Quality Software. Quantum Science.

ADF www.scm.com Contents

Key benefits of ADF package...... 3

Our DFT programs ADF and BAND...... 5

Spectroscopic properties...... 6

Structure and reactivity...... 9

Model Hamiltonians...... 10

Chemical analysis...... 12

Accuracy and efficiency...... 14

DFTB and MOPAC...... 16

ReaxFF...... 17

COSMO-RS...... 18

Integrated Graphical User Interface...... 19

Background information...... 21

Feature list...... 22 Quality Software. Quantum Science.

Heavy elements & spectroscopy Molecules, surfaces & crystals Understand & predict Accurate & efficient User-friendly & expert support

The Amsterdam Density Functional software suite for chemistry and materials science: ● ADF: accurate DFT for molecules in gas and solution ● BAND: periodic DFT for solids, surfaces and polymers ● DFTB, MOPAC: fast approximate quantum methods (0-3D) ● ReaxFF: reactive MD of complex chemical systems ● COSMO-RS: quantum-based fluid thermodynamics ● GUI: easy preparation, execution and analysis

Key benefits of ADF package

Excels in modeling transition metals Spectroscopy and heavy elements ADF is a popular tool to predict and understand To treat molecules with heavy elements magnetic, electric, optical and vibrational accurately, relativistic effects need to be spectroscopy, in particular in systems with taken into account. ADF and BAND feature transition metals where relativistic effects play scalar relativistic and full spin-orbit coupling a defining role. The long list of available Hamiltonians through the zeroth-order regular spectroscopic properties, most of which can approximation (ZORA) of the Dirac equation. be calculated efficiently in parallel, continues All-electron basis sets for the entire periodic to expand. We provide the latest exchange- table remove the need for pseudopotentials/ correlation (xc) functionals, including model effective core potentials. Our modern SCF potentials specifically targeted at improved algorithms converge even for difficult systems, optical and magnetic spectra. such as open-shell transition metal compounds.

3 Structure & Reactivity Accurate, robust, fast, and easy to use ADF and BAND have an efficient and stable ADF has an accurate and tunable integration geometry optimizer for both minima and scheme and flexible and stable SCF convergence transitions states (TSs). Even notoriously difficult algorithms. Our software developers follow the TSs can be located with a properly defined TS latest trends in xc functionals, ensuring the reaction coordinate (TSRC). Nudged elastic availability of modern as well as old-time favorite band and IRC are available to trace full reaction xc functionals, including hybrids, metaGGAs and paths. Analytical second derivatives yield normal dispersion corrections. All-electron and frozen- modes and IR spectra, while Raman intensities core basis sets are available up to quadruple-zeta can be calculated for selected modes. Modern for the entire periodic table (H - Uuo). ADF’s meta-GGA, dispersion-corrected, and hybrid Slater-type basis sets resemble the true atomic functionals give excellent results for reaction orbitals more closely than commonly used barrier heights and various chemical analysis Gaussian functions, and are more efficient than tools provide unprecedented insight in structure plane waves for 1D, 2D, and empty 3D periodic and reactivity. structures. Linear scaling techniques and good parallelism up to hundreds of processor Molecules, clusters, polymers, cores makes ADF a very fast program. All our surfaces, solids, liquids programs and the easy graphical user interface The molecular ADF code treats molecules and run out of the box on Mac, Windows or Linux/ clusters in the gas phase or embedded in a UNIX. solvent or protein environment. Our periodic BAND program with localized orbitals deals Expert staff and support with solids as well as with periodic systems SCM provides expert technical and scientific in one (polymers) or two (slabs or surfaces) support by our highly trained team of theoretical dimensions, without resorting to an artificial chemists and physicists with many decades of and inefficient slab-gap approach. The DFTB combined experience in ADF development and and MOPAC programs are fast approximate applications. Active collaborations with a large quantum programs to calculate molecules or number of academic development groups and periodic systems (1D, 2D or 3D) while ReaxFF interactions with users ensure a rapid growth of is a reactive force field approach to study the ADF functionality at the forefront of research. chemical reaction dynamics of large 3D periodic boxes of complex systems (e.g. gas mixtures, solutions, liquid-surface interactions). Going beyond the atomistic level, the COSMO-RS module enables prediction of thermodynamic properties of solutions and mixed fluids (liquids and gases).

