NAME¶
oeprop - One-Electron Property Program
DESCRIPTION¶
The program
oeprop computes expectation values of one-electron property
operators using a one-particle density matrix computed from an eigenvector in
PSIF_CHKPT or read in from an external file. It is currently capable of
performing Mulliken population analysis, computing electric multipole moments
through octopole, electrostatic properties at atomic centers (electrostatic
potential, electric field, electric field gradient, electron and spin density,
dipolar anisotropic contribution to the hyperfine coupling constants),
electron and spin density, electron and spin density gradient, Laplacian of
electron and spin densities, electrostatic potential over an arbitrary
two-dimensional (planar) rectangular grid, and molecular orbitals values over
an arbitrary three-dimensional rectangular grid. Miscellaneous capabilities
include computation of the relativistic first-order one-electron corrections
to the energy (mass-velocity and Darwin terms), construction of natural
molecular orbitals from one-particle density read from an external file (NOs
can be written to PSIF_CHKPT) and computation of spatial extents - expectation
values of X^2, Y^2, Z^2, and R^2 operators - of total electron density and of
individual MOs (if
READ_OPDM = false) or natural (if
READ_OPDM =
true) orbitals (
MPMAX must be set to a value greater than 1 for
computing these entities). Spatial extents should be used cautiously, since
they depend on the reference point.
REFERENCES¶
Mulliken population analysis
- 1.
- Electronic Population Analysis on LCAO-MO Molecular Wave
Functions. R. S. Mulliken, J. Chem. Phys. 23, 1833 (1955), ibid. 23, 1841
(1955), ibid. 36, 3428 (1962).
Recurrence relations for one-electron integrals over Cartesian Gaussian
functions.
- 1.
- Efficient recursive computation of molecular integrals over
Cartesian Gaussian functions. S. Obara and A. Saika, J. Phys. Chem. 84,
3963 (1986).
Fundamental physical constants and conversion factors.
- 1.
- CRC Handbook of chemistry and physics. Edited by D. R.
Lide. 73rd edition (1992-1993).
FILES REQUIRED¶
input.dat - Input file
PSIF_CHKPT - Checkpoint file
FILES UPDATED¶
output.dat
dipmom.dat - Dipole moments
esp.dat - Electrostatic potential on a 2D grid
edens.dat - Electron density on a 2D grid
edgrad.dat - Electron density gradient on a 2D grid
edlapl.dat - Laplacian of the electron density on a 2D grid
sdens.dat - Spin density on a 2D grid
sdgrad.dat - Spin density gradient on a 2D grid
sdlapl.dat - Laplacian of the spin density on a 2D grid
mo.dat - Molecular orbital/Density values on a 3D grid
mo.pov - MegaPov input file for rendering an image of mo.dat
mo.cube - Molecular orbital(s) on a 3D grid in Gaussian94 Cube format
dens.cube - Electron/spin density(s) on a 3D grid in Gaussian94 Cube format
Most of the keywords are not neccessary for routine tasks. The following
keywords are valid:
- WFN = boolean
- Type of the wavefunction. This keyword is a
"macro" that allows user to set most of the necessary keywords.
The following values are recognized :
WFN = SCF - equivalent to READ_OPDM = false;
WFN = DETCI - equivalent to READ_OPDM = true, OPDM_FILE =
40, OPDM_BASIS = AO, OPDM_FORMAT = TRIANG;
WFN = CCSD - equivalent to EAD_OPDM = true, OPDM_FILE =
79, OPDM_BASIS = AO, OPDM_FORMAT = TRIANG;
WFN = QVCCD - equivalent to READ_OPDM = true, OPDM_FILE =
76, OPDM_BASIS = SO, OPDM_FORMAT = TRIANG;
- READ_OPDM = boolean
- This flag specifies if the one-particle density matrix to
be read from disk. Default is false.
- OPDM_FILE = integer
- Specifies one-particle density matrix file number. Default
is 40 (master file). To provide backward compatibility with the earlier
PSI property packages ( proper, ciprop, ccprop)
special format of the density file is assumed when OPDM_FILE = 40
(computing properties from CI density - ciprop compatibility mode)
and OPDM_FILE = 79 (computing properties from CC density -
ccprop compatibility mode). As of now, in generic case onepdm must
be written in the very beginning of the file. In the future PSI will have
a standard onepdm file.
