x-ray charge density analysis and the xd programming package buffalo ny,usa 13-17 may 2003
DESCRIPTION
X-ray Charge Density Analysis and the XD programming package Buffalo NY,USA 13-17 May 2003. Carlo Gatti CNR-ISTM, Milano, Italy. Search of critical points of various scalar fields in crystals. TOPXD Sections. f( r cp ) = 0 f or 2 . (3,-3). Local maxima. NNA (nuclei *). - PowerPoint PPT PresentationTRANSCRIPT
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X-ray Charge Density Analysis and the XD programming package
Buffalo NY,USA13-17 May 2003
Search of critical points of various scalar fields in crystals
Carlo Gatti
CNR-ISTM, Milano, Italy
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TOPXD Sections
TRHO Topological analysis of (r)
TLAP Topological analysis of 2 (r)
ATBP Atomic basin properties
PL2D 2D plots
PL3D 3D plots
VZ3D 3D visualization of atomic basins
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CP search
Search algorithms (NR, EF)
Search strategies (selection of starting points)
f(rcp) = 0 f or 2
cagesLocal minima(3,+3)
rings2D saddle(3,+1)
bonds1D saddle(3,-1)
NNA (nuclei *)Local maxima(3,-3)
* No CP if Slater bfs are used as in TOPXD
f
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I. CP search: Newton Raphson Method
(x0+h) = (x0) + g+h + 1/2 h+ h+ ……
NR step x0 CP h= - -1g
-1= ii-1 vi vi
+; h= -ii-1 vi vi
+g = -ii-1 viFi
with Fi = vi+g projection of the gradient along the local eigenmode vi
viFi
gi > 0 h
i < 0 h
NR step
Minimizes the scalar (, -2 ) along modes with positive Hessian eigenvalues
Maximizes the scalar (goes in the same direction of g) along modes with negative Hessian eigenvalues
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II. CP search: Newton Raphson Method
NR method is suitable for the location of a CP only when one moves in a region where has the same structure (i.e. the
same number of positive and negative eigenvalues) as the CP that is searched for.
This is a problem, in particular with 2 field, since 2 generally varies quite rapidly in R3.
No hope in generalx0
BCP , 3,+1 , 3,-1
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III. CP search: Eigenvector Following Method (*)
(*) A. Banerjee, et. al., J. Phys. Chem. 89, 52 (1985)
(*) P.L.A. Popelier, Chem. Phys. Lett. 228, 160 (1994)
A modified NR algorithm with a suitable and locally
defined shift s for the NR step
hNR= -ii-1 viFi hEF= -i(i – s)-1 viFi
s
Sp for eigenmodes along which the
function is to be maximized
Sn for eigenmodes along which the
function is to be minimized
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IV. CP search: Eigenvector Following Method
0F2F1
F220
F101
1
h2
h1
= Sp
1
h2
h1
Sp = highest eigenvalue
= Sn 0F3
F33
1
h3
1
h3
Sn = lowest eigenvalue
hNR= -ii-1 viFi hEF= -i(i – s)-1 viFi
Example: search of a (3,-1) CP
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V. CP search: Eigenvector Following Method
0F3F2
F330
F202
1
h3
h2
= Sn
1
h3
h2
Sn = lowest eigenvalue
= Sp 0F1
F11
1
h1
1
h1
Sp = highest eigenvalue
hNR= -ii-1 viFi hEF= -i(i – s)-1 viFi
Example: search of a (3,+1) CP
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VI. CP search: Eigenvector Following Method (*)
hNR= -ii-1 viFi hEF= -i(i – s)-1 viFi
Example: search of a (3,+3) CP
0F3F2F1
F3300
F2020
F1 001
1
h3
h2
h1
= Sn Sn = lowest eigenvalue
1
h3
h2
h1
EF method locates reliably all kind of CPs. The method seeks for the CPs of a given kind (e.g. 3,+3) regardless of the structure at
the starting point. Separate searches for (3,-3), (3,-1), (3,+1) and
(3,+3) CPs are implemented
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I. Search strategies
Fully automated and chain-like search for some (or all) kinds of CPs
Exhaustive grid search in the asymmetric unit
More standard searches (along a line, from a given set of starting points, etc.)