4 Our DFT programs: ADF and BAND

Key benefits for our molecular ADF and periodic BAND programs are summarized on the previous pages. Below we highlight a few of the ever-expanding list of capabilities.

ADF is an efficiently parallelized, powerful computational chemistry program to model, comprehend, and predict chemical structure and reactivity (p. 9). A vast range of spectroscopic properties can be calculated (p. 6), with inclusion of relativistic effects across the entire electromagnetic spectrum from radio waves (NMR) to γ-rays (Mössbauer spectroscopy). ADF can also optimize excited states and calculate phosphorescence with TDDFT, and calculate All-electric single-molecule motor calculated with ADF. electronic transport properties through Green’s See www.scm.com/News/Seldenthuis. functions.

Modern xc functionals (dispersion corrections, BAND shares a lot of functionality with the (hybrid) metaGGAs) as well as established molecular ADF code, including chemical analysis functionals (PBE0, B3LYP, BP86) are available (p. 12) and spectroscopic properties: NMR, EPR, and environment effects of solvents, electric and Electric Field Gradients (p. 6). BAND is the fields and large non-reactive parts (e.g. proteins, perfect companion to ADF for surface science, catalysts) can be accounted for in various ways featuring a true 2D approach for molecule- (p. 10). An extensive amount of comprehensive surface interactions, homogeneous electric analysis tools (p. 12) afford precious in-depth field, and local density of state (LDOS) for understanding in chemical structure and STM images. The analysis of molecule-surface reactivity. interactions is facilitated by a consistent accurate description of molecules and surfaces alike, with the same algorithms as ADF for explicit relativity, modern xc functionals, dispersion corrections, and solvent effects via COSMO. Specific properties for periodic systems include: phonon spectra and smooth band structures which can be visualized in our GUI with accompanying points and paths in the Brillouin zone, and frequency-dependent dielectric functions.

Solvated Ru complex on a TiO2 surface calculated with the COSMO model in BAND.

5 Spectroscopic properties

One of ADF’s strong points is the enormous IR, (resonance) Raman, VROA, VCD breadth of properties, which can be calculated Analytic and numerical second derivatives with high accuracy (basis sets, relativistic effects, yield IR frequencies and intensities. Raman modern functionals) and efficiency (linear scattering intensities and depolarization ratios scaling techniques, parallel implementation). may be calculated for all or for selected vibrations. ADF also features resonance Raman spectra, vibrational (resonance) Raman optical activities (VR(R)OAs), and vibrational circular dichroism (VCD) spectra.

The IR spectrum of Cr(CO)6 with animation of the vibrational modes.

(Vibrationally resolved) UV/Vis or X-ray spectra; (hyper)polarizabilities, vdW coefficients Excitation energies, oscillator strengths, for vibrationally resolved UV/Vis and X-ray frequency-dependent (hyper)polarizabilities spectra. X-ray structure factors for crystals can (nonlinear optics), and van der Waals dispersion be computed with BAND. Excitation energies coefficients, are all available in ADF as may be calculated state-selectively for open- applications of time-dependent DFT (TDDFT). and closed-shell systems. Unique to ADF, with self-consistent spin-orbit coupling TDDFT Dynamic polarizabilities are available through phosphorescence lifetimes can be calculated, calculated lifetimes at or near resonance. TDDFT important for Organic Light Emitting Diodes gradients allow excited state optimization (OLEDs), see http://www.scm.com/News/ and the calculation of Franck-Condon factors OLEDs.html.

6 Calculated vibronic fine structure of OLED emitter Pt(4,6-dFppy)(acac) in excellent agreement with experiment.

CD, ORD, MCD, Verdet constant, magnetizabilities Circular dichroism (CD) and optical rotatory dispersion (ORD) spectra of chiral molecules are available as an application of TDDFT in ADF. Also frequency-dependent magnetizabilities, Verdet constants, and the A, B, and C-terms of magnetic circular dichroism (MCD) can be calculated.

Calculated VCD spectra identify the absolute configuration of chiral molecules. V. P. Nicu and E.-J. Baerends, Phys. Chem. Chem. Phys. 11, 6107, (2009).

