[molpro-user] symmetric vibrational displacement coordinates

Dima Khoroshun dima at mpi-muelheim.mpg.de
Sun Oct 24 07:18:50 BST 2004


Dear Molpro Users!

This is my second approach to the mail interface while writing this letter.

I am trying to optimize several small molecules using numerical optimization
facilities of Molpro. Although the examples below are CAS, and should be
possible to optimize analytically, it is desired to perform numerical
optimizations (subsequently, RS2 optimizations would be performed, which
have to be numerical).

I also want to keep these molecules planar. The initial guess of the geometries
is planar, all Z coordinates are 0, but the X and the Y coordinates are rather
arbitrary. 

Because the systems are cyclic, I refrained from using the Z-matrix coordinates.
Instead, I am trying to 

(a) input coordinates as xyz's
(b) request the BMAT as the optimizer coordinate system
(c) rely on the "symmetric vibrational displacements" displacement type in
    obtaining the numerical gradients

It is this last part of the strategy, the "symmetric vibrational displacements",
which I want to understand more.

It looks like the ** number ** of these displacement coordinates varies with the
starting point of the optimization. I expected this number to be 2N-3 (2 in-plane
displacements, 1 in-plane rotation). But turns out that for "more symmetric" starting
guesses this number might be ** smaller **. This is very suspicious, because optimizing in
an incomplete coordinate space without explicit constraints might result.

Is it a very clever trick, which guarantees a decent gradient using less points for 
numerical differentiation? Or does the displacement coordinate setup algorythm have
very loose threshold for establishing symmetry elements?

I am attaching four partial output examples. Again, the focus is on the starting geometry 
and the displacement coordinate setup, not on the casscf or anything else.

For instance, Examples 1 and 2 are same molecule, C3H3, three C-H groups. In Example 1, 
the C-C distances are 1.372188874, 1.340853825, 1.403480765. Hardly any symmetry (again, 
except the planarity). Yet there are only 8 displacement coordinates! One expects 2*6-3=9.

And if the starting geometry is distorted even further, to distances C-C of 1.327771180, 
1.462215094, 1.503255221, there are indeed 9 displacement coordinates (Example 2).

Similarly Examples 3 and 4 are the same molecule, C3NH4, three C-H and one N-H group.
For a "less distorted" starting geometry, one gets 12 coordinates, for "more distorted" --
the correct (?) 2*8-3=13 coordinates.

Because I am optimizing many states, I'd like to have as less constraints as possible,
to arrive at true (planar) stationary points. Even less desired are the implicit constraints,
of which only the program knows.

So my questions are:

1. How many displacement coordinates * should * there be? 

2. Why does the number of coordinates depend on the initial geometry?

3. Is this dependence an error in the program, or am I missing something in 
   understanding what these displacement coordinates are?

4. My understanding is that for a planar Cs molecule one should get 2N-3 coordinates.
   If this is conceptually so, how to enforce this behavior in the program? Some
   numerical threshold? Are there any patches missing? The executable was downloaded, not 
   locally compiled.

5. If for a Cs molecule the number of coordinates may vary with the starting geometry,
   and be even less than 2N-3, how to understand this behavior? Any explanation would be
   most welcome.

Thank you very much for your time and attention!

Sincerely,
Dmitry Khoroshun
dima at mpi-muelheim.mpg.de

----- Example 1
This Molpro2002.3 job is running on host:
op22th13
---------------
---------------

 MPP nodes  nproc
 op22th13     1
 ga_uses_ma=true, calling ma_init with heap size        8010000 determined by size of -G / nprocs

 Primary working directories:    /usr/scratch/dima/c3h3-start1.18900.scratch
 Secondary working directories:  /usr/scratch/dima/c3h3-start1.18900.scratch
 
 blaslib=atlas           

 MPP tuning parameters: Latency=  1000 Microseconds,   Broadcast speed=   20 MB/sec
 default implementation of scratch files=df  

