Examples¶
Introduction¶
The ADF package contains a series of sample runs. They consists of UNIX scripts (to run the calculations) and the resulting output files.
The examples serve:
- To demonstrate how to do calculations. The number of options available in ADF is substantial and the sample runs do not cover all of them. They should be sufficient, however, to get a feeling for how to explore the possibilities.
- To work out special applications that do not fit well in the User’s Guide.
Note: Most of the provided samples have been devised to be short and simple, at the expense of physical or chemical relevance and precision or general quality of results. They serve primarily to illustrate the use of input, necessary files, and type of results. The descriptions have been kept brief. Extensive information about using keywords in input and their implications is given in the User’s Manual.
Where references are made to the operating system (OS) and to the file system on your computer, the terminology of a UNIX type OS is used.
All sample files are stored in subdirectories under $ADFHOME/examples/
, where $ADFHOME
is the main directory of the ADF package. There are many subdirectories in $ADFHOME/examples/
: the examples presented in this section are located in $ADFHOME/examples/adf/
.
Each sample run has its own directory. For instance, $ADFHOME/examples/adf/HCN/
contains an ADF calculation on the HCN molecule.
Each sample subdirectory contains:
- A file TestName.run: the UNIX script to execute the calculation(s). A sample may involve several calculations, for instance a few CREATE runs (with ADF), then a molecular calculation (also ADF), and finally a NMR calculation (with the NMR program) to compute chemical shifts.
- A file TestName_orig.out.gz: the resulting output(s) against which you can compare the outcome of your own calculation. Note: the files are compressed using gzip.
- Zero or more files with a .adf extension. These files, if present, are intended for ADFinput and demonstrate the same functionality as the two files above. However, there are also differences between the .adf and the TestName.run files so the results obtained with the .adf files cannot be compared directly with TestName_orig.out. Also, the TestName.run file usually contains more than one calculation, for which more than one .adf file is required. That’s why in some directories you may find more than one .adf file.
Technical notes:
- Running the examples on Windows: You can run an example calculation by double-clicking on the appropriate .run file. After the calculation has finished, you can compare the TestName.out file with the reference TestName_orig.out file. See remarks about comparing output files below.
- The UNIX scripts make use of the rm (remove) command. Some UNIX users may have aliased the rm command. They should accordingly adapt these commands in the sample scripts so as to make sure that the scripts will remove the files. New users may get stuck initially because of files that are lingering around after an earlier attempt to run one of the examples. In a subsequent run, when the program tries to open a similar (temporary or result) file again, an error may occur if such a file already exists. Always make sure that no files are left in the run-directory except those that are required specifically.
- It is a good idea to run each example in a separate directory that contains no other important files.
- The run-scripts use the environment variables
ADFBIN
andADFRESOURCES
. They stand respectively for the directory that contains the program executables and the main directory of the basis set files. To use the scripts as they are you must have defined the variablesADFBIN
andADFRESOURCES
in your environment. If a parallel (PVM or MPI) version has been installed, it is preferable to have also the environment variableNSCM
. This defines the default number of parallel processes that the program will try to use. Consult the Installation Manual for details. - As you will note the sample run scripts refer to the programs by names like ‘adf’, ‘nmr’, and so on. When you inspect your
$ADFBIN
directory, however, you may find that the program executables have names ‘adf.exe’, ‘nmr.exe’. There are also files in$ADFBIN
with names ‘adf’, ‘nmr’, but these are in fact scripts to execute the binaries. We strongly recommend that you use these scripts in your calculations, in particular when running parallel jobs: the scripts take care of some aspects that you have to do otherwise yourself in each calculation. - You need a license file to run any calculations successfully. If you have troubles with your license file, consult the Installation manual. If that doesn’t help contact us at support@scm.com
When you compare your own results with the sample outputs, you should check in particular (as far as applicable):
- Occupation numbers and energies of the one-electron orbitals;
- The optimized geometry;
- Vibrational frequencies;
- The bonding energy and the various terms in which it has been decomposed;
- The dipole moment;
- The logfile. At the end of a calculation the logfile is automatically appended (by the program itself) to the standard output.
General remarks about comparisons:
- For technical reasons, the discussion of which is beyond the scope of this document, differences between results obtained on different machines (or with different numbers of parallel processes) may be much larger than you would expect. They may significantly exceed the machine precision. What you should check is that they fall well (by at least an order of magnitude) within the numerical integration precision used in the calculation.
- For similar reasons the orientation of the molecule used by the program may be different on different machines, even when the same input is supplied. In such cases the different orientations should be related and only differ in some trivial way, such as by a simple rotation of all coordinates by 90 degrees around the z-axis. When in doubt, contact an ADF representative.