7 NMR, ESR, EFG, Mössbauer, NRVS Scalar relativistic or spin-orbit coupling in combination with all-electron Slater-type basis sets in ADF afford accurate NMR chemical shifts and spin-spin couplings, ESR (EPR) g-tensors, magnetic hyperfine tensors (A-tensors), zero-field splittings (ZFS, D-tensors), and nuclear quadrupole coupling constants (EFG, Q-tensors). Electron densities at the nucleus are available for Mössbauer spectroscopy and partial vibrational densities of states (PVDOS) yield nuclear resonance vibrational spectra (NRVS). For periodic structures NMR chemical shifts, EFG, and ESR (A-tensor, g-tensor) spectra are available through BAND. The experimental 29Si NMR spectrum of a PtSi complex can only be reproduced with full spin-orbit coupling calculations. Stars indicate spinning side bands and 195Pt satellites. L. A. Truflandier et al. Angew. Chem. Int. Ed. 50, 255 ( 2011).

Dielectric functions and EELS The TDDFT implementation in BAND enables the accurate calculation of frequency-dependent dielectric functions and the electron energy loss function (EELS). Metallic systems, including spin- orbit effects, are supported with the Vignale-Kohn approximation.

15 Copper

10

5

0 Dielectric function

-5 Dielectric function of Cu: calcd comparison between TDCDFT exp calculations (using the Vignale-

-10 Kohn functional) and experimental 0 2 4 6 8 10 results. Berger et al., Phys. Rev. B, Frequency (eV) 74, 245117 (2007).

8 Structure and reactivity

Minima and transition states (TSs) are most and restraints can also help to locate the desired effectively optimized with ADF’s delocalized stationary point more quickly. Apart from coordinates, which can also handle shallow eigenvector following, TSs may be optimized potential energy surfaces (PESs), for instance with the Nudged Elastic Band algorithm or by weak bonds and floppy modes. Scalar and spin- defining any combination of coordinates as a orbit relativistic effects may be included and Transition State Reaction Coordinate (TSRC). excited states can be optimized with TDDFT. Reaction paths are analyzed with intrinsic Especially beneficial to ensure expedient reaction coordinates (IRC) or linear transit convergence to the correct TS is the option (LT). Extensive analysis tools (p. 12) enable to generate an initial (partial) Hessian quickly deep insight in chemical reactivity, facilitating with MOPAC or DFTB or more accurately with prediction of structure-activity relationships for analytical GGA second derivatives. Constraints instance to generate new catalyst leads.

Increased activity of Pd-catalyzed allylic alkylation understood by destabilization of the Pd-allyl intermediate. Wassenaar, J. et al. Nature Chem. 2, 417-421 (2010).

TSs and minima in periodic systems can be calculated with BAND, which now also features full spin-orbit coupled gradients and lattice parameter optimization with numerical gradients. Several speed-ups enable BAND calculations on increasingly larger unit cells. Frequencies and phonon dispersion curves are available through numerical second derivatives. The latest xc functionals, including metaGGAs and dispersion corrections (D3, D3-BJ), are available as well as specialized xc functionals to obtain improved band gaps (GGA+U and TB-mBJ). Like with ADF, many analysis tools facilitate a detailed understanding of electronic structure and chemical reactivity (p. 12).

9 Model Hamiltonians

Transition metals and heavy elements ADF and BAND stand out in treating systems Users recommend our DFT software for the with metals and heavy atoms. Relativistic effects balanced, stable treatment of simple organics can be included accurately with ZORA (scalar and complex open-shell transition metal relativistic or spin-orbit coupling). All-electron compounds alike. Consequently, ADF and as well as frozen core basis sets up to quadruple BAND are popular computational tools in zeta are available for all elements (1-118) of organometallic and inorganic chemistry as well the periodic table. This removes the need for as materials science. pseudopotential/effective core potential (ECP) approximations, even for systems containing lanthanides or (trans)actinides.

Relativity in heavy elements at work: the voltage of lead batteries is greatly increased by relativistic shifts of the unoccupied Pb 6s states closer to the Fermi level. NR: non-relativistic, SR: scalar relativistic, FR: full relativistic (spin-orbit coupling). R. Ahuja et al. Phys. Rev. Lett. 106, 018301 ( 2011).

