Plotting gradient paths
Overview
Gradient paths are the solution of the differential equation where is a scalar field. They play an important role in QTAIM theory because gradient paths of the electron density cannot cross the boundary between atomic regions. In consequence, a gradient path plot is a simple way to investigate the shape and properties of a basin. Gradient paths originate at maxima (if the field is the density they are usually the nuclei) and end at the minima (the crystal voids) or at infinity in case of a gasphase molecule.
There are two keywords for making gradient path representations in critic2: GRDVEC (2D gradient paths plus a contour plot) and FLUXPRINT (3D).
Gradient Path Representations in a Plane (GRDVEC)
GRDVEC
{FILESROOTONAME} rootname.s
PLANE x0.r y0.r z0.r x1.r y1.r z1.r x2.r y2.r z2.r
SCALE sx.r sy.r
EXTENDX zx0.r zx1.r
EXTENDY zy0.r zy1.r
OUTCP sx.r sy.r
HMAX hmax.r
ORIG x.r y.r z.r atr.i up.i down.i
CP cp.i up.i down.i
CPALL
BCPALL up.i down.i
RBCPALL bup.i bdown.i rup.i rdown.i
CHECK
x.r y.r z.r
...
ENDCHECK/END
CONTOUR {F,GX,GY,GZ,GMOD,HXX,HXY,HXZ,HYY,HYZ,HZZ,LAP}
nptsu.i nptsv.i {LIN niso.i [cini.r cend.r]
LOG niso.i [zmin.r zmax.r]ATAN niso.i [zmin.r zmax.r]
BADERi1.i i2.i...}
ENDGRDVEC/END
GRDVEC makes a plot in a plane. The plot contains the gradient paths originating from a set of points, critical or otherwise, inside that plane, in addition to a contour representation of a scalar field. The GRDVEC syntax consists of a GRDVEC…ENDGRDVEC environment that accepts a set of input lines (in any order) that control the characteristics of the plot. The syntax of GRDVEC originated from (and is similar to) Bader’s AIMPAC suite of programs.
By using the FILES keyword (equivalently, ROOT or ONAME), the user sets the root name of the output files containing the information for the plot (default: <root>). These files include:

<root>.grd : gradient path data.

<root>.dat : values of the reference field on the plane.

<root>.iso, <root>.neg.iso : positive (green) and negative (blue) contour lines.

<root>.gnu : gnuplot script file that generates the merged gradient/contour plot.