Model Hamiltonians¶
Special exchange-correlation functionals¶
- Example: Asymptotically correct XC potentials: CO
- Example: Meta-GGA energy functionals: OH
- Example: Hartree-Fock: HI
- Example: B3LYP: H2PO
- Example: Long-range corrected GGA functional LCY-BP: H2O
- Example: Range-separated functional CAMY-B3LYP: H2O
- Example: Use of the xcfun library: H2O
- Example: Grimme Molecular Mechanics dispersion-corrected functionals (DFT-D3-BJ)
- Example: Density-Dependent Dispersion Correction (dDsC): CH4-dimer
- Example: DFT-ulg Dispersion Correction: Benzene dimer T-shaped
ZORA and spin-orbit Relativistic Effects¶
Solvents, other environments¶
FDE: Frozen Density Embedding¶
- Example: FDE: H2O in water
- Example: FDE freeze-and-thaw: HeCO2
- Example: FDE energy: NH3-H2O
- Example: FDE energy: unrestricted fragments: Ne-H2O
- Example: FDE geometry optimization: H2O-Li(+)
- Example: FDE geometry optimization: NH3-H2O: FDE geometry optimization
- Example: FDE NMR shielding: Acetonitrile in water
- Example: FDE NMR spin-spin coupling: NH3-H2O
- Example: Subsystem TDDFT, coupled FDE excitation energies
- Example: FDE and COSMO: H2O-NH3
- Example: FDE and COSMO: H2O-NH3
QM/MM calculations¶
- QM/MM manual: QM/MM Examples
- QM/MM manual: pdb2adf example
Quild: Quantum-regions Interconnected by Local Descriptions¶
- Quild manual: Quild examples
DIM/QM: Discrete Interaction Model/Quantum Mechanics¶
- Example: DRF: hyperpolarizability H2O in water
- Example: DRF: scripting tool
- Example: CPIM: excitation energies N2 on silver cluster Ag68
- Example: PIM: optimization N2 on silver cluster Ag68
- Example: PIM: polarizability N2 on silver cluster Ag68
- Example: PIM: Raman scattering N2 on silver cluster Ag68
- Example: PIM: SEROA calculation N2 on silver cluster Ag68
- Example: PIM: Multipole Method N2 on silver cluster Ag1415
Structure and Reactivity¶
Geometry Optimizations¶
- Example: Geometry Optimization: H2O
- Example: Geometry Optimization: Formaldehyde
- Example: Geometry optimization in delocalized coordinates: Aspirin
- Example: Scalar-Relativistic ZORA Optimization: AuH
- Example: Restraint Geometry Optimization: H2O
- Example: Constraint Geometry Optimization: H2O
- Example: Initial Hessian
- Example: Geometry optimization with an external electric field or point charges: LiF
- Example: Excited state geometry optimization with a constraint: CH2O
Transition States, Linear Transits, Intrinsic Reaction Coordinates¶
- Example: LT, Frequencies, TS, and IRC: HCN
- Example: Transition state search with the CINEB method: HCN
- Example: TS search using partial Hessian: C2H6 internal rotation
- Example: Relativistic ZORA TS search: CH4 + HgCl2 <==> CH3HgCl + HCl
- Example: TS reaction coordinate: F- + CH3Cl
- Example: Constraint Linear Transit: H2O
- Example: (non-)Linear Transit: H2O
Total energy, Multiplet States, S2, Localized hole, CEBE¶
Spectroscopic Properties¶
IR Frequencies, (resonance) Raman, VROA, VCD, Franck-Condon factors¶
- Example: Numerical Frequencies: NH3
- Example: Numerical Frequencies, spin-orbit coupled ZORA: UF6
- Example: Numerical Frequencies, accurate Hartree-Fock: H2O
- Example: Numerical Frequencies of an excited state: PH2
- Example: Analytic Frequencies: CN
- Example: Analytic Frequencies: CH4
- Example: Analytic Frequencies, scalar ZORA: HI
- Example: Mobile Block Hessian (MBH): Ethanol
- Example: Mobile Block Hessian: CH4
- Example: Raman: NH3
- Example: Resonance Raman, excited state finite lifetime: HF
- Example: Resonance Raman, excited state gradient: Uracil
- Example: Vibrational Raman optical activity (VROA): H2O2
- Example: Resonance VROA: H2O2
- Example: Vibrational Circular Dichroism (VCD): NHDT
- Example: Franck-Condon Factors: NO2
Excitation energies: UV/Vis spectra, X-ray absorption, CD, MCD¶
- Example: Excitation energies and polarizability: Au2