Modern xc energy functionals and potentials A variety of the most accurate modern (meta-)GGA and (meta) hybrid xc energy functionals are all evaluated simultaneously in ADF. Analytic second derivatives are available for (meta-)GGAs and analytic gradients for (meta)hybrid functionals (e.g. B3LYP, M06). Model xc potentials with correct asymptotic behavior, such as SAOP and GRAC are also available for reliable property calculations. BAND also offers the latest (meta-)GGAs, Hubbard U parameters, and LB94 and TB-mBJ model potentials. For weakly bound systems Grimme’s dispersion-corrected functionals (D3, D3-BJ) may be employed for geometry optimizations and frequency calculations in ADF and BAND.

10 Large systems: solvents, proteins and other environments Various strategies are available to study offers a subtractive ONIOM-like multi-level molecules or unit cells with many atoms. Fast approach in which many partitioned regions DFTB, semi-empirical (p. 16), and ReaxFF (p. can be treated at different levels of accuracy. 17) methods can treat up to thousands of Each region can be treated with MM, semi- atoms on a modern computer or small-sized empirical methods, DFTB or DFT, with the computer cluster, which makes them ideal tools added flexibility to vary basis set and xc to gain global, approximate insight in large functional per region. DFT-only calculations chemical systems. of large systems can be sped up with the frozen-density embedding (FDE) approach that Partitioning a molecule or protein in an active freezes part of the electron density of the site and its surroundings allows the chemically system. With the GUI it is straightforward to reactive part to be treated with high accuracy partition a large system into regions and set up DFT while the remainder is handled with QM/MM, QUILD, or FDE calculations. approximate, fast methods. Mixed quantum mechanics and molecular mechanics (QM/ Implicit solvent effects for molecules, polymers MM) calculations are available with standard and surfaces may be included with the (SYBYL, Amber, UFF) or user-specified force conductor-like screening model (COSMO), fields. The Discrete Reaction Field (DRF) model or for molecules with the three-dimensional enables QM/MM calculation with polarizable reference interaction site model (3D-RISM). MM atoms. The QUILD (QUantum regions Static homogeneous fields can be applied to Interconnected by Local Descriptions) tool molecules and surfaces.

With the GUI it is easy to partition systems into regions and set up QM/ MM, QUILD or FDE calculations.

MD, scripting, complex tasks Advanced molecular dynamics runs, including adaptive QM/MM or multi-level and biased MD (meta-dynamics) are available with the python interface PyMD. PyMD can use any combination of forces from our DFT, semi-empirical and MM codes. For advanced, complex jobs and multi-step workflows the open-source PyADF scripting environment can be used in addition to the ADF tools adfprepare and adfreport.

11 Chemical analysis

ADF contains several unique analysis options MOs of the complete system result from the to obtain a detailed understanding of the interaction of the Fragment Orbitals (FOs) of chemical problem at hand. These methods these chemically meaningful sub-units, handily stress the underlying philosophy that the Kohn- visualized as an interaction diagram with the Sham orbitals in DFT are meaningful for a GUI. quantitative Molecular Orbital (MO) theory. With the completely integrated GUI one can With Morokuma’s bond energy decomposition seamlessly switch between various analysis scheme the interaction energy is decomposed tools. in chemically intuitive quantities: symmetry adapted orbital interactions, electrostatic Molecule built from fragments energy and Pauli repulsion. With the extended In ADF the total system is built up from transition state - natural orbitals for chemical fragments, which can be entirely user- valence (ETS-NOCV) method charge, bond specified units such as atoms, molecules, order, and energetic analysis are combined in a and combinations or parts of molecules. The single framework.

ADF’s bond energy analysis from fragment orbitals gives unique insight in the bonding of complex systems like this Molybdenum - Zinc cluster. T. Cadenbach et al., Angew. Chem. Int. Ed. 47, 9150 - 9154 (2008).

