oeprop - Online in the Cloud

PROGRAM:

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

INPUT FORMAT

Most of the keywords are not necessary 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
([email protected]), 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

March 30, 2001 oeprop(1)

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