<root>label.gnu : gnuplot script file loaded in <root>.gnu containing the information for the position of the CPs in the plot plane.
PLANE specifies the plane for the plot using three points: x0
is the
origin, x1
the end of the xaxis and x2
the end of the yaxis. By
default, these points are in crystallographic coordinates in a
crystal, and in molecular Cartesian coordinates in a molecule (default
units: angstrom). The two axes of the plane can be scaled using the
SCALE keyword. If sx.r
(sy.r
) is given, the total length of the
xaxis (yaxis) is scaled by sx.r
(sy.r
). If EXTENDX is used,
extend the xaxis by zx0.r
(initial point of the xaxis) and zx1.r
(end point). The keyword EXTENDY performs the equivalent operation on
the yaxis. The units for EXTENDX and EXTENDY are bohr (crystals) or
angstrom (molecules) unless changed by the
UNITS keyword.
The plot plane may contain regions that are traversed by gradient
lines originating at critical points located inside the plane but
outside the plot region. If this is the case, the OUTCP option allows
the user to extend the plane for the CP labels. The sx.r
and sy.r
in OUTCP are scale parameters for the plane, same as in SCALE, but
only apply to CP labels. The xaxis extends in
each direction, where is sx.r
and is the length of
the xaxis. The sy.r
variable works the same way. The plane
determined by the vectors given in PLANE acts as a clipping plane
while the scaled plane determines the gradient path origins.
With HMAX, you can set the maximum distance from a CP to the plane to be included in the plot (units: bohr in crystals, angstrom in molecules). Default: 1d4 bohr.
The ORIG keyword adds a source of gradient lines to the plot. Its
coordinates are x.r
, y.r
and z.r
. Crystallographic coordinates
are used in a crystal, and molecular Cartesian coordinates in a
molecule (default units: angstrom). atr.i
is 1 if the point is to be
treated as a ncp or ccp (the up and down trajectories start from
points located on a sphere centered on the origin) and it is 0 if the
point is to be treated as a bcp or ccp (a circle is built around the
CP in the plane determined by two eigenvectors whose eigenvalues have
equal sign. The remaining eigenvector determines a unique
direction). up.i
and down.i
are the number of gradient paths to be
started in the upwards and downwards direction, respectively.
The CP keyword accepts a critical point identifier from the complete
CP list (or the complete atom list). The number of upwards and
downwards gradient paths must be given. A special case is the CPALL
keyword, which adds as origins every critical point in the CP list on
the selected plane. The default number of gradient paths is 36 down
for ncps and 36 up for ccps, and 2 up and 2 down for bcps and
rcps. The BCPALL keyword is similar to CPALL, except that only the
bond critical points are included as origins. If BCPALL is used, the
user must supply the number of gradient lines in the upwards and
downwards directions. In a similar way, RBCPALL includes bond and ring
critical points, and the user must give the number of upwards and
downwards gradient paths for bonds (bup.i
, bown.i
) and rings
(rup.i
, rdown.i
).
The CHECK environment allows the user to enter the crystallographic coordinates of a CP of the scalar field to add it as an origin. If the point given is not a CP or if it lies outside the selected plane, it is excluded from the list of points that are sources of gradient paths. The valid CPs in the CHECK list are identified and an adequate number of gradient paths are started according to its character: for a ncp and ccp, 36 upwards or downwards and for a bcp or rcp, 2 upwards and 2 downwards.
The CONTOUR keyword makes critic2 generate a plot in which the
gradient paths calculated in GRDVEC are merged with a contour plot, in
the spirit of the CONTOUR option to
PLANE. The scalar field for the
contour plot can be selected with
F (current reference field), GX, GY,… The syntax for the derivatives
is the same as in PLANE. After this, the user must specify the
number of points in each direction of the plane (nptsu.i
and
nptsv.i
) and the contour values and type of mapping. The contour
distribution can be: logarithmic (LOG, with niso.i
contours),
arctangent (ATAN, with niso.i
contours), same as in the aimpac
program (BADER, {1,2,4,8}x10^{3,2,1,0,1}), linear (LIN, niso.i
contours from r0.r
to r1.r
), or the user can specify the contour
values manually (no keyword). In LOG and ATAN, the default contours
range from the minimum to the maximum value of the field in the
plot. These quantities can be changed by passing the optional zmin.r
and zmax.r
parameters to LOG/ATAN.
Note that GRDVEC is able to handle nonorthogonal axes for the plot
plane. If the two plane axes determined in the PLANE keyword are
nonorthogonal, the final graph will correctly reflect the actual
appearance of the plane by conserving the original angle between the
x and y axis. Also, note that at most 2 gradient lines may be traced
from bcps and rcps, either upwards or downwards. Thus, for example,
BCPALL 2 2
is equivalent to BCPALL 2 100
or BCPALL 100 100
.
ThreeDimensional Gradient Path Representations (FLUXPRINT)
FLUXPRINT
POINT {110} x.r y.r z.r [step.r epsi.r]
NCP cp.i ntheta.i nphi.i [step.r epsi.r]
[LVEC x.i y.i z.i]
BCP cp.i 1 [step.r epsi.r] [LVEC x.i y.i z.i]
BCP cp.i {01} n.i [step.r epsi.r]
[LVEC x.i y.i z.i]
[BRAINDEADQUOTIENTDYNAMICAL]
RCP cp.i 1 [step.r epsi.r] [LVEC x.i y.i z.i]
RCP cp.i {01} n.i [step.r epsi.r]
[LVEC x.i y.i z.i]
[BRAINDEADQUOTIENTDYNAMICAL]
CCP cp.i ntheta.i nphi.i [step.r epsi.r]
[LVEC x.i y.i z.i]
GRAPH igraph.i [step.r epsi.r]
COLOR r.i g.i b.i
TEXTTESSELTESSOBJPLYOFFCML
SHELLS ishl.i
NOSYM
ENDFLUXPRINT/END
The FLUXPRINT keyword prints threedimensional gradient paths. There are several plotting commands:

POINT: plot a gradient path starting at point (
x.r
y.r
z.r
) in crystallographic coordinates (crystals) or in molecular Cartesian coordinates (molecules, default unit: angstrom).step.r
is the maximum step (Cartesian coordinates) for the gradient path tracing algorithm. Ifstep.r
> 0, use it also as the initial step. Ifstep.r
< 0, use a small step as initial the initial step (1d3).epsi.r
is the gradient norm stop criterion. The default values are 0.1 for step and 1e9 forepsi.r
. The {110} field controls the direction of the path. An ascending gradient path is obtained with 1 while 1 issues a descending path. 0 = 1 + 1 makes FLUXPRINT represent both ascending and descending paths. 
NCP: print gradient paths starting from a (small) sphere centered on the nuclear CP identified by
cp.i
(this identifier comes from the complete CP list). The number of points is controlled byntheta.i
(number of points sampling the azimuthal angle) andnphi.i
(number of points sampling the polar angle).cp.i
specifies a ncp in the main cell up to a lattice translation. The LVEC optional keyword allows the user to enter a lattice vector to displace the represented gradient paths from their initial position, which is given by the complete CP list written by AUTO. 
BCP: print gradient paths starting at the vicinity of a bond CP, identified by
cp.i
. If the gradient path is ascending (1 in the fourth field), the (unique) bond path associated to the bcp is represented. If 1 is given instead, the IAS associated to the bcp is sampled starting from a small circle surrounding the bcp, withn.i
points on it. With a 0 value, both tasks are performed.The three keywords BRAINDEAD, QUOTIENT and DYNAMICAL establish the method employed in generating the starting angular grid. With BRAINDEAD, critic2 uses a uniform angular grid. Using QUOTIENT, the uniform grid is remapped by where and are the two negative eigenvalues at the bcp. This way, the points get accumulated around the bcp with lowest eigenvalue (highest if absolute value is taken). DYNAMICAL uses a linearized model of the interatomic surface and predicts the initial angles critic2 has to take in order to generate a uniform distribution of points a given distance away. This distance is calculated as 90% of the distance to the nearest ccp found in a coarse exploration of the IAS omegalimits. Unfortunately, this algorithm works only in cases where the bcp has significant but not too large ellipticty. Also, there is no gain in using this method in cases where the number of ccps is different than 4.
By default, BRAINDEAD is used. H1 is experimental.

RCP: print gradient paths starting at the neighbourhood of a ring CP. The situation is analogous to that of the bcps.

CCP: print gradient paths starting at the vicinity of a cage CP. Again, the situation is symmetric to the ncp case.

GRAPH: represent the complete graph in the unit cell. This means:

All the bond paths for which both ncps and the bcp lay inside the main unit cell.

All the ring paths for which both ccps and the rcp lay inside the main unit cell.
The critical points on the boundary of the main cell are also represented.
The
igraph.i
value represents the amount of information that is to be printed. It is the sum of these two values, each representing an element to plot:
1 : print ring paths associated to the rcps.

2 : print bond paths associated to the bcps.

Several parameters of the plot generated by FLUXPRINT can be changed. The color to be applied to the paths resulting from FLUXPRINT commands can be changed using the COLOR keyword (three integers from 0 to 255 for the red, green, and blue components). By default, NCP uses the color corresponding to the originating atom, and a gold color is used otherwise. The format of the output file can be controlled with the following keywords: TEXT (plain text file), TESS or TESSEL (tessel), OBJ (Wavefront obj), PLY (ply format), OFF (Geomview’s off), and CML (Chemical Markup Language). The CML format, which can be read with the avogadro program, is used by default. The color specifications are not passed to the CML format. To keep the number of points manageable, critic2 writes one gradient path point every certain distance along the path.
Finally, the SHELLS keyword applies only to graph and graphcp. It represents the number of unit cell shells where the graph is going to be plotted. Thus, 0 represents the main unit cell; 1, the main unit cell and its 26 neighbours; and so on. By default, SHELLS adopts the 1 value, which is equivalent to 0 for the graph keyword and means that the partial graph generated in GRAPHCP is not replicated by symmetry.
The NOSYM keyword instructs critic2 to write the complete list of CPs in the unit cell, together with the identity matrix as the only operation in the space group, to the output.