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II. Search strategies
TRHO (*)seed (*)all (*)ail (*)debug nstep nstep nnb nnb rmax rmax th th
[ (*)fra | (*)car ] x y z
. . . . . . . . . . . . . . . . . . .
Fully-automated and chain like search strategy for all kinds of critical points (*) using at each stage the EF step specific for the kind of CP searched for.
The search is performed within a finite region of space, which encloses a finite molecular cluster built up around a specified “seed point” A. Size and origin of the cluster are defined by input.
* Search of(3,-3) CPs associated to nuclear maxima is skipped in TOPXD. NNAs recovered either as termini of a BP or in the grid search for CPs.
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III. Search strategies
search of (3,-3) associated to nuclear maxima, starting from the nuclear position of each of the unique atoms of the unit cell
Not performed in TOPXD
search of all (3,-1) unique bcps associated to the unique bonded atom pairs within the cluster. Search started from internuclear axis midpoint. Non-nuclear (3,-3) attractors, if any, are recovered at this stage by determining the nature of the termini of the atomic interaction lines associated to the unique (3,-1) CPs found.
Fully automated and chain-like CP search
search of unique (3,+1) rcps by considering all unique nuclear triplets having at least two associated atoms bonded to each other and center of mass (with mass 1 given to any nucleus) not too differently distant from each of the three nuclei. CP search started from the center of mass.
search of unique (3,+3) CPs between all pairs of ring CPs.
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IV. Search strategies
(*) ail if activated atomic AIL lengths and termini are evaluated numerically for each unique (3,-1)CP. This is costly, but the only safe way to know to which nuclei a bcp is linked to. The associated ordinary differential equations are solved using a 5th order Runge-Kutta method with monitoring of local truncation error and an adaptive stepsize control. Atomic interaction lines are generally determined with less than 80-130 integration steps and 500-1200 and evaluations.
(*) debug if activated debug printing during the CP search
TRHO (*)seed (*)all (*)ail (*)debug nstep nstep nnb nnb rmax rmax th th
[ (*)fra | (*)car ] x y z
. . . . . . . . . . . . . . . . . . .
(*) all if activated all kinds of CPs are searched for, otherwise chain-like search is stopped after (3,-1) CPs search
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V. Search strategies
TRHO (*)seed (*)all (*)ail (*)debug nstep nstep nnb nnb rmax rmax th th
[ (*)fra | (*)car ] x y z
. . . . . . . . . . . . . . . . . . .
nstep nstep maximum number of EF steps along each CP search
nnb nnb maximum number of symmetry related stars of atoms to be included in the cluster generated around the “seed point”.
nnb =3
3 stars of symmetry related atoms Each star may have a different atom’s multiplicity (here 3,4,3)
Seed point
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VI. Search strategies
TRHO (*)seed (*)all (*)ail (*)debug nstep nstep nnb nnb rmax rmax th th
[ (*)fra | (*)car ] x y z
. . . . . . . . . . . . . . . . . . .
rmax rmax maximum radius of the cluster (Å). Each cluster includes all atoms within a sphere of radius rmax, centered on the “seed-point”. rmax may reduce the actual value of nnb.
th th if th0., (3, 1) CP search is performed among all the unique atom pairs whose internuclear distance falls below th (Å), otherwise (th=0.) the default value is used (5Å)
Red sphere has radius rmax. If nnb was settled as to include all the yellow nuclei, rmax excludes some of them
Seed point
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VII. Search strategies
TRHO (*)cluster (*)all (*)ail (*)debug nstep nstep nnb nnb rmax rmax th th
Fully-automated and chain like search strategy for all kinds of critical points (*) using at each stage the EF step specific for the kind of CP searched for.
The search is performed within a finite region of space, which is defined by building-up a “supercluster” defined as the union of the separate clusters build around each of the unique atoms in the unit cell. Size of the atomic clusters is given in input.
* Search of(3,-3) CPs associated to nuclear maxima is skipped in TOPXD. NNAs recovered either as termini of a BP or in the grid search for CPs.
