard implementation. Two-component methods are not supported. Analytic derivatives are available for all of these methods; geometry optimizations using scalar-relativistic Hamiltonians 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 elements, the all-electron basis sets of Weigend et al. were recontracted. All-electron and small-core ECP calculations are usually of comparable efciency. Note a comprehensive study of the performance of scalar relativistic and ECP-based DFT for transition metal geometries.2

tion improves results (CIS(D) method). The RIJCOSX approximation leads to dramatic speedups at no loss of accuracy. For HDFT, the TammDancoff approximation (TDA) is presently obligatory. In conjunction with the (D) correction, excited states can be calculated for DHDFs.3 Intensities for electronic transitions are computed within the dipole length and dipole velocity formalisms. Quadrupole and magnetic dipole intensities are optionally available. The latter become important for the computation of X-ray absorption spectra for which orca cis is widely used.46 Analytic gradients are available for CIS and TD-DFT/TDA and form the basis for the efcient calculation of resonance Raman spectra, and absorption and uorescence bandshapes, all of which are available (orca asa module).7

MANY-BODY PERTURBATION THEORY AND DHDFT

ORCA features an efcient implementation of second-order MollerPlesset perturbation theory (MP2) and its spin-component-scaled variant (SCSMP2) for energies and analytic gradients on the basis of RHF, UHF, or ROHF wavefunctions. Whereas the canonical MP2 implementation is fairly efcient, most calculations are done within the RI-MP2 approximation. Analytic gradients for DHDFs in RI and non-RI variants are implemented.8 Despite the unfavorable O(N5 ) scaling, the RIMP2 step is usually much faster than the preceding SCF calculation, even for systems with more than 2000 basis functions. The combination of RIMP2 with the RIJCOSX approximation is particularly 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

EXCITED STATE CALCULATIONS

Excited states can be calculated with all multireference 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. Conguration interaction (CI) with single excitations (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 deciencies and rarely (if ever) provides balanced predictions for electronic spectra. In cases, where it is reasonable starting point, a double correc-

COUPLED PAIR AND COUPLED CLUSTER METHODS Canonical Methods

ORCA features an efcient and parallel module to calculate closed-shell and spin-unrestricted coupled cluster energies including single and double excitations (CCSD), as well as perturbative triple excitations

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(CCSD(T)). The closely related quadratic CI (QCI) method is available. A comprehensive set of the recently revived coupled-electron pair (CEPA) methods is implemented.11 , 12 For all methods, implementations exist that involve either a full four-index transformation or only a partial transformation involving integrals with up to two external labels, whereas the remaining terms are directly formed in the atomicorbital 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 Bruckner orbitals are supported. Spin-component-scaled thirdorder perturbation theory (SCS-MP3) can be performed. Analytic gradients and use of symmetry has not been implemented. Arbitrary-order coupled cluster energies (but not gradients or densities) can be obtained via an interface to Mihail Kallys MRCC program (http://tc03.fkt.bme.hu/).

Multireference Perturbation Theory

A highly efcient way to obtain second-order perturbation energies even for large orbital and active spaces is provided by N-electron valence perturbation theory (NEVPT2) that is available in a particularly efcient implementation. NEVPT2 is similar in scope to the popular CASPT2 method, but in our opinion, features a number of advantages: (1) it is intruder state free due to the choice of the zeroth-order Hamiltonian (Dyall Hamiltonian), (2) it is diagonal such that no linear equation systems need to be solved and no large sets of coefcients need to be stored, and (3) it is strongly contracted such that no linear dependencies and nonorthogonal conguration 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 generation of the up to fourth-order density matrix. Efcient approximations for both steps are available, and in general, the calculation of the second-order perturbation energies for all roots involved in the CASSCF is usually much faster than the CASSCF step itself.

Local Correlation Methods

The local-pair natural orbital (LPNO) approach has been recently developed.13 , 14 The LPNOCEPA and LPNOCCSD methods have been shown to faithfully (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 approximation 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 CI and Related Methods

A exible module for the generation of multireference CI (MR-CI) and related wavefunctions is available. It is using spin- and space-symmetry-adapted single-conguration CSFs to expand the wavefunction 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 integrals can be generated on the y from RI-generated three-index integrals. The program also features MRAverage Coupled Pair Functional (ACPF) and MRAverage 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.

MULTIREFERENCE METHODS Complete Active Space SCF

A exible and efcient 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 rst- and second-order convergence accelerating methods is available. Use of the RI approximation can be made in the integral transformation steps. The calculation of Fock-like matrices supports the RIJCOSX and RI-JK approximations. Large orbital (up to 2000 basis functions) and active spaces (1416 active orbitals) can be treated. Analytic gradients are available.

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), spinspin coupling (SSC), and linear external magnetic elds in a basis of roots of the BornOppenheimer Hamiltonian [quasi-degenerate perturbation theory (QDPT)]. All magnetic sublevels

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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 WignerEckart algebra.18 Any number of multiplicities 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 correction brought in by NEVPT2. A number of spectroscopic parameters, including absorption and circular dichroism (CD) spectra, Magnetic Circular Dichroism (MCD) spectra, g-values, and zero-eld splittings (ZFSs), can be calculated in this way.