 ***,
 Including file /ds20th/san/users/dima/MY-EXECS/molpro2002-opterons/molpro-mpp-Linux-i686-i4-2002.6/molproi.rc
 ***,comment
 memory,100,m
 basis,vdz
  
 geomtyp=xyz
 geometry={
 6
 text
 C1,0.043610,0.756620,0.0
 C2,0.693240,-0.452050,0.0
 C3,-0.706850,-0.354550,0.0
 H4,0.174710,1.891970,0.0
 H5,1.551420,-1.097260,0.0
 H6,-1.726110,-0.794900,0.0
 }
  
 hf
 wf,20,1,0
 occ,9,1
 closed,9,1
  
 multi
 occ,9,3
 closed,9,0
 pspace,5.0
 maxiter,200
  
                                                                                 ! --- 2A ---
  
 wf,21,2,1
 state,6
  
                                                                                 ! --- 4A ---
  
 wf,21,2,3
 state,1
  
  
 text,start
  
  
 multi
 occ,9,3
 closed,9,0
 pspace,5.0
 maxiter,200
  
 wf,21,2,1
 state,1
 weight,1
  
 geomvar=energy(1)
  
 opt,startcmd=text,numerical
 variable,geomvar
 coord,,bmat

 Variables initialized (303), CPU time= 0.00 sec
 Default parameters read. Elapsed time= 0.02 sec
 Checking input...
 Passed
1


                                         ***  PROGRAM SYSTEM MOLPRO  ***
                                      Copyright, University of Birmingham, 1997

                                    Version 2002.6 linked 7 Nov 2003 10:22:41 


 **********************************************************************************************************************************
 LABEL *   COMMENT                                                                       
 Linux-2.6.5-7.108-smp/op22th13(x86_64) 32 bit mpp version                               DATE:  24-Oct-04         TIME: 07:12:22  
 **********************************************************************************************************************************

 Installed patches: cidps_orthp configure_xeon darwin_conf dft_orbital_hi enest_dummy fujitsu-ssl2
                    fujitsu_conf ga_conflict2 ia64root_check merge_orbdom mkl60 modelopt
                    molden_orbital_normalization mpputil mxm_fujitsu nec_parse opteron2 patcher_printf
                    posinp pseudo_libmol2 readop_multipole_nps sun_forte8
 **********************************************************************************************************************************
 SETTING BASIS          =    VDZ
 SETTING GEOMTYP        =    XYZ

 Variable memory set to  100000000 words,  buffer space   230000 words
 


 Using spherical harmonics

 Library entry C      S cc-pVDZ              selected for orbital group  1
 Library entry C      P cc-pVDZ              selected for orbital group  1
 Library entry C      D cc-pVDZ              selected for orbital group  1
 Library entry H      S cc-pVDZ              selected for orbital group  2
 Library entry H      P cc-pVDZ              selected for orbital group  2

1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets)     Author: Roland Lindh, 1990

 Geometry written to block  1 of record 700


 Point group  Cs  



 ATOMIC COORDINATES

 NR  ATOM    CHARGE       X              Y              Z

   1  C1      6.00    0.082410950    1.429804477    0.000000000
   2  C2      6.00    1.310033644   -0.854250633    0.000000000
   3  C3      6.00   -1.335752815   -0.670002349    0.000000000
   4  H4      1.00    0.330154027    3.575304879    0.000000000
   5  H5      1.00    2.931758693   -2.073520738    0.000000000
   6  H6      1.00   -3.261874926   -1.502143188    0.000000000

 Bond lengths in Bohr (Angstrom)

  1--2  2.593060976   1--3  2.533846320   1--4  2.159756607   2--3  2.652194076   2--5  2.028943499
       (1.372188874)       (1.340853825)       (1.142894060)       (1.403480765)       (1.073670739)

  3--6  2.098190831
       (1.110314852)

 Bond angles

  1--2--3   57.75952417   1--2--5  155.19405844   1--3--2   59.94932003   1--3--6  147.39998462

  2--1--3   62.29115580   2--1--4  145.15624929   2--3--6  152.65069535   3--1--4  152.55259491