- Example: Excitation energies open shell molecule: CN
- Example: Spin-flip excitation energies: SiH2
- Example: TDHF excitation energies: N2
- Example: excitation energies CAM-B3LYP: Pyridine
- Example: CAMY-B3LYP excitation energies: H2O
- Example: Full XC kernel in excitation energy calculation: H2O+
- Example: Use of xcfun in excitation energy calculations: H2O
- Example: Core excitation energies: TiCl4
- Example: X-Ray Absorption and Emission Quadrupole Oscillator strengths at the Cl K-edge: TiCl4
- Example: (Core) Excitation energies including spin-orbit coupling: Ne
- Example: Excitation energies perturbative spin-orbit coupling: AgI
- Example: Excitation energies including spin-orbit coupling for open shell: PbF
- Example: Excited state geometry optimization: N2
- Example: Spin-flip excited state geometry optimization: CH2
- Example: Circular Dichroism (CD) spectrum: DMO
- Example: CD spectrum, hybrid functional: Twisted ethene
- Example: MCD: H2O
- Example: MCD including zero-field splitting: H2O
- Example: CV(n)-DFT excitation energies: Formamide
- Example: TD-DFT+TB excitation energies: beta-Carotene
- Example: sTDA excitation energies: Adenine
- Example: sTDDFT excitation energies: Adenine
- Example: sTDA excitation energies RS functional: Bimane
- Example: sTDA excitation energies wB97: TCNE-Benzene
(Hyper-)Polarizabilities, dispersion coefficients, ORD, magnetizabilities, Verdet constants¶
- Example: Polarizabilities including spin-orbit coupling: AgI
- Example: damped first hyperpolarizability: LiH
- Example: damped second hyperpolarizability: LiH
- Example: Verdet constants: H2O
- Example: Dispersion Coefficients: HF
- Example: Optical Rotation Dispersion (ORD): DMO
- Example: ORD, lifetime effects (key AORESPONSE): DMO
- Example: Hyperpolarizabilities of He and H2
- Example: Damped Verdet constants: Propene
- Example: Static magnetizability: H2O
- Example: Dynamic magnetizability: H2O
- Example: Time-dependent current-density-functional theory: C2H4:
- Example: Damped complex polarizabilities with POLTDDFT: Au10
Ligand Field DFT (LFDFT)¶
NMR chemical shifts and spin-spin coupling constants¶
- Example: NMR Chemical Shifts: HBr
- Example: NMR Chemical Shifts: HgMeBr
- Example: NMR Chemical Shifts, SAOP potential: CH4
- Example: NMR Nucleus-independent chemical shifts (NICS): PF3
- Example: NMR with B3LYP: PF3
- Example: NMR Spin-spin coupling constants: C2H2
- Example: NMR Spin-spin coupling constants, hybrid PBE0: HF
- Example: NMR Spin-spin coupling constants, finite nucleus: PbH4
ESR/EPR g-tensor, A-tensor, Q-tensor, ZFS¶
- Example: ESR g-tensor, A-tensor, Q-tensor, D-tensor: HfV
- Example: ESR g-tensor, A-tensor, self consistent spin-orbit coupling: VO
- Example: ESR g-tensor, A-tensor, perturbative spin-orbit coupling: HgF
- Example: ESR spin-restricted and spin-unrestricted: TiF3
- Example: ESR, X2C and RA-X2C: PdH
- Example: Zero-field splitting (ZFS), ESR D-tensor: NH
- Example: ZFS D tensor, including direct electron spin-spin part: Phenylnitrene
Transport properties¶
Charge transfer integrals (transport properties)¶
Non-self-consistent Green’s function calculation¶
Analysis¶
Fragment orbitals, bond energy decomposition, charge analysis¶
- Example: Compound Fragments: Ni(CO)4
- Example: Fragments: PtCl4H2 2-
- Example: Spin-unrestricted Fragments: H2
- Example: Bond Energy analysis open-shell fragments: PCCP
- Example: Bond Energy analysis meta-GGA, (meta-)hybrids: Zn2, Cr2, CrH
- Example: Spin-Orbit SFO analysis: TlH
- Example: (Perturbed) localized molecular orbitals in twisted Ethene
- Example: Bader Analysis (AIM)
- Example: Bader Reactivity
- Example: Aromaticity indices with QTAIM
- Example: Charge model 5 (CM5)
- Example: Bond Orders
- Example: NOCV: ethylene – Ni-diimina and H+ – CO
- Example: NOCV: CH2 – Cr(CO)5
- Example: NOCV: CH3 – CH3