AB
C
(3,-1) CPs are searched for among the unique atom pairs y-z, in the cluster AB C, with Ry-z th ( A,B,C being the unique atoms in the unit cell)
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VIII. Search strategies
TRHO (*)pairs meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax th th {pc pc }
This is CP search among the unique atoms pairs in the cluster ABC…. Y (A,B,C…Y being the unique atoms in the unit cell)
It differs from TRHO cluster search since:
1. it is not a chain-like search;
2. it allows to select the search algorithm (NR, EF or Cioslowski’s analytical simultaneous determination of bcps and AILs [J. Cioslowski et al., CPL 219, 151 (1994)]
3. it allows to make a search for a specific kind of CP (if EF method is selected)
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IX. Search strategies
TRHO (*)pairs meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax th th {pc pc }
meth meth is the algorithm used for the CP search :
nr NR
ef type (one of the following keywords: ncp, bcp, rcp, ccp)
an Cioslowsky’s analytical simultaneous determination of AIL and bcp
ail don’t use if meth = an
{pc pc } only if meth = nr
pc0 : if a CP is not found between A B atom pair, the starting point of
the NR search is displaced, along the internuclear axis, from the axis
mid-point to: rstart = rA+pc *(rB rA ); r''start = rA+(1. pc)*(rB rA ),
pc=0 : specifies the default value of pc (0.4).
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X. Search strategies
nnb nnb In this case there is no “cluster(s)” construction and nnb defines
just the number of start of neighbors in the nearest neighbor
analysis around each unique recovered CP.
[fra | car ] Fractional (fra) or cartesian (car), Å, coordinates
x y z Coord. of the starting point. Repeat this line n times for n starting points
TRHO (*)points meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax [fra | car ]
x y z
…..
This is CP search from a starting set of points. It differs from XDPROP CPSEARCH point since it allows to select the CP search algorithm and (meth = EF) the kind of CP to be searched for.
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XI. Search strategies
Meth nr strongly recommended unless one is looking for a specific kind
of CP and does not care of the other CPs which may be
present along the line)
ef type (one of the following keywords: ncp, bcp, rcp, ccp)
Nstep nstep NR or EF steps for each search. Use a small nstep value, say no more
than 8, since the search is repeated 40 times, starting from 40 evenly
distributed points along the line
TRHO (*)line meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax
line specification
This is CP search along a line. It differs from XDPROP CPSEARCH bond since it allows to select any line (not necessary an internuclear axis), the CP search algorithm and (meth = EF) the kind of CP to be searched for.
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XII. Search strategies
TRHO (*)line meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax
line specification
line specification given in one of the formats:
(*)atom label toneighbor i1… i(n)
CP search along the line(s) joining the unique atom A with label label and its i1..i(n) neighbor(s) (atom B), where i is the “NEW'” number in the “Clusters around each of the unique atoms” printing at the beginning of the TOPXD output.
(*)point [ car | fra ] x1 y1 z1 x2 y2 z2
CP search along the line joining two points a and b with coordinates (x1 y1 z1) and (x2 y2 z2), respectively. The coordinates are in Cartesian (Å) (car) or fractional (fra) units. The search will only be performed if keyword point is activated (i.e., *point). Repeat this line n times for n point pairs
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XIII. Search strategies
line specification
(*)atom label toneighbor i1… i(n)
CP search along the line(s) joining the unique atom A with label label and its i1..i(n) neighbor(s) (atom B), where i is the “NEW'” number in the “Clusters around each of the unique atoms” printing at the beginning of the TOPXD output.
