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.