HINT
(Hilderbrandt INTernal Coordinates)
Diese Art von internen Koordinaten ist extrem schwierig zu verstehen. Es nutzt dabei auch nicht viel, die empfohlene Literaturstelle zu lesen (R. L. Hilderbrandt, Cartesian Coordinates of Molecular Models, J. Chem. Phys. 51, 1654 (1969)). Da die Geometrieoptimierung angeregter Zustände nur mit diesen Koordinaten funktioniert, ist es aber notwendig, damit arbeiten zu können. Ich versuche es anhand einiger Beispiele.
COORD=HINT: only symmetry unique atoms will be given, in Hilderbrandt style internals
!
! H2O
!
!
!
$CONTRL
SCFTYP=RHF MULT=1 RUNTYP=TRUDGE CITYP=GUGA COORD=HINT $END
$SYSTEM
TIMLIM=100 MEMORY=5000000 $END
$BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END
$GUESS GUESS=HUCKEL $END
$TRUDGE
OPTMIZ=GEOMETRY NPAR=2 IEX(1)=21,22 P(1)=0.96 $END
$CIDRT
GROUP=C2V SOCI=.TRUE. NFZC=1 NDOC=4 NVAL=14 NEXT=-1 $END
$DATA
Water CI-SD Geometry Optimization
CNV 2
O 8.0 LC
0.0 0.0 0.0
- O K
H 1.0 PCC
0.94 53.0 0.0
+ O K I
$END
!
! H2O
!
!
!
$CONTRL
SCFTYP=RHF MULT=1 RUNTYP=TRUDGE COORD=HINT $END
$SYSTEM
TIMLIM=100 MEMORY=1000000 $END
$BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END
$GUESS GUESS=HUCKEL $END
$TRUDGE
OPTMIZ=GEOMETRY NPAR=2 IEX(1)=21,22 P(1)=0.96 $END
!
OPTMIZ=GEOMETRY: IEX define the pointer to the hint
!
internal coordinates which will be optimized. The pointer
! is
defined as: (number of atom)*10 + (number of internal
!
coordinate for that atom). For each atom the hint are
!
numbered as 1, 2, and 3 for BOND, ALPHA, and BETA, resp.)
-- $DRT GROUP=C2V IEX=2 NFZC=1 NDOC=4 NVAL=14 $END
$DATA
Water CI-SD Geometry Optimization
CNV 2
O 8.0 LC 0.0 0.0
0.0 - O K
H 1.0 PCC
0.94 53.0 0.0
+ O K I
$END
NAME, ZNUC,
CONX, R, ALPHA, BETA, SIGN, POINT1, POINT2, POINT3
NAME: 10
character atomic name (used only for print out).
ZNUC:
nuclear charge.
CONX:
connection type, choose from:
LC: linear connection
PCC: planar central connection
NPCC: non-planar central connection
PTC : planar terminal
connection
CCPA : central connection with
polar atom
TCT: terminal connection with
torsion
R:
connection distance
ALPHA: first
connection angle
BETA:
second connection angle
SIGN:
connection sign “+” or “-“
POINT1,
POINT2, POINT3: connection points, a serial number of a previously input atom,
or one of 4 standard points: O, I, J, K (origin and unit points on axes of
master frame). Default: POINT1=O, POINT2=I, POINT3=J
$TRUDGE:
non-gradient optimization
NPAR=
number of parametres to be optimized
IEX=
defines the parameters to be optimized. Pointers to the HINT internal
coordinates which will be optimized. The pointers to the internal coordinates
are defined as: (the number of atom in the input list)*10 + (the nunmber of
internal coordinate for that atom). For each atom, the HINT internal
coordinates are numbered as 1, 2, and 3 for BOND, ALPHA, and BETA,
respectively.
P= Defines
the initial values of the parameters to be optimized. If omitted, the $DATA
values are used.