CLUSTERS AROUND EACH OF THE UNIQUE ATOMS
UNIQUE ATOM 1 O(1) (N. 1 in UNIT CELL), CLUSTER OF 11 ATOMSNEW OLD CELL ATOM COORD.(ANG) DISTANCE (ANG) 1 9 0 0 0 H(1) 0.000 0.393 1.311 0.968 2 23 0 0 0 H(1) 0.000 1.935 1.311 0.968 3 12 0 0-1 H(1) 1.557 1.164 -0.383 1.911 4 19 -1 0-1 H(1) -1.557 1.164 -0.383 1.911 5 13 0-1-1 H(1) 0.000 -0.393 -1.311 2.563 6 24 0 0-1 H(1) 0.000 2.721 -1.311 2.563 7 5 0-1-1 O(1) 0.000 -1.164 -0.726 2.743 8 5 0 0-1 O(1) 0.000 3.492 -0.726 2.743 9 15 -1 0 0 H(1) -2.328 0.393 2.077 2.800 10 15 0 0 0 H(1) 2.328 0.393 2.077 2.800 11 22 -1 0 0 H(1) -2.328 1.935 2.077 2.800
Label of
unique atom 1
Ice VIII
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XIV. Search strategies
TRHO (*)grid meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax
xmin xmin xmax xmax xstep xstep
ymin ymin ymax ymax ystep ystep
zmin zmin zmax zmax zstep zstep
This is a grid-search for CPs in a given portion of the cell. Warning: the grid search is very costly if the whole asymmetric unit is explored.
The CP search algorithm can be chosen (EF or NR). NR is strongly recommend here, unless one is looking for a specific kind of CP in the cell volume explored and does not care of other CP types that may be there present.
Use a small value for nstep provided the grid step is small enough ( 0.2-0.3 Å)
Grid intervals and steps in fractional units. Space group constraints among x,y,z fractional coordinates to be included in TOPXD (implemented in TOPOND)
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I. Search strategies -2
TLAP (*)auto meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax ntheta ntheta nphi nphi
< atom(s) specifications >
< NNA specifications >
. . . . . . . . . . . . . . . . . . . . .
This is a systematic search of -2 Cps. It bears some resemblance to XDPROP CPSEARCH SHELL, but differs from it since:
1. it allows to select the search algorithm (NR, EF)
2. it allows to make a search for a specific kind of CP (if EF method is selected)
Choice of starting points takes into account that the Laplacian distribution retains an atomic-like portrait, even following chemical combination.
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II. Search strategies -2
TLAP (*)auto meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax ntheta ntheta nphi nphi
meth meth is the algorithm used for the -2 CP search :
nr NR
ef type (one of the following keywords: cccp, s1cp, s2cp, cdcp)
(3,-3) (3,-1) (3,+1) (3,+3)
ail if activated AGL lengths and termini are evaluated numerically for each
unique (3,-1) CP. AGL is the union of the unique pair of (-2 )
trajectories that originate at the (3,-1) -2 CP and terminate at
neighboring (3,-3) -2 CPs
nstep nstep maximum number of EF or NR steps for each search (10-15)
ntheta ntheta CP search is started from points located on the surface of a sphere
centered on the nucleus of a given unique atom or at NNA location
nphi nphi ntheta and nphi : intervals for polar coordinates and
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III. Search strategies -2
TLAP (*)auto meth (*)ail (*)debug nstep nstep nnb nnb rstar rstar ntheta ntheta nphi nphi
< atom(s) specifications >
< NNA specifications >
. . . . . . . . . . . . . . . . . . . . .
Atom(s) specifications
(*)atoms label1 ….label (n) nmax nmax rstar rstar
nmax = 0 normal search
0 the search is stopped when nmax different CPs of the required type are
found (only with EF)
rstar = 0 default value
0 sphere radius (Å)
NNA specifications
(*)nna x x y y z z nmax nmax rstar rstar
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IV. Search strategies -2
rstar by default: the distance from the nucleus to the spherical surface where -2 attains its maximum value in the VSCC of the isolated atom).
By using different values of rstar, one explores different region of CC (negative laplacian) or CD (positive Laplacian) or one may take into account that the size of the VSCC has undergone a substantial change in size as due to the considerable CT which occurs in some solids, like the ionic crystals [ Ca (2+) vs Ca or O(2-) vs O]
2nd row atom
VSCC max
VSCD max
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V. Search strategies -2
TLAP (*)points meth (*)ail (*)debug nstep nstep nnb nnb rmax rmax nmax nmax
[(*)car | (*)fra ] x y z
…..
If meth = ef Insert also type
cccp (3,-3)
s1cp (3,-1)
s2cp (3,+1)
cdcp (3,+3)
To stop the search when it has been already successful