  3--2--5  147.04641739

 NUCLEAR CHARGE:                   21
 NUMBER OF PRIMITIVE AOS:         102
 NUMBER OF SYMMETRY AOS:           99
 NUMBER OF CONTRACTIONS:           57   (  42A'  +  15A"  )
 NUMBER OF CORE ORBITALS:           3   (   3A'  +   0A"  )
 NUMBER OF VALENCE ORBITALS:       15   (  12A'  +   3A"  )


 NUCLEAR REPULSION ENERGY   58.69270844

<------------------------ skipped ---------------------------->

 **********************************************************************************************************************************
 SETTING GEOMVAR        =      -115.19438637  HARTREE

 PROGRAM * OPT (Geometry optimization step)     Author: F. Eckert

 Optimizing variable GEOMVAR; current value: -115.19438637 HARTREE     

 symmetric vibrational displacements
                   1             2             3             4             5             6             7             8
         1     0.0890740     0.5321178     0.1444091    -0.4103799    -0.0062405    -0.0679629     0.4740862    -0.0280160
         2     0.2010166    -0.0237383     0.1180629     0.0914272    -0.0249745     0.6515565     0.1483601    -0.5612294
         3     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         4     0.1455607    -0.2840833     0.2235416    -0.1831693    -0.0166063    -0.3674462    -0.4453686    -0.4959261
         5     0.2945197    -0.4502618     0.3588564     0.0173055     0.0284267    -0.2638068     0.4492647     0.3211768
         6     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         7     0.0568473    -0.2143061    -0.0302782    -0.2214763     0.0253069     0.5582656    -0.2873458     0.5223347
         8     0.2544543     0.4846505     0.3245623     0.2356789     0.0182941    -0.1048593    -0.4854741     0.2446532
         9     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        10    -0.1638428    -0.2559415    -0.0351516    -0.0969559     0.0515886    -0.0266911     0.0347476    -0.0007750
        11     0.1749668     0.0339746    -0.6511728    -0.1974127     0.5556834    -0.1551896    -0.0478229    -0.0300522
        12     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        13    -0.4322834     0.1229920     0.1559159     0.5178343     0.4792695     0.0055609     0.1222797    -0.0234827
        14    -0.5361058     0.1500347    -0.0074462    -0.3913845    -0.3386791    -0.0524641    -0.0765953     0.0138719
        15     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        16     0.3046441     0.0992210    -0.4584368     0.3941471    -0.5333183    -0.1017263     0.1016010     0.0258651
        17    -0.3888516    -0.1946597    -0.1428626     0.2443857    -0.2387506    -0.0752366     0.0122674     0.0115797
        18     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000

 Doing optimization in   8 symmetrical displacement coordinates
 
 Computing numerical gradient for displacement coordinate   1
----- End of Example 1

----- Example 2
This Molpro2002.3 job is running on host:
op22th17
---------------
---------------

 MPP nodes  nproc
 op22th17     1
 ga_uses_ma=true, calling ma_init with heap size        8010000 determined by size of -G / nprocs

 Primary working directories:    /usr/scratch/dima/c3h3-start2.23869.scratch
 Secondary working directories:  /usr/scratch/dima/c3h3-start2.23869.scratch
 
 blaslib=atlas           

 MPP tuning parameters: Latency=  1000 Microseconds,   Broadcast speed=   20 MB/sec
 default implementation of scratch files=df  

