Saddelpunkt: Bicyclopropen - Drehung um zentrale Doppelbindung

   

Input

 

Output

$CONTRL OPTIONS
---------------
SCFTYP=RHF RUNTYP=SADPOINT EXETYP=RUN
MPLEVL= 0 LOCAL =NONE UNITS =ANGS
MULT = 1 ICHARG= 0 MAXIT = 30
NPRINT= 7 IREST = 0 COORD =ZMT
ECP =NONE NORMF = 0 NORMP = 0
ITOL = 20 ICUT = 9 NZVAR = 0
NOSYM = 0 INTTYP=POPLE GEOM =INPUT
PLTORB= F MOLPLT= F RPAC = F
AIMPAC= F FRIEND= CITYP =NONE
 --- ENCODED Z MATRIX ---
COORD TYPE I J K L M N
1 1 2 1
2 1 3 2
3 2 3 2 1
4 1 4 2
5 2 4 2 1
6 3 4 2 1 3
7 1 5 1
8 2 5 1 2
9 3 5 1 2 3
10 1 6 1
11 2 6 1 2
12 3 6 1 2 3
13 1 7 3
14 2 7 3 2
15 3 7 3 2 4
16 1 8 4
17 2 8 4 2
18 3 8 4 2 3
19 1 9 5
20 2 9 5 1
21 3 9 5 1 6
22 1 10 6
23 2 10 6 1
24 3 10 6 1 5
 -----------------------------
STATIONARY POINT LOCATION RUN
-----------------------------

OBTAINING INITIAL HESSIAN, HESS=READ

$HESS GROUP READ FROM CARDS
ENERGY IS -228.3005663164 E(NUC) IS 180.6570889061

PARAMETERS CONTROLLING GEOMETRY SEARCH ARE
METHOD =QA UPHESS =POWELL
NNEG = 1 NFRZ = 0
NSTEP = 20 IFOLOW = 1
HESS =READ RESTAR = F
IHREP = 0 HSSEND = F
NPRT = 0 NPUN = 0
OPTTOL = 1.000E-04 RMIN = 1.500E-03
RMAX = 1.000E-01 RLIM = 7.000E-02
DXMAX = 2.000E-01 PURIFY = F
MOVIE = F TRUPD = T
TRMAX = 3.000E-01 TRMIN = 5.000E-02
ITBMAT = 10 STPT = F
STSTEP = 1.000E-02 PROJCT= T
MAXDII = 20 NSKIP = 2
NSERCH= 20 ENERGY= -228.6050498

-----------------------
GRADIENT (HARTREE/BOHR)
-----------------------
ATOM ZNUC DE/DX DE/DY DE/DZ
--------------------------------------------------------------
1 C1 6.0 0.0008390 -0.0078708 0.0075285
2 C2 6.0 0.0043498 -0.0073422 -0.0318653
3 C3 6.0 -0.0024079 0.0219300 0.0080732
4 C4 6.0 -0.0156089 0.0183447 0.0233218
5 C5 6.0 0.0036765 -0.0096291 0.0039276
6 C6 6.0 0.0063001 -0.0084278 0.0162843
7 H7 1.0 0.0199035 -0.0211760 -0.0101760
8 H8 1.0 -0.0112672 0.0135647 -0.0069990
9 H9 1.0 -0.0150366 0.0048309 -0.0142575
10 H10 1.0 0.0092517 -0.0042245 0.0041624