12 Advanced charge density and paths and basins can be easily visualized with bond order analysis our GUI. Weinhold’s Natural Bond Order Mulliken charges are printed, however, (NBO - through GENNBO) and the Electron ADF offers much more robust, basis-set Localization Function (ELF) are also available. independent algorithms to assign atomic charges. The multipole-derived charge (MDC) Densities of States (DOS), band structures analysis reproduces dipole and higher multipole For both molecules and periodic systems, moments of the molecule exactly. Voronoi the total DOS and partial DOS (PDOS) can deformation density (VDD) and Hirshfeld be visualized with the GUI, and these can atomic charges are often in agreement with be further refined in terms of the atomic chemical intuition. Nalewajski bond orders orbital angular moment (s, p, d, f). Crystal can be calculated and correlate well with orbital overlap populations (COOP) can also experimental trends and chemical intuition, be calculated. Orbitals and density properties even for transition metal compounds. ADF and (AIM, ELF) are quickly evaluated and visualized BAND contain an extremely fast grid-based on a grid. With local DOS (LDOS) in BAND, implementation to calculate atoms-in-molecules STM images can be modeled. BAND produces (AIM, Bader analysis) properties, so that an smooth band structures through interpolation AIM analysis of a 300-atom carbon nanotube in k-space. only takes 2 minutes. Critical points, bond

Silicon band structure with Brillouin zone path visualization.

Molecular symmetry ADF uses the full molecular symmetry, including proper symmetry labels of orbitals, excitations, non-Abelian groups, such as C∞v, D∞h, Td, Oh, and vibrational modes are provided in the Ci, Cs, Cn, Cnv, Cnh, Dn, Dnv and Dnh. The output and in the GUI.

13 Accuracy and efficiency

Slater-type basis sets ADF uses Slater-Type Orbitals (STOs) as basis functions. These resemble the true atomic orbitals more closely than the more common Gaussian-Type Orbitals (GTOs). In particular, STOs have the correct behavior at the nucleus (cusp) and at long distances (e-r decay), which significantly improves the description of spectroscopic properties. Therefore, far fewer STOs than GTOs are needed for a given level Slaters give consistent and rapidly converging results of accuracy. ADF has a database consisting outperforming Gaussians and ECP. M. Güell, J. M. Luis, of thoroughly tested basis set files, ranging M. Solà, and M. Swart, J. Phys. Chem. A 112, 6384 (2008). in quality from single-zeta to quadruple-zeta basis sets with various diffuse and polarization Integration scheme functions. All-electron and frozen-core basis sets ADF uses the unique Te Velde - Baerends are available for all elements of the periodic table numerical integration scheme, in which the up to the transactinide Uuo (118). The frozen- grid is automatically adapted to the available core approximation can be used to considerably basis functions and to the number of significant reduce the computation time for systems with digits demanded by the user through a single heavy nuclei in a controlled manner. input parameter. It is straightforward to do very accurate integrations with far fewer points than in less highly developed schemes.

Single-CPU and parallel performance SCM cooperates with major hardware vendors to optimize performance of all our program modules for all popular computer platforms (Mac, Windows, Linux/UNIX). The code is fine- tuned and optimized for different compilers and hardware configurations.

The majority of our programs has been efficiently parallelized for both shared-memory and distributed memory systems, including multi-core desktop machines or simple Linux clusters. For many standard types of calculation, including NMR, analytical Hessian, and TDDFT calculations, ADF may scale well up to hundreds of processor cores. A shared-memory library Geometry optimization of a 197-atom system, DZP now removes previous memory bottlenecks basis set (2475 Cartesian basis functions) with M06-L, related to the memory available per processor performed by JACI on the TSUBAME2.0 supercomputer. core, thus enabling treatment of large molecules.

14 Linear scaling techniques Density fitting reduces the cost of calculating Coulomb integrals. Overlap integrals are negligible for atoms that are far apart and do not need to be evaluated, reducing the computational complexity for the most time- consuming parts from a cubic dependence to a linear dependence on the number of orbitals - from O(N3) to O(N). Linear scaling can be approached more efficiently for larger systems, leading to considerably faster results.

Symmetry ADF properly exploits symmetry to the fullest by calculating only symmetry-unique integration points and matrix elements. The considerable reduction of integration grids and matrices speed up the calculations accordingly.

By using symmetry, large nanotubes can be handled rapidly on a modern desktop computer.

Efficiency in BAND The localized atomic orbital (LCAO) basis sets employed in BAND allow for the proper modeling of one-dimensional (polymers) and two-dimensional (surfaces) periodic systems without artifacts and reduced performance arising from the artificial three-dimensional periodicity necessary in popular plane wave codes. BAND may employ precisely the same Slater orbitals as ADF, to facilitate comparison between molecules and condensed phase, but also features more accurate numerical atomic orbitals (exact solutions for the free atom).