 ***,
 Including file /ds20th/san/users/dima/MY-EXECS/molpro2002-opterons/molpro-mpp-Linux-i686-i4-2002.6/molproi.rc
 ***,comment
 memory,100,m
 basis,vdz
  
 geomtyp=xyz
 geometry={
 6
 text
 C1,0.143610,0.756620,0.0
 C2,0.693240,-0.452050,0.0
 C3,-0.806850,-0.354550,0.0
 H4,0.174710,1.891970,0.0
 H5,1.551420,-1.197260,0.0
 H6,-1.726110,-0.794900,0.0
 }
  
 hf
 wf,20,1,0
 occ,9,1
 closed,9,1
  
 multi
 occ,9,3
 closed,9,0
 pspace,5.0
 maxiter,200
  
                                                                                 ! --- 2A ---
  
 wf,21,2,1
 state,6
  
                                                                                 ! --- 4A ---
  
 wf,21,2,3
 state,1
  
  
 text,start
  
  
 multi
 occ,9,3
 closed,9,0
 pspace,5.0
 maxiter,200
  
 wf,21,2,1
 state,1
 weight,1
  
 geomvar=energy(1)
  
 opt,startcmd=text,numerical
 variable,geomvar
 coord,,bmat

 Variables initialized (303), CPU time= 0.00 sec
 Default parameters read. Elapsed time= 0.10 sec
 Checking input...
 Passed
1


                                         ***  PROGRAM SYSTEM MOLPRO  ***
                                      Copyright, University of Birmingham, 1997

                                    Version 2002.6 linked 7 Nov 2003 10:22:41 


 **********************************************************************************************************************************
 LABEL *   COMMENT                                                                       
 Linux-2.6.5-7.108-smp/op22th17(x86_64) 32 bit mpp version                               DATE:  24-Oct-04         TIME: 07:14:07  
 **********************************************************************************************************************************

 Installed patches: cidps_orthp configure_xeon darwin_conf dft_orbital_hi enest_dummy fujitsu-ssl2
                    fujitsu_conf ga_conflict2 ia64root_check merge_orbdom mkl60 modelopt
                    molden_orbital_normalization mpputil mxm_fujitsu nec_parse opteron2 patcher_printf
                    posinp pseudo_libmol2 readop_multipole_nps sun_forte8
 **********************************************************************************************************************************
 SETTING BASIS          =    VDZ
 SETTING GEOMTYP        =    XYZ

 Variable memory set to  100000000 words,  buffer space   230000 words
 


 Using spherical harmonics

 Library entry C      S cc-pVDZ              selected for orbital group  1
 Library entry C      P cc-pVDZ              selected for orbital group  1
 Library entry C      D cc-pVDZ              selected for orbital group  1
 Library entry H      S cc-pVDZ              selected for orbital group  2
 Library entry H      P cc-pVDZ              selected for orbital group  2

1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets)     Author: Roland Lindh, 1990

 Geometry written to block  1 of record 700


 Point group  Cs  



 ATOMIC COORDINATES

 NR  ATOM    CHARGE       X              Y              Z

   1  C1      6.00    0.271383549    1.429804477    0.000000000
   2  C2      6.00    1.310033644   -0.854250633    0.000000000
   3  C3      6.00   -1.524725414   -0.670002349    0.000000000
   4  H4      1.00    0.330154027    3.575304879    0.000000000
   5  H5      1.00    2.931758693   -2.262493337    0.000000000
   6  H6      1.00   -3.261874926   -1.502143188    0.000000000

 Bond lengths in Bohr (Angstrom)

  1--2  2.509123705   1--3  2.763185864   1--4  2.146305183   2--3  2.840740458   2--5  2.147822071
       (1.327771180)       (1.462215094)       (1.135775872)       (1.503255221)       (1.136578575)

  3--6  1.926174136
       (1.019287531)

 Bond angles

  1--2--3   61.82805986   1--2--5  155.42294181   1--3--2   53.17612859   1--3--6  156.13830377

  2--1--3   64.99581155   2--1--4  153.97775285   2--3--6  150.68556764   3--1--4  141.02643561

  3--2--5  142.74899833

 NUCLEAR CHARGE:                   21
 NUMBER OF PRIMITIVE AOS:         102
 NUMBER OF SYMMETRY AOS:           99
 NUMBER OF CONTRACTIONS:           57   (  42A'  +  15A"  )
 NUMBER OF CORE ORBITALS:           3   (   3A'  +   0A"  )
 NUMBER OF VALENCE ORBITALS:       15   (  12A'  +   3A"  )