MAXIMUM GRADIENT = 0.0318653 RMS GRADIENT = 0.0132447
HESSIAN UPDATED USING THE POWELL FORMULA
LOCAL CURVATURE 1 OF THE APPROXIMATE HESSIAN HAS EIGENVALUE= -0.027495
*** THIS MODE HAS AN INCORRECT CURVATURE ***
THE COMPONENTS OF THIS MODE FOLLOWS:
-0.009619 -0.006551 0.488405 0.059277 0.176502
0.511340 0.067954 0.010207 0.023076 0.172057
0.056756 0.079947 -0.043841 0.016889 -0.008378
-0.114786 -0.026237 -0.053516 -0.001590 -0.017861
-0.309881 0.118869 -0.243636 -0.254966 -0.044025
0.079531 -0.210715 -0.204295 -0.045600 -0.265313
LOCAL CURVATURE 7 OF THE APPROXIMATE HESSIAN HAS EIGENVALUE= 0.053699
*** THIS MODE HAS AN INCORRECT CURVATURE ***
THE COMPONENTS OF THIS MODE FOLLOWS:
0.060864 -0.106938 -0.111068 0.052232 0.152108
-0.102599 0.107092 0.247054 0.098996 0.027678
0.174102 -0.069510 0.003595 -0.162796 0.138998
0.071171 -0.196188 0.203886 0.476753 -0.163685
-0.047013 -0.203397 0.098625 0.006697 -0.473416
0.235210 -0.036403 -0.122573 -0.277494 -0.081984
ACTUAL ENERGY CHANGE WAS -0.0013001845
PREDICTED ENERGY CHANGE WAS -0.0012901124 RATIO= 1.008
OVERLAP OF CURRENT MODE 7 WITH PREVIOUS MODE IS 0.786984
FOLLOWING MODE 7 WITH EIGENVALUE 0.05370 AND COMPONENTS
0.06086 -0.10694 -0.11107 0.05223 0.15211 -0.10260
0.10709 0.24705 0.09900 0.02768 0.17410 -0.06951
0.00360 -0.16280 0.13900 0.07117 -0.19619 0.20389
0.47675 -0.16368 -0.04701 -0.20340 0.09862 0.00670
-0.47342 0.23521 -0.03640 -0.12257 -0.27749 -0.08198
TRIM/QA LAMBDA FOR TS MODE = 1.41120428
TRIM/QA LAMBDA FOR NON-TS MODES = -1.41120428
TRIM/QA STEP HAS LENGTH = 0.050000
RADIUS OF STEP TAKEN= 0.05000 CURRENT TRUST RADIUS= 0.05000
1 ***** FAILURE TO LOCATE STATIONARY POINT, TOO MANY STEPS TAKEN *****
UPDATED HESSIAN, GEOMETRY, AND VECTORS WILL BE PUNCHED FOR RESTART

Bicyclopropen, 90° verdrillt
**** THE GEOMETRY SEARCH IS NOT CONVERGED! ****

THE NEXT PREDICTED SET OF COORDINATES FOLLOWS. THEIR
ENERGY AND GRADIENT IS UNKNOWN. YOU MAY PREFER TO RESTART
WITH SOME OTHER COORDINATES THAN THESE.

YOU SHOULD RESTART "OPTIMIZE" RUNS WITH THE COORDINATES
WHOSE ENERGY IS LOWEST. RESTART "SADPOINT" RUNS WITH THE
COORDINATES WHOSE RMS GRADIENT IS SMALLEST. THESE ARE NOT
ALWAYS THE LAST POINT COMPUTED!

COORDINATES OF ALL ATOMS ARE (ANGS)
ATOM CHARGE X Y Z
------------------------------------------------------------
C1 6.0 -0.6113628488 -0.0412000092 0.0057926179
C2 6.0 0.6712478920 0.0055296741 -0.2820764227
C3 6.0 1.9700507740 0.7488846577 -0.1329620139
C4 6.0 1.8757330759 -0.4290122664 0.4004704863
C5 6.0 -1.9419588376 -0.6728718904 0.0476310289
C6 6.0 -1.8750061216 0.6204644053 0.1776296894
H7 1.0 2.8015080599 1.2753910864 -0.5944044892
H8 1.0 2.3847312015 -1.2467521883 0.8303423493
H9 1.0 -2.6713212596 -1.4470658469 -0.1709113794
H10 1.0 -2.3435268867 1.5645841310 0.3257594888

THE CURRENT FULLY SUBSTITUTED Z-MATRIX IS
C1
C2 1 1.3153488
C3 2 1.5038952 1 146.9286139
C4 2 1.4510278 1 134.0946079 3 85.2590798 0
C5 1 1.4735147 2 154.4191294 3 -171.5997965 0
C6 1 1.4367053 2 150.1654700 3 40.3696740 0
H7 3 1.0869496 2 149.0883800 4 125.9785835 0
H8 4 1.0547831 2 145.5323594 3 -166.3787649 0
H9 5 1.0858668 1 155.0212373 6 154.8383394 0
H10 6 1.0643384 1 144.3255535 5 178.9710863 0

INTERNUCLEAR DISTANCES (ANGS.)
------------------------------

C1 C2 C3 C4

1 C1 0.0000000 1.3153488 * 2.7031801 * 2.5479041 *
2 C2 1.3153488 * 0.0000000 1.5038952 * 1.4510278 *
3 C3 2.7031801 * 1.5038952 * 0.0000000 1.2964903 *
4 C4 2.5479041 * 1.4510278 * 1.2964903 * 0.0000000
5 C5 1.4735147 * 2.7198870 * 4.1662723 3.8417099
6 C6 1.4367053 * 2.6594894 * 3.8597178 3.9011670
7 H7 3.7069309 2.4996210 * 1.0869496 * 2.1798684 *
8 H8 3.3331393 2.3961866 * 2.2544360 * 1.0547831 *
9 H9 2.5002223 * 3.6462529 5.1347807 4.6945302
10 H10 2.3835507 * 3.4480404 4.4139261 4.6671365