-----------------------------------------------------------
INTERNAL
COORDINATES (ANGSTROMS/DEGREE)
I BOND
ALPHA BETA SIGN ICONX IATCON INATOM
1
0.0000000 0.00000 0.00000 -1.0 1501504503 1
2
0.9600000 53.00000 0.00000
1.0 2501504502 3
-----------------------------------------------------------
----- TRUDGE
RESTART DATA AT NSTEP 0 --------
$TRUDGE
OPTIMIZE=GEOMETRY NPAR= 2
IEX(1)= 21, 22,
P(1)= 0.960000, 53.000000,
$END
TRUDGE ENERGY VALUE AT NSTEP= 0 IS
-76.0103894679
-----------------------------------------------------------
INTERNAL
COORDINATES (ANGSTROMS/DEGREE)
I BOND
ALPHA BETA SIGN
ICONX IATCON INATOM
1
0.0000000 0.00000 0.00000 -1.0 1501504503 1
2
0.9600000 58.57406 0.00000
1.0 2501504502 3
-----------------------------------------------------------
----- TRUDGE RESTART
DATA AT NSTEP 1 --------
$TRUDGE
OPTIMIZE=GEOMETRY NPAR= 2
IEX(1)= 21, 22,
P(1)= 0.960000, 58.574059,
$END
TRUDGE ENERGY VALUE AT NSTEP= 1 IS
-76.0064779202
LOOKS = 1 ALF =
0.1000 FUNC = -76.006477920
AMIN = 0.0000 FMIN = -76.010389468 ANEXT = 0.1000 FNEXT = -76.006477920
-----------------------------------------------------------
INTERNAL
COORDINATES (ANGSTROMS/DEGREE)
I BOND
ALPHA BETA SIGN ICONX IATCON INATOM
1
0.0000000 0.00000 0.00000 -1.0 1501504503 1
2
0.9600000 47.95638 0.00000
1.0 2501504502 3
-----------------------------------------------------------
----- TRUDGE
RESTART DATA AT NSTEP 2 --------
$TRUDGE
OPTIMIZE=GEOMETRY NPAR= 2
IEX(1)=
21, 22,
P(1)= 0.960000, 47.956383,
$END
TRUDGE ENERGY VALUE AT NSTEP= 2 IS
-76.0078393859
LOOKS = 2 ALF = -0.1000 FUNC = -76.007839386 AMIN = 0.0000 FMIN = -76.010389468 ANEXT = -0.1000 FNEXT = -76.007839386
-----------------------------------------------------------
INTERNAL
COORDINATES (ANGSTROMS/DEGREE)
I BOND
ALPHA BETA SIGN ICONX IATCON INATOM
1
0.0000000 0.00000 0.00000 -1.0 1501504503 1
2
0.9600000 52.44458 0.00000
1.0 2501504502 3
-----------------------------------------------------------
----- TRUDGE
RESTART DATA AT NSTEP 3 --------
$TRUDGE
OPTIMIZE=GEOMETRY NPAR= 2
IEX(1)=
21, 22,
P(1)= 0.960000, 52.444576,
$END
TRUDGE ENERGY VALUE AT NSTEP= 16 IS
-76.0107457254
NON-GRADIENT
ENERGY MINIMIZATION ... CONVERGED
CONJUGATE
DIRECTION = 0
PARAMETER
= 1
VALUE OF THE
FUNCTION = -76.0107457254
FNOT = -76.0107457254
$TRURST
KSTART= 0 JSTART= 1 TOLF= 0.001000 TOLR= 0.050000
FNOISE= 0.000500 FNOT= -76.010745725
RNOT(1)= 0.007667 -0.006251
CURV(1)= 1.901800 0.321617
ALPH(1)= 0.012500 0.012500
V(1)= 1.000000 0.000000
0.000000 1.000000
$END
-----------------------------------------------------------
INTERNAL
COORDINATES (ANGSTROMS/DEGREE)
I BOND
ALPHA BETA SIGN ICONX IATCON INATOM
1
0.0000000 0.00000 0.00000 -1.0 1501504503 1
2
0.9472348 52.66973 0.00000
1.0 2501504502 3
-----------------------------------------------------------
COORDINATES OF
ALL ATOMS ARE (ANGS)
ATOM CHARGE X Y Z
------------------------------------------------------------
O 8.0 0.0000000000
0.0000000000 0.0000000000
H 1.0 -0.7531968076
0.0000000000 0.5744113322
H 1.0 0.7531968076
0.0000000000 0.5744113322
INTERNUCLEAR DISTANCES (ANGS.)
------------------------------
O H H
1 O 0.0000000
0.9472348 * 0.9472348 *
2 H 0.9472348 *
0.0000000 1.5063936 *
3
H 0.9472348 * 1.5063936 * 0.0000000
Benzol
!
! Benzol,
HINT
!
$CONTRL
SCFTYP=RHF MULT=1 RUNTYP=TRUDGE COORD=HINT $END
$TRUDGE
OPTMIZ=GEOMETRY NPAR=2 IEX(1)=11,21 $END
$SYSTEM
TIMLIM=10 MEMORY=6000000 $END
$BASIS GBASIS=N31 NGAUSS=6 $END
$GUESS GUESS=HUCKEL $END
$DATA
Benzene
Dnh 6
C 6.0 LC
1.390 0.0 0.0
+ O
H 1.0 LC
2.470 0.0 0.0
+ O
$END
Man erkennt, dass sich Linear Connection (LC) auf den Abstand zum Ursprung (O, Origin) bezieht. Das Vorzeichen spielt hier keine Rolle.