COMBINED QUANTUM MECHANICAL/MOLECULAR MECHANICAL AND RELATED METHODS

ORCA can be easily interfaced with existing Combined Quantum Mechanical/Molecular Mechanical (QM/MM) package and supports the incorporation of large sets of external point charges into the quantum Hamiltonian as well as the calculation of all necessary analytic gradients. ORCA is successfully used together with ChemShell. An interface is supported by Gromacs and pDynamo.

estimates are supported. Calculated Hessians (e.g., from a lower level of theory) can be fed into the program. The popular BroydenFletcherGoldfarb 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 usersupplied 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 Boll update is used by default. A special application is a method for the location 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 analytic gradients. Single- or double-sided numerical frequencies can be calculated. This part of the program is parallelized for many cores using a master/slave strategy. A similar parallel implementation is available for numerical gradients of methods for which no analytic gradients have been coded (e.g., CCSD(T)).

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.

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 hyperne coupling tensor, as well as for electric eld gradient tensors. Scalar-relativistic corrections including picture change effects are available for all of these parameters using the DKH and ZORA Hamiltonians. The spinorbit mean-eld approximation to the SOC operator is used in an efcient 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 calculations using QDPT methods, as described above.

GEOMETRY OPTIMIZATION
Geometry optimization is most conveniently performed using a set of program-generated redundant internal coordinates. These coordinates can be user modied. Special provision is made for disjoint molecular fragments. Any number of constraints can be imposed on the positions of individual atoms, bonds, angles, or dihedrals. If desired, the program only optimizes the positions of hydrogen atoms or can invert all constraints. Relaxed surface scans can be generated. Constraints do not need to be satised in the starting geometries. The program will automatically reassign coordinates if the set of redundant internal coordinates becomes invalid, e.g., because an angle is approaching linearity. Several initial Hessian

Mossbauer Spectroscopy
The calculation of Mossbauer parameters is a minor addition that can be achieved with the orca eprnmr

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module following a simple calibration procedure.21 , 22 Such calculations on the basis of DFT have seen many successful applications.

Absorption and Fluorescence Bandshapes, and Resonance Raman Spectroscopy

ORCA features a highly efcient implementation based on analytic gradient techniques in conjunction with Hellers time-dependent semiclassical theory.7 The orca asa module that carries out these calculations can also be operated in a stand-alone mode that allows for the tting and analysis of experimental spectra.

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 calculated 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 specically advanced module.23 Vibrational modes can be animated and conveniently analyzed according to the contributions of individual bond stretches.

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.46 X-ray emission spectra are successfully 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 Kedges.4 , 5 Standard protocols for the calculation of these spectra have been proposed.6

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.

CONCLUSION
It has hopefully become plausible that ORCA is a powerful, efcient, and exible multipurpose research tool that can be used for a wide range of computational chemistry applications. It is user friendly and free of charge for academic researchers.

Magnetic CD Spectroscopy
ORCA features a fairly advanced implementation on the basis of QDPT for MR-CI and NEVPT2 multireference approaches.24

REFERENCES
1. Neese F, Wennmohs F, Hansen A, Becker U. Efcient, approximate and parallel HartreeFock and hybrid DFT calculations. A chain-of-spheres algorithm for the HartreeFock exchange. Chem Phys 2009, 356:98 109. 2. Buhl 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, 4:14491459. 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 timedependent density functional theory based protocol for the prediction of X-ray absorption spectra. I. Ligand K-edges. Inorg Chim Acta 2007, 361:965972. 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, 112:1293611294.
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6. DeBeer S, Neese F. Calibration of scalar relativistic density functional theory for the prediction of sulfur Kedge absorption spectra. Inorg Chem 2010, 49:1849 1853. 7. Petrenko T, Neese F. A general efcient quantum chemical method for predicting absorption bandshapes, resonance Raman spectra and excitation proles 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. Efcient structure optimization with second-order many-body perturbation theory. The RJCOSX MP2 method. J Chem Theo Comp 2010, 6:23252338. 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, 5:30603073. 77

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11. Neese F, Wennmohs F, Hansen A, Grimme S. Accurate theoretical chemistry with coupled electron pair models. 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, 343:217230. 13. Neese F, Wennmohs F, Hansen A. Efcient and accurate local approximations to coupled electron pair approaches. An attempt to revive the pair-natural orbital method. J Chem Phys 2009, 130:114108. 14. Neese F, Liakos D, Hansen A. Efcient 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 olen 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 methods. J Chem Theo Comp 2010, 6:31373144. 17. Neese F. A spectroscopy oriented conguration interaction procedure. J Chem Phys 2003, 119:94289443. 18. Neese F, Petrenko T, Ganyushin D, Olbrich G. Advanced aspects of ab initio theoretical spectroscopy of open-shell transition metal ions. Coord Chem Rev 2007, 251:288327.

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, 110:22352245. 20. Neese F. Efcient and accurate approximations to the molecular spin-orbit coupling operator and their use in molecular g-tensor calculations. J Chem Phys 2005, 122:034107/034101034113. 21. Romelt M, Ye S, Neese F. Calibration of Mossbauer isomer shift calculations for modern density functional theory: meta-GGA and double hybrid functionals. Inorg Chem 2009, 48:784785. 22. Neese F. Prediction and interpretation of isomer spectra by density funcshifts in 57 Fe Mossbauer tional theory. Inorg Chim Acta 2002, 337C:181 192. 23. Petrenko T, Sturhahn W, Neese F. First principles calculation of nuclear resonance vibrational spectra. Hyperne Int 2007, 175:165174. 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 K X-ray emission spectroscopy. J Am Chem Soc 2010, 132:97159727.

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/

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