C5 C6 H7 H8

1 C1 1.4735147 * 1.4367053 * 3.7069309 3.3331393
2 C2 2.7198870 * 2.6594894 * 2.4996210 * 2.3961866 *
3 C3 4.1662723 3.8597178 1.0869496 * 2.2544360 *
4 C4 3.8417099 3.9011670 2.1798684 * 1.0547831 *
5 C5 0.0000000 1.3015764 * 5.1680186 4.4342104
6 C6 1.3015764 * 0.0000000 4.7848459 4.6965832
7 H7 5.1680186 4.7848459 0.0000000 2.9265702 *
8 H8 4.4342104 4.6965832 2.9265702 * 0.0000000
9 H9 1.0858668 * 2.2428286 * 6.1272326 5.1581296
10 H10 2.2901576 * 1.0643384 * 5.2346651 5.5240058

H9 H10

1 C1 2.5002223 * 2.3835507 *
2 C2 3.6462529 3.4480404
3 C3 5.1347807 4.4139261
4 C4 4.6945302 4.6671365
5 C5 1.0858668 * 2.2901576 *
6 C6 2.2428286 * 1.0643384 *
7 H7 6.1272326 5.2346651
8 H8 5.1581296 5.5240058
9 H9 0.0000000 3.0698806
10 H10 3.0698806 0.0000000

* ... LESS THAN 3.000


NUCLEAR ENERGY = 176.2463590776
ELECTRONIC ENERGY = 0.0000000000
TOTAL ENERGY = 0.0000000000


NSERCH= 19 ENERGY= -228.6037496
MAXIMUM GRADIENT = 0.0332273 RMS GRADIENT = 0.0134504
NSERCH= 18 ENERGY= -228.6043639
MAXIMUM GRADIENT = 0.0338058 RMS GRADIENT = 0.0134204
NSERCH= 17 ENERGY= -228.6047548
MAXIMUM GRADIENT = 0.0353835 RMS GRADIENT = 0.0135347

Nächster Versuch: Erhöhung von NSTEP in $STATPT auf 60


NSERCH= 60 ENERGY= -228.5817670   ist zwar höher als vorher, aber RMS auch (s. unten)

-----------------------
GRADIENT (HARTREE/BOHR)
-----------------------
ATOM ZNUC DE/DX DE/DY DE/DZ
--------------------------------------------------------------
1 C1 6.0 0.0155833 -0.0139347 0.0270385
2 C2 6.0 -0.0066286 0.0114362 -0.0092862
3 C3 6.0 0.0134207 0.0150183 -0.0106964
4 C4 6.0 0.0050201 0.0105994 -0.0075451
5 C5 6.0 -0.0199258 -0.0237871 0.0069049
6 C6 6.0 0.0088994 -0.0310125 0.0145812
7 H7 1.0 0.0262045 0.0044166 -0.0040944
8 H8 1.0 -0.0372880 0.0143328 0.0083874
9 H9 1.0 -0.0221506 0.0152164 -0.0145283
10 H10 1.0 0.0168650 -0.0022855 -0.0107617