Density properties, such as this STM image (LDOS) of Pt on Ge(100) are quickly calculated and visualized on a grid.

15 DFTB and MOPAC

Fast and effective Density Functional approach Density Functional based Tight Binding (DFTB) provides relatively accurate results at a fraction of the cost of a DFT evaluation through parameterization of the integrals. We continue to implement more DFTB parameters in view of the QUASINANO project in collaboration with Prof. Heine’s group. Parameters can also be obtained from www.dftb.org. Long-range interactions are described with empirical dispersion corrections and the novel DFTB3 approach handles charged systems accurately. As such, relatively accurate simulations of large systems and long time scales (molecular dynamics), can be achieved even on desktop computers.

With the GUI a large, complex system is set up with ease, and calculations can be run with DFTB or MOPAC on a desktop computer.

Semi-empirical program Pre-optimization for transition metals Three options are available for pre-optimization Stewart’s MOPAC2009 program is integrated for molecules as well as periodic systems (1D, 2D, in our GUI, and can currently be included 3D). By far the quickest method is the universal free of charge for academic ADF users. PM6 force field (UFF), which can be applied to the parameters are available for 70 elements, entire periodic table. If parameters are available including all transition metals (H - Bi, excluding for your system, the semi-empirical methods most Lanthanides). Recent refinements include MOPAC2009 and DFTB are also available as corrections for dispersion and hydrogen fast pre-optimizers that are generally more bonding (PM6-DH series). accurate than UFF. Through the integrated GUI, geometries and Hessians can be passed on easily between modules.

16 ReaxFF

Reactive molecular dynamics of large, complex systems The reactive force field method of van Duin and coworkers (J. Phys. Chem. A 105, 9396 (2001)) is aimed at understanding chemical reaction dynamics of complex mixtures and solid-liquid interfaces. SCM has parallelized the original ReaxFF code and further optimized it by removing memory bottlenecks. Systems Force field parameters are continuously being developed consisting of a 3D box of multiple molecules in order to tackle increasingly complex problems in totaling tens of thousands of atoms can now be material science, such as this H2O/Cu/ZnO system modeled on a desktop computer. (ongoing work van Duin/Hermansson)

Parameter sets are included for many molecules reacting with metal and metal oxide elements and new sets for specific and surfaces. Dynamics employ velocity Verlet with generic reaction systems are continuously a Berendsen thermostat for NVT, NPT or NVE being developed. Traditional force field ensembles and reactions may also be enforced lack this breadth and flexibility. ReaxFF has with constrained dynamics. Temperatures can been used over the past decade in various be initialized and ramped separately for each studies of inhomogeneous reactive systems, different region. With the GUI the systems can including solvent environments, interfaces, and be set up, run and visualized with ease.

A ReaxFF dynamics run (methane combustion) is visualized, tracking temperature, energy components and the concentrations of reactants, products and intermediates interactively.

17 COSMO-RS

Our COSMO-RS (COnductor like Screening COSMO-RS and COSMO-SAC utilize potentials MOdel for Realistic Solvents) program allows and sigma profiles from quantum mechanical the prediction of many properties of pure calculations on individual molecules as a basis fluids, fluid mixtures, and solutions: for its thermodynamical analysis. As such COSMO-RS has more predictive power outside  activity coefficients, solvation free energies the fit sets of more empirical, parameterized  Henry’s law constants methods (e.g. UNIFAC). A database with almost  solubility 1900 compounds, primarily solvents and small  partition coefficients (log P) molecules, is available to users to facilitate  partial/total vapor pressures, boiling points easy and rapid calculations. Performing DFT of solvents and mixtures calculations with ADF creates parameters for  vapor-liquid and liquid-liquid diagrams any additional compound of choice. The GUI binary and ternary mixtures (VLE/LLE) offers flexible visualization of diagrams and  excess energies GE, HE and TSE graphs for easy analysis.  azeotropes, miscibility gaps  pKa values

Vapor-liquid diagram (VLE) for ternary mixture of methanol, acetone and chloroform.

Solvent/water partition coefficients: experimental and computed with COSMO-RS.

