modified on 18 June 2012 at 11:02 ••• 26,069 views


From NWChem

Revision as of 11:02, 18 June 2012 by Marat (Talk | contribs)
Jump to: navigation, search



Properties can be calculated for both the Hartree-Fock and DFT wave functions. The properties that are available are:

  • Natural bond analysis
  • Dipole, quadrupole, and octupole moment
  • Mulliken population analysis and bond order analysis
  • Electrostatic potential (diamagnetic shielding) at nuclei
  • Electric field and field gradient at nuclei
  • Electron and spin density at nuclei
  • NMR shielding (GIAO method)
  • NMR hyperfine coupling (Fermi-Contact and Spin-Dipole expectation values)
  • NMR indirect spin-spin coupling
  • Response
  • Raman

The properties module is started when the task directive TASK <theory> property is defined in the user input file. The input format has the form:

   [property keyword]
   [CENTER ((com || coc || origin || arb <real x y z>) default coc)]

Most of the properties can be computed for Hartree-Fock (closed-shell RHF, open-shell ROHF, and open-shell UHF), and DFT (closed-shell and open-shell spin unrestricted) wavefunctions. The NMR chemical shift is limited to closed-shell wave functions, whereas the NMR hyperfine and indirect spin-spin coupling require a UHF or ODFT wave function.

Property keywords

Each property can be requested by defining one of the following keywords:

 SHIELDING [<integer> number_of_atoms <integer> atom_list]
 SPINSPIN [<integer> number_of_pairs <integer> pair_list]

The "ALL" keyword generates all currently available properties.

Both the NMR shielding and spin-spin coupling have additional optional parameters that can be defined in the input. For the shielding the user can define the number of atoms for which the shielding tensor should be calculated, followed by the list of specific atom centers. In the case of spin-spin coupling the number of atom pairs, followed by the atom pairs, can be defined (i.e., spinspin 1 1 2 will calculate the coupling for one pair, and the coupling will be between atoms 1 and 2).

For both the NMR spin-spin and hyperfine coupling the isotope that has the highest abundance and has spin, will be chosen for each atom under consideration.

The user also has the option to choose the center of expansion for the dipole, quadrupole, and octupole calculations.

   [CENTER ((com || coc || origin || arb <real x y z>) default coc)]

com is the center of mass, coc is the center of charge, origin is (0.0, 0.0, 0.0) and arb is any arbitrary point which must be accompanied by the coordinated to be used. Currently the x, y, and z coordinates must be given in the same units as UNITS in GEOMETRY.

Response calculations can be calculated as follows:

 response  1 7.73178E-2   # response order and frequency in hartree
 velocity                 # use modified velocity gauge for electric dipole 

Response calculations are currently supported only for order 1 (linear response), single frequency, electric field and mixed electric-magnetic field perturbations. The output consists of the electric polarizability and optical rotation tensors (alpha, beta for optical rotation) in atomic units. If the 'velocity' keyword is absent, the dipole-length form will be used for the dipole integrals. This is a bit faster. The isotropic optical rotation is origin independent when using the velocity gauge. Works with HF and density functionals for which linear response kernels are implemented in NWChem.

Please refer to the following papers for further details:

  1. J. Autschbach, Comp. Lett. 3, 131(2007)
  2. M. Krykunov, J. Autschbach, J. Chem. Phys. 123, 114103 (2005)
  3. J.R. Hammond, N. Govind, K. Kowalski, J. Autschbach, S.S. Xantheas, J. Chem. Phys. 131, 214103 (2009)

Raman calculations can be performed by specifying the Raman block. These calculations are performed in conjunction with polarizability calculations.

 [ (NORMAL | | RESONANCE) default NORMAL ]
 [ LOW <double low default 0.0> ]
 [ HIGH <double high default ‘highest normal mode’> ]
 [ FIRST <integer first default ‘7’> ]
 [ LAST < integer last default ‘number of normal modes’ > ]
 [ WIDTH <double width default 20.0> ]
 [ DQ!<double dq default 0.01> ]
task dft raman


task dft raman numerical

Sample input block:

 response 1 8.8559E-2
 damping 0.007


The keyword NBOFILE does not execute the Natural Bond Analysis code, but simply creates an input file to be used as input to the stand-alone NBO code. All other properties are calculated upon request.

Following the successful completion of an electronic structure calculation, a Natural Bond Orbital (NBO) analysis may be carried out by providing the keyword NBOFILE in the PROPERTY directive. NWChem will query the rtdb and construct an ASCII file, <file_prefix>.gen, that may be used as input to the stand alone version of the NBO program, gennbo. <file_prefix> is equal to string following the START directive. The input deck may be edited to provide additional options to the NBO calculation, (see the NBO user's manual for details.)

Users that have their own NBO version can compile and link the code into the NWChem software. See the INSTALL file in the source for details.

Gaussian Cube Files

Electrostatic potential (keyword esp) and the magnitude of the electric field (keyword efield) on the grid can be generated in the form of the Gaussian Cube File. This behavior is triggered by the inclusion of grid keyword as shown below

grid [pad dx [dy dz]] [rmax x y z] [rmin x y z] [ngrid nx [ny nz]] [output filename]


  • pad dx [dy dz] - specifies amount of padding (in angstroms) in x,y, and z dimensions that will be applied in the automatic construction of the rectangular grid volume based on the geometry of the system. If only one number is provided then the same amount of padding will be applied in all dimensions. The default setting is 4 angstrom padding in all dimensions.
  • rmin x y z - specifies the coordinates (in angstroms) of the minimum corner of the rectangular grid volume. This will override any padding in this direction.
  • rmax x y z - specifies the coordinates (in angstroms) of the maximum corner of the rectangular grid volume. This will override any padding in this direction.
  • ngrid nx [ny nz] - specifies number of grid points along each dimension. If only one number is provided then the same number of grid points are assumed all dimensions. In the absence of this directive the number of grid points would be computed such that grid spacing will be close to 0.2 angstrom, but not exceeding 50 grid points in either dimension.
  • output filename - specifies name of the output cube file. The default behavior is to use <prefix>-elp.cube or <prefix>-elf.cube file names for electrostatic potential or electric field respectively. Here <prefix> denotes the system name as specified in start directive. Note that Gaussian cube files will be written in the run directory (where the input file resides).

Example file

  start nacl
  permanent_dir ./perm
  scratch_dir ./data
  memory total 2000 Mb
  geometry nocenter noautoz noautosym
   Na                   -0.00000000     0.00000000    -0.70428494
   Cl                    0.00000000    -0.00000000     1.70428494

    * library 6-31g*
  #electric field would be written out to nacl.elf.cube file
  #ngrid     : 20 20 20
  #rmax      : 4.000     4.000     5.704
  #rmin      :-4.000    -4.000    -4.704
  grid pad 4.0 ngrid 20
  task dft property
  #electrostatic potential would be written to esp-pad.cube file
  # with the same parameters as above
  grid pad 4.0 ngrid 20 output esp-pad.cube
  task dft property
  #illustrating explicit specification of minumum box coordinates
  grid pad 4.0 rmax 4.000 4.000 5.704 ngrid 20
  task dft property