 NUCLEAR REPULSION ENERGY   57.04045925

<------------------------ skipped ---------------------------->

 **********************************************************************************************************************************
 SETTING GEOMVAR        =      -115.19531037  HARTREE

 PROGRAM * OPT (Geometry optimization step)     Author: F. Eckert

 Optimizing variable GEOMVAR; current value: -115.19531037 HARTREE     

 symmetric vibrational displacements
                   1             2             3             4             5             6             7             8
         1     0.0138148    -0.2702924    -0.5230259     0.2606856    -0.3431345    -0.0833603    -0.2567096    -0.4169209
         2     0.2002367    -0.0302806     0.0928174     0.0793863     0.1095658    -0.0070816    -0.6013416     0.3294409
         3     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         4    -0.0061602    -0.2857363     0.2697199     0.2743700    -0.0306670    -0.0686444     0.5877108     0.1275594
         5     0.2173894    -0.1164534     0.4482614     0.2945322     0.1864933    -0.1135524    -0.0701231    -0.5454603
         6     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         7    -0.0882705    -0.2535760     0.1910869     0.0682675    -0.2200469    -0.0613236    -0.2273945     0.5365686
         8     0.3607466     0.0448389    -0.4806781     0.1843745     0.3457179    -0.0827116     0.3411091     0.2931935
         9     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        10     0.1294491     0.6531994     0.3122396     0.0014334    -0.0941390    -0.0449621    -0.0084117    -0.0416489
        11     0.1477413    -0.0839128     0.0078181    -0.6574728    -0.4282187    -0.3905308     0.1730149    -0.0555962
        12     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        13    -0.3857412     0.2117916    -0.1871940    -0.1982165     0.5177229    -0.4188307    -0.0966277    -0.0853493
        14    -0.3134625     0.4573287    -0.1714152     0.2536769    -0.3847434     0.2972236     0.1131785     0.0291233
        15     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        16     0.3369079    -0.0553864    -0.0628265    -0.4065399     0.1702646     0.6771212     0.0014328    -0.1202089
        17    -0.6126516    -0.2715208     0.1031965    -0.1544971     0.1711851     0.2966527     0.0441622    -0.0507011
        18     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
                   9
         1     0.0834726
         2     0.5419668
         3     0.0000000
         4     0.4713631
         5    -0.3132541
         6     0.0000000
         7    -0.5655668
         8    -0.2376820
         9     0.0000000
        10     0.0069329
        11     0.0320802
        12     0.0000000
        13     0.0270333
        14    -0.0146830
        15     0.0000000
        16    -0.0232351
        17    -0.0084279
        18     0.0000000

 Doing optimization in   9 symmetrical displacement coordinates
 
 Computing numerical gradient for displacement coordinate   1
----- End of Example 2

----- Example 3
This Molpro2002.3 job is running on host:
op22th10
---------------
---------------

 MPP nodes  nproc
 op22th10     1
 ga_uses_ma=true, calling ma_init with heap size        8010000 determined by size of -G / nprocs

 Primary working directories:    /usr/scratch/dima/c3nh4-start1.9824.scratch
 Secondary working directories:  /usr/scratch/dima/c3nh4-start1.9824.scratch
 
 blaslib=atlas           

 MPP tuning parameters: Latency=  1000 Microseconds,   Broadcast speed=   20 MB/sec
 default implementation of scratch files=df  

 ***,
 Including file /ds20th/san/users/dima/MY-EXECS/molpro2002-opterons/molpro-mpp-Linux-i686-i4-2002.6/molproi.rc
 ***,comment
 memory,100,m
 basis,vdz
  
 geomtyp=xyz
 geometry={
 8
 text
 N1,0.964500,0.002760,0.0
 C2,-0.038260,1.010090,0.0
 C3,-1.035690,-0.002950,0.0
 C4,-0.032200,-1.020300,0.0
 H5,1.984500,0.005530,0.0
 H6,-0.041150,2.100190,0.0
 H7,-2.135880,-0.005930,0.0
 H8,-0.029280,-2.100600,0.0
 }
  