18 Graphical User Interface for our modeling programs

With our single integrated Graphical User Structure builder Interface (GUI) it is straightforward to prepare, The powerful GUI has a sophisticated but execute, and visualize calculations with ADF, facile structure builder with a large database of BAND, DFTB, MOPAC, ReaxFF, and COSMO- structural motifs, (bio)molecules, and crystals. RS. Switching between different modeling Crystals can be manipulated to create supercells programs and analysis or visualization tools is or slabs and complex solvent or gas mixtures seamless with just the click of a mouse. The GUI can be created with Packmol, e.g. for use with works out of the box on any popular machine ReaxFF. Structures can be pre-optimized with (Windows, Mac or Linux) and calculations can UFF, MOPAC or DFTB and smoothly further be run and visualized cross-platform effortlessly. optimized and analyzed with full DFT in ADF or Tutorials and videos ensure that anyone can BAND. The preparation and analysis of multiple set up and visualize calculations within an hour jobs is a breeze. after downloading.

Build molecules with the extensive library or prepare surfaces with the easy crystal builder.

19 Visualization and analysis Jobs can be run on your local machine or on remote Linux clusters, and output can also be visualized cross-platform. With the GUI it is easy to analyze a wealth of calculated properties: level diagrams, Kohn-Sham orbitals, densities, contours, density of states (DOS), band structures (with Brillouin zone paths), and many spectra. All modeling and visualization modules are highly integrated to facilitate analysis. For instance, a vibration is visualized when its IR peak is clicked and orbitals involved in an excitation are shown when the one-electron contribution is clicked. Movies of vibrations, optimizations, IRCs, and molecular dynamics can be visualized and properties tracked. Various thermodynamic properties of fluid mixtures and solutions can be plotted with the COSMO-RS module.

Integration of visualization modules for easy operation and analysis.

20 Background

Supported platforms and source code SCM availability Originating from the small software The SCM suite of modeling software runs, development group at the Vrije Universiteit in in parallel with the provided Platform-MPI or Amsterdam, Scientific Computing & Modelling OpenMPI libraries, out of the box on 32 and N.V. (SCM) is now a thriving private company. 64 bits Windows PCs, Macs (10.5+), and Linux Our customers range from academic research machines. Most of the source code for ADF and groups to government laboratories to private BAND is available at an additional fee. Pre-built businesses with an interest in research and binaries are also available for other platforms development. SCM initiates its own ADF (Cray, AIX, SGI, Altix) and custom ports to developments through its team of highly other systems are considered upon request. trained theoretical chemists and physicist and coordinates development efforts from academic Free trial development groups worldwide. Maintenance, A free trial can be requested from the SCM updates, and distributions of our programs are web site: http://www.scm.com/trial. The handled by SCM. demo license is fully functional and runs on any machine to ensure that you can experience the License options usefulness of our powerful computational tools SCM’s software licenses can be tailored to in your R&D program. your specific situation. We offer regional and teaching-only discounts on top of academic Documentation and support discounts. Licenses are multi-platform and may On our web site www.scm.com step-by-step be host-locked or floating, and single year, tutorials, advanced documented examples multi-annual or perpetual. Each module may and detailed user’s guides are available. be licensed separately and for academic ADF Furthermore, detailed scientific background users we currently offer MOPAC and DFTB at is available through review papers and Ph.D. no additional charge in combination with other theses. Expert support is available from SCM modules. at [email protected]. Consultancy services, contract research, Academic development groups custom development The foundations of ADF were laid mainly by SCM also has the expertise to offer companies the work of professors Baerends and Ziegler, consultancy services and contract research starting already in the 1970s. Through extensive related to ADF, BAND, DFTB, ReaxFF, academic collaborations with development and COSMO-RS. A new feature can also groups around the world 82 developers have be implemented upon request of a specific contributed to what our programs are today. customer. Contact SCM for further details on Thanks to these academic groups and our these options. own developers, the scope and functionality of our software is continuously expanding. We Visit our web site www.scm.com for pricing always welcome suggestions from users for and ordering information, or send an e-mail to: features that would help to advance their R&D [email protected] with your questions or feedback. in academia and industry.