MAXIMUM GRADIENT = 0.0372880 RMS GRADIENT = 0.0164677
HESSIAN UPDATED USING THE POWELL FORMULA
LOCAL CURVATURE 1 OF THE APPROXIMATE HESSIAN HAS EIGENVALUE= -0.028269
*** THIS MODE HAS AN INCORRECT CURVATURE ***
THE COMPONENTS OF THIS MODE FOLLOWS:
0.043563 0.085009 -0.262105 -0.054367 0.101378
-0.269235 0.027449 0.015734 -0.016119 -0.157227
-0.091567 -0.239335 0.138808 -0.030702 0.047626
0.066839 0.076273 -0.110765 0.099222 0.061381
0.513800 -0.361100 -0.002085 -0.071966 0.157058
-0.128638 0.480633 0.039755 -0.086783 -0.072534
LOCAL CURVATURE 2 OF THE APPROXIMATE HESSIAN HAS EIGENVALUE= -0.012866
*** THIS MODE HAS AN INCORRECT CURVATURE ***
THE COMPONENTS OF THIS MODE FOLLOWS:
-0.024739 -0.198007 -0.248685 -0.020063 -0.209658
-0.292883 -0.023120 -0.010536 -0.096368 -0.004422
0.011133 -0.012461 -0.089541 -0.025230 -0.232060
0.084248 -0.104301 0.029554 -0.032444 0.121888
-0.005506 0.013360 0.291644 0.426319 -0.255854
-0.073724 0.033829 0.352576 0.196791 0.398259
LOCAL CURVATURE 3 OF THE APPROXIMATE HESSIAN HAS EIGENVALUE= -0.004513
*** THIS MODE HAS AN INCORRECT CURVATURE ***
THE COMPONENTS OF THIS MODE FOLLOWS:
-0.027387 0.127249 -0.254068 0.040834 0.234912
0.041020 0.234312 0.001818 -0.076937 0.035162
0.075700 0.064877 -0.027737 -0.045130 -0.201639
-0.122669 -0.089139 0.076404 0.500543 -0.228518
-0.097281 -0.077794 0.067214 0.159276 -0.034410
-0.054740 -0.001568 -0.520855 -0.089367 0.289916
LOCAL CURVATURE 6 OF THE APPROXIMATE HESSIAN HAS EIGENVALUE= 0.036698
*** THIS MODE HAS AN INCORRECT CURVATURE ***
THE COMPONENTS OF THIS MODE FOLLOWS:
-0.084298 0.127025 -0.247585 0.006511 -0.059772
0.152114 -0.067785 -0.113085 0.156831 -0.022951
-0.114471 0.134601 0.079895 0.189640 -0.227903
-0.060623 0.188599 -0.258718 -0.258440 0.004394
-0.105875 0.285802 -0.211009 -0.049853 0.257657
-0.339719 0.230114 -0.135768 0.328397 0.216274
ACTUAL ENERGY CHANGE WAS 0.0009828005
PREDICTED ENERGY CHANGE WAS 0.0008940475 RATIO= 1.099
OVERLAP OF CURRENT MODE 5 WITH PREVIOUS MODE IS 0.803883
WARNING!! MODE SWITCHING WAS FOLLOWING MODE 6, NOW FOLLOWING MODE 5
FOLLOWING MODE 5 WITH EIGENVALUE 0.02852 AND COMPONENTS
-0.03562 -0.05166 0.11422 -0.02862 0.22167 0.36010
0.04354 0.10136 0.02302 -0.04220 0.18709 0.14217
-0.07242 -0.10938 -0.14565 0.01596 -0.15119 -0.19494
0.20230 0.04409 -0.24180 -0.41596 -0.06623 -0.22021
-0.09107 -0.29507 0.12718 0.42410 0.11931 0.03592
TRIM/QA LAMBDA FOR TS MODE = 0.54877719
TRIM/QA LAMBDA FOR NON-TS MODES = -0.54877719
TRIM/QA STEP HAS LENGTH = 0.150000
RADIUS OF STEP TAKEN= 0.15000 CURRENT TRUST RADIUS= 0.15000
1 ***** FAILURE TO LOCATE STATIONARY POINT, TOO MANY STEPS TAKEN *****
UPDATED HESSIAN, GEOMETRY, AND VECTORS WILL BE PUNCHED FOR RESTART

Bicyclopropen, 90° verdrillt
**** THE GEOMETRY SEARCH IS NOT CONVERGED! ****

THE NEXT PREDICTED SET OF COORDINATES FOLLOWS. THEIR
ENERGY AND GRADIENT IS UNKNOWN. YOU MAY PREFER TO RESTART
WITH SOME OTHER COORDINATES THAN THESE.

YOU SHOULD RESTART "OPTIMIZE" RUNS WITH THE COORDINATES WHOSE ENERGY IS LOWEST. RESTART "SADPOINT" RUNS WITH THE COORDINATES WHOSE RMS GRADIENT IS SMALLEST. THESE ARE NOT ALWAYS THE LAST POINT COMPUTED!
Bringt also auch keine Lösung

RMS-Werte:
NSERCH= 59 ENERGY= -228.5827498
MAXIMUM GRADIENT = 0.0401578 RMS GRADIENT = 0.0176253
NSERCH= 58 ENERGY= -228.5884545
MAXIMUM GRADIENT = 0.0313875 RMS GRADIENT = 0.0149318

NSERCH= 57 ENERGY= -228.5730315
MAXIMUM GRADIENT = 0.0308372 RMS GRADIENT = 0.0158240
NSERCH= 56 ENERGY= -228.5614452
MAXIMUM GRADIENT = 0.0317094 RMS GRADIENT = 0.0169446
NSERCH= 55 ENERGY= -228.5548670
MAXIMUM GRADIENT = 0.0359490 RMS GRADIENT = 0.0177120

Nochmal NSTEP erhöhen

NSERCH=100 ENERGY= -228.6661794
MAXIMUM GRADIENT = 0.0023083 RMS GRADIENT = 0.0008151

Da das ein wesentlich geringerer Gradient ist, nochmal NSTEP erhöhen.
Aber auch das bringt keine Konvergenz:
NSERCH=200 ENERGY= -228.6119525
MAXIMUM GRADIENT = 0.0174053 RMS GRADIENT = 0.0079854