 hf
 wf,28,1,2
 occ,12,3
 closed,12,1
  
  
 multi
 occ,12,4
 closed,12,0
 pspace,5.0
 maxiter,200
  
                                                                                 ! --- 1A ---
  
 wf,28,1,0
 state,7
  
                                                                                 ! --- 3A ---
  
 wf,28,1,2
 state,5
  
                                                                                 ! --- 5A ---
  
 wf,28,1,4
 state,1
  
  
 geomvar=energy(12)
  
 opt,startcmd=multi,numerical
 variable,geomvar
 coord,,bmat

 Variables initialized (303), CPU time= 0.00 sec
 Default parameters read. Elapsed time= 0.10 sec
 Checking input...
 Passed
1


                                         ***  PROGRAM SYSTEM MOLPRO  ***
                                      Copyright, University of Birmingham, 1997

                                    Version 2002.6 linked 7 Nov 2003 10:22:41 


 **********************************************************************************************************************************
 LABEL *   COMMENT                                                                       
 Linux-2.6.5-7.108-smp/op22th10(x86_64) 32 bit mpp version                               DATE:  24-Oct-04         TIME: 07:16:39  
 **********************************************************************************************************************************

 Installed patches: cidps_orthp configure_xeon darwin_conf dft_orbital_hi enest_dummy fujitsu-ssl2
                    fujitsu_conf ga_conflict2 ia64root_check merge_orbdom mkl60 modelopt
                    molden_orbital_normalization mpputil mxm_fujitsu nec_parse opteron2 patcher_printf
                    posinp pseudo_libmol2 readop_multipole_nps sun_forte8
 **********************************************************************************************************************************
 SETTING BASIS          =    VDZ
 SETTING GEOMTYP        =    XYZ

 Variable memory set to  100000000 words,  buffer space   230000 words
 


 Using spherical harmonics

 Library entry N      S cc-pVDZ              selected for orbital group  1
 Library entry N      P cc-pVDZ              selected for orbital group  1
 Library entry N      D cc-pVDZ              selected for orbital group  1
 Library entry C      S cc-pVDZ              selected for orbital group  2
 Library entry C      P cc-pVDZ              selected for orbital group  2
 Library entry C      D cc-pVDZ              selected for orbital group  2
 Library entry H      S cc-pVDZ              selected for orbital group  3
 Library entry H      P cc-pVDZ              selected for orbital group  3

1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets)     Author: Roland Lindh, 1990

 Geometry written to block  1 of record 700


 Point group  Cs  



 ATOMIC COORDINATES

 NR  ATOM    CHARGE       X              Y              Z

   1  N1      7.00    1.822640716    0.005215644    0.000000000
   2  C2      6.00   -0.072300916    1.908793324    0.000000000
   3  C3      6.00   -1.957170309   -0.005574692    0.000000000
   4  C4      6.00   -0.060849177   -1.928087426    0.000000000
   5  H5      1.00    3.750161224    0.010450185    0.000000000
   6  H6      1.00   -0.077762224    3.968783624    0.000000000
   7  H7      1.00   -4.036227944   -0.011206075    0.000000000
   8  H8      1.00   -0.055331177   -3.969558412    0.000000000

 Bond lengths in Bohr (Angstrom)

  1--2  2.685965706   1--3  3.779826427   1--4  2.699110027   1--5  1.927527616   2--3  2.686547511
       (1.421351943)       (2.000198150)       (1.428307619)       (1.020003761)       (1.421659821)

  2--4  3.836897840   2--6  2.059997539   3--4  2.700386834   3--7  2.079065262   4--8  2.041478443
       (2.030399043)       (1.090103831)       (1.428983276)       (1.100194036)       (1.080303946)

 Bond angles

  1--2--3   89.42488080   1--2--4   44.69872931   1--2--6  135.28216182   1--3--2   45.28129229