- OPDM_BASIS = string
- This option may not exist in the future. As of February
1st, 1998, a standard for the onepdm file format has not been set. This
keyword should be set to either "SO" (read in onepdm matrix in
SO basis) or "AO" (in AO basis). Default is "SO".
- OPDM_FORMAT = string
- This option may not exist in the future. This keyword
should be set to either "TRIANG" (read in onepdm matrix in lower
triangular form) of "SQUARE" (in square form). Default is
"TRIANG"
- ASYMM_OPDM = boolean
- This flag specifies whether one-particle density matrix has
to be symmetrized. Must be set to true if generic non-symmetric onepdm to
be read (for example, from a coupled-cluster program). This keyword is for
code development only. Existing PSI CC codes now in use produce symmetric
onepdm, therefore there is no need to use this keyword. Default is false.
- ROOT = integer
- This specifies which root to do the excited state analysis
for. The appropriate one particle density matrix will be read from disk.
Currently implemented for DETCI and DETCAS wavefunctions.
- MPMAX = integer
- This integer between 1 and 3 specifies the highest electric
multipole moment to be computed.
MPMAX = 1 - only electric dipole moment will be computed (default);
MPMAX = 2 - electric dipole and quadrupole moments will be computed;
MPMAX = 3 - electric dipole, quadrupole, and octopole moments will
be computed.
- MP_REF integer
- This parameter specifies the reference point for the
electric multipole moments calculation.
MP_REF = 0 (default) or 1 - the center of mass;
MP_REF = 2 - the origin of the space coordinate system;
MP_REF = 3 - the center of electronic charge;
MP_REF = 4 - the center of nuclear charge;
MP_REF = 5 - the center of net charge.
CAUTION : According to classical electrodynamics, the electric
2^(n+1)-pole moment is independent of the reference point only if the
electric 2^(n)-pole moment is vanishing. It means that the dipole moment
will depend on the reference point if the total charge of the system is
non-zero. By analogy, electric quadrupole moment will depend on the
reference point if the system possesses non-zero electric dipole moment,
etc.
- MP_REF_XYZ = real_vector
- This vector specifies the coordinates of the reference
point. If this keyword is present in the input MP_REF keyword will
be disregarded.
- NUC_ESP = boolean
- This flag specifies if electrostatic properties will be
computed at the nuclei. Current list includes electrostatic potential,
electric field, electric field gradient, electron and spin density, and
anisotropic constribution to the hyperfine coupling constants (the latter
two require setting SPIN_PROP to true). Default is true.
- GRID = integer
- Specifies type of property to be evaluated over a grid.
GRID = 0 (default) - compute nothing;
GRID = 1 - electrostatic potential on a two-dimensional grid;
GRID = 2 - electron density (spin density if SPIN_PROP is set
to true) on a two-dimensional grid;
GRID = 3 - electron density gradient (spin density gradient if
SPIN_PROP is set to true) on a two-dimensional grid;
GRID = 4 - Laplacian of the electron density (Laplacian of the spin
density if SPIN_PROP is set to true) on a two-dimensional grid.
According to the convention used in the field, what actually gets plotted
are the Laplacians taken with negative sign.
GRID = 5 - values of molecular orbitals on a three-dimensional grid.
GRID = 6 - values of the electron density (spin density gradient if
SPIN_PROP is set to true) on a three-dimensional grid.
- GRID_FORMAT = string
- Specifies in which format the grid output will be produced.
Currently, PLOTMTV (default for 2-d grids), MEGAPOVPLUS
(available for 3-d grids), and GAUSSCUBE(default for 3-d grids) are
supported.
- MO_TO_PLOT = vector
- Specifies indices of the molecular orbitals to be computed
on the 3-d grid. Indices can be specified as:
unsigned integer - index in Pitzer ordering (ordered accoring to irreps, not
eigenvalues). Ranges from 1 to the number of MOs.
signed integer - index with respect to Fermi level. +1 means LUMO, +2 means
second lowest virtual orbital, -1 means HOMO, etc.
All indices have to be either unsigned or signed, you can't mix and match,
or you will get unpredictable results. Default is to compute HOMO and
LUMO.
- GRID_ORIGIN = real_vector
- Specifies the origin of the grid. A rectangular grid box
which envelops the entire molecule will be computed automatically if
GRID_ORIGIN is missing, however, there is no default for 2-d grids.