21 Feature list

The molecular ADF program • Structure and Reactivity • Analysis o optimization (ground and excited states) o molecule from fragments, symmetry o transition states o bond energy analysis, ETS-NOCV (TS reaction coordinate, EF, NEB), IRC, LT o Mulliken, Voronoi, and Hirshfeld o (analytical) frequencies, initial Hessian charges, bond orders, NBO, AIM, ELF estimates, constraints and restraints o (partial) DOS o Cartesian, internal, delocalized • Accuracy and Efficiency coordinates o basis sets Z = 1 to 118, all-electron, • Model Hamiltonians frozen core, SZ to QZ4P o relativistic effects o parallelized, linear scaling, distance (ZORA, spin-orbit coupling) cut-offs, density fit, te Velde-Baerends o modern xc: LDA, GGA, hybrid-GGA, integration meta-GGA, meta-hybrid-GGA o LISTi, ADIIS, EDIIS, ARH, and spin-flip o dispersion corrections: for flexible and robust SCF convergence D, D3, D3-BJ, dDsC o potential-only: SAOP, GRAC, LB94, OEP o energy-only: more (hybrid) (meta-)GGAs o solvents, environments: COSMO, QM/ MM, DRF, FDE, SCRF, 3D-RISM, QUILD o electric field, point charges o finite nuclei • Electronic transport: transfer integrals, non-self-consistent Green’s function • Spectroscopic properties o IR, (resonance) Raman, MBH, VCD, VROA, Franck-Condon factors o (vibrationally resolved) UV/Vis spectra, X-ray, core excitations, state selection o CD, ORD, magnetizabilities, MCD, Verdet constants, Faraday terms o (hyper-)polarizabilities, dispersion coefficients, lifetime effects o NMR chemical shifts, spin-spin couplings o ESR (EPR): g-tensor, A-tensor, Q-tensor, D-tensor (ZFS) o nuclear quadrupole interaction (EFG), Mössbauer, NRVS

22 The periodic BAND program intermediates, products) during MD run • bulk crystals, polymers, surfaces • easy set up of complex mixtures and solid- • geometry optimization (including lattice), liquid interfaces in 3D box with Packmol transition state search, frequencies • define different temperature regimes, • XC energies, potentials, and forces: pressure constraints, bond constraints LDA, GGA, meta-GGA, dispersion corrections (D, D3, D3-BJ), GGA+U, HTBS, TB-mBJ COSMO-RS • relativistic effects with ZORA and spin-orbit • predict properties solutions and liquids with coupling: SCF and forces COSMO-RS or COSMO-SAC • COSMO solvation model for surfaces • solubilities, activity coefficients, solvation free • static homogeneous electric field energies, pKa, VLE (LLE) diagrams • TDDFT - frequency-dependent dielectric • database of almost 1900 molecules functions, EELS, metallic systems, SO effects, Vignale-Kohn functional Integrated GUI • DOS (total, partial, population, local), Mulliken • set up, run and analyze (complex) jobs for all population analysis, form factors, AIM, ELF programs • STM images, smooth band structures, • queue and monitor jobs on different machines phonon dispersion curves • search: panels, documentation, database • bond energy analysis (fragment approach) • draw molecules or import (extensive database, • NMR chemical shifts, shielding tensors .xyz, .pdb, .cif, SMILES) • electric field gradient (NQCC) • seamless switching between all calculation • ESR (EPR): A-tensor, g-tensor and visualization modules • parallel, linear scaling techniques • 3D data fields for orbitals, densities, potentials • numerical orbitals and STOs and cut planes, contour plots • visualize DOS, IR, Raman, CD, MCD, VCD, DFTB optical spectra, and more • 2nd, 3rd order self-consistent charges • electronic band structures, phonon dispersion (SCC, DFTB3), dispersion corrections curves with Brillouin Zone • minima and TS optimization molecules • display (partial) Density-Of-States for ADF, and periodic (1D, 2D, 3D) systems BAND and DFTB • molecular dynamics with Velocity Verlet, • draw orbital interaction diagrams Berendsen and scaling thermostats (fragment approach) • phonons, DOS, band structure • movies of vibrations, optimization, MD steps • parallelized • prepare multiple ADF calculations and compare results graphically and numerically MOPAC2009 • monitor calculation progress, browse output • molecules and periodic systems • minima and TSs, COSMO solvation Tools • MNDO, AM1, PM3, PM6, PM6-DH+ • QM/MM, QUILD: perform multi-layer calculations ReaxFF • PyMD: advanced MD • parallelized molecular dynamics and (multi-scale, adaptive, biased) minimizations with reactive force fields • scripting to prepare and report multiple • analyze changing composition (reactants, complex jobs

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