- GRID_UNIT_X = real_vector
- This vector specifies the direction of the first (x) side
of the grid. It doesn't have have to be of unit length. There is no
default for 2-d grids.
- GRID_UNIT_Y = real_vector
- The same for the second (y) side. It doesn't have to be of
unit length or even orthogonal to GRID_UNIT_X. There is no default
for 2-d grids.
- GRID_XY0 = real_2d_vector
- Specifies the coordinates of the lower left corner of the
grid rectangle in the 2D coordinate system defined by GRID_ORIGIN,
GRID_UNIT_X, and GRID_UNIT_Y. There is no default.
- GRID_XY1 = real_2d_vector
- Specifies the coordinates of the upper right corner of the
grid rectangle in the 2D coordinate system defined by GRID_ORIGIN,
GRID_UNIT_X, and GRID_UNIT_Y. There is no default.
- GRID_XYZ0 = real_3d_vector
- Specifies the coordinates of the far lower left corner of
the grid box in the 3D coordinate system defined by GRID_ORIGIN,
GRID_UNIT_X, GRID_UNIT_Y, and the cross-product of the latter two. There
is no default.
- GRID_XYZ1 = real_3d_vector
- Specifies the coordinates of the near upper right corner of
the grid box in the 3D coordinate system defined by GRID_ORIGIN,
GRID_UNIT_X, GRID_UNIT_Y, and the cross-product of the latter two. There
is no default.
- NIX = integer
- The number of grid point along x direction. This parameter
has to be greater than 1. Default is 20.
- NIY = integer
- The same as NIX for y direction. Default is 20.
- NIZ = integer
- The same as NIX for z direction. Default is 20.
- GRID_ZMIN = double
- Lower limit on displayed z-values for contour plots of
electron density and its Laplacian. Default is 0.0
- GRID_ZMAX = double
- Upper limit on displayed z-values for contour plots of
electron density and its Laplacian. Default is 3.0
- EDGRAD_LOGSCALE = integer
- Controls logarithmic scaling of the produced electron
density gradient plot. Turns the scaling off if set to zero, otherwise the
higher value - the stronger the gradient field will be scaled. Recommended
value (default) is 5.
- SPIN_PROP = boolean
- Flag for computing spin properties (Mulliken population
analysis of alpha and beta densities, spin densities and anisotropic
contributions to the hyperfine coupling constants at atomic centers).
Default is false.
- PRINT = integer
- This is the most important keyword - it determines amount
of information printed. The following values are currently used :
PRINT = 0 - quiet mode - print out essential results only -
"compact" results of Mulliken population analysis, electric
multipole moments, and electrostatic properties;
PRINT = 1 (default) - all of the above plus list of tasks to be
performed and list of caculation parameters;
PRINT = 2 - all of the above plus Mulliken AO population matrix and
electronic and nuclear components of electric dipole moment;
PRINT = 3 - all of the above plus density matrix in AO basis and
dipole moment integrals in AO (and SO) basis;
PRINT = 4 - all of the above plus basis set information, natural
orbitals in terms of symmetry orbitals, overlap matrix;
PRINT >= 5 - all of the above plus coupling coefficient vectors,
an occupation vector, and a modified Z-vector in MO basis.
- PRINT_NOS = boolean
- If WRTNOS = TRUE and this option is also TRUE, the natural
orbitals will be printed to output before they are written to the
checkpoint file.
- WRTNOS = boolean
- If TRUE, the natural orbitals will be written to the
checkpoint file.
GRID OUTPUT AND PLOTTING¶
Currently,
oeprop produces output of two-dimensional grids ready for
plotting with a program
PLOTMTV version 1.3.2. The program is written
by Kenny Toh (ktoh@td2cad.intel.com), software developer for the Technology
CAD Department, Intel Corp, Santa Clara. It is a freeware package, and can be
downloaded off the Internet.
Three-dimensional grids are output in format suitable for plotting with a
program
MegaPov version 0.5. This freeware program is a patched version
of POV-Ray. It is developed by a number of people, and can be downloaded off
the Internet (go to
http://nathan.kopp.com/patched.htm to find out more
info). To render an MO or density image, edit (if necessary) command file
mo.pov created by
oeprop , and execute
megapovplus
+Imo.pov For more options run
megapovplus -h