  1--3--4   45.55652236   1--3--7  179.99162882   1--4--2   44.42327929   1--4--3   88.85931315

  1--4--8  135.59286054   2--1--3   45.29382692   2--1--4   90.87799140   2--1--5  134.71413957

  2--3--4   90.83781465   2--3--7  134.71033654   2--4--3   44.43603386   2--4--8  179.98386017

  3--1--4   45.58416448   3--1--5  179.99203351   3--2--4   44.72615149   3--2--6  135.29295738

  3--4--8  135.54782631   4--1--5  134.40786903   4--2--6  179.98089113   4--3--7  134.45184882

 NUCLEAR CHARGE:                   29
 NUMBER OF PRIMITIVE AOS:         136
 NUMBER OF SYMMETRY AOS:          132
 NUMBER OF CONTRACTIONS:           76   (  56A'  +  20A"  )
 NUMBER OF CORE ORBITALS:           4   (   4A'  +   0A"  )
 NUMBER OF VALENCE ORBITALS:       20   (  16A'  +   4A"  )


 NUCLEAR REPULSION ENERGY  107.49567799

<------------------------ skipped ---------------------------->

 **********************************************************************************************************************************
 SETTING GEOMVAR        =      -169.69755918  HARTREE

 PROGRAM * OPT (Geometry optimization step)     Author: F. Eckert

 Optimizing variable GEOMVAR; current value: -169.69755918 HARTREE     

 symmetric vibrational displacements
                   1             2             3             4             5             6             7             8
         1     0.2054758    -0.0007699    -0.0025493     0.0727729    -0.2010844     0.0021809    -0.0329180    -0.0193991
         2     0.0009448     0.2318689     0.4510855     0.0004515     0.0007603     0.3167942     0.0290074    -0.2672083
         3     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         4     0.2478427     0.0058697    -0.4503016    -0.0076967    -0.3166394    -0.0008146    -0.1029017    -0.4254628
         5     0.0011551     0.2049134     0.0028837    -0.0809044    -0.0147826     0.2071845     0.0523889    -0.2343302
         6     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         7     0.2052014    -0.0007948    -0.0000163    -0.0797530    -0.1795578     0.0080246    -0.0998138    -0.0306143
         8     0.0004235     0.2647682    -0.4416949     0.0000004    -0.0017837     0.3280976     0.0290680     0.6422218
         9     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        10     0.2490002    -0.0072844     0.4523922    -0.0081467    -0.3170031     0.0183020    -0.1010861     0.4659552
        11     0.0003889     0.2046165     0.0055462     0.0804714     0.0131862     0.2137361    -0.0146865    -0.2236522
        12     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        13     0.1579934     0.0019118     0.0001299     0.5132266     0.7023532     0.0246941    -0.2802688     0.0035448
        14     0.0005409    -0.5616652    -0.2530148     0.0017737     0.0025172     0.0538668     0.0040143    -0.0400873
        15     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        16    -0.6084142     0.0448450     0.2009411     0.0026178    -0.0507525     0.0035180    -0.0150536    -0.0478347
        17    -0.0034296     0.1539156     0.0066533    -0.4845344     0.1687646    -0.5436203    -0.5306663     0.0339969
        18     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        19     0.1539622     0.0012535    -0.0011805    -0.4929071     0.4130143    -0.0587197     0.6500168     0.0044350
        20    -0.0001748    -0.6521831     0.2229675    -0.0010483     0.0007435     0.0544288     0.0063575     0.0565004
        21     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        22    -0.6110616    -0.0450308    -0.1994155    -0.0001137    -0.0503303     0.0028146    -0.0179748     0.0493759
        23     0.0001513     0.1537658     0.0055734     0.4837901    -0.1694055    -0.6304878     0.4245166     0.0325590
        24     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
                   9            10            11            12
         1     0.5210182     0.0307702     0.4798484     0.5318974
         2     0.0057084     0.6250676    -0.0565306     0.0026969
         3     0.0000000     0.0000000     0.0000000     0.0000000
         4    -0.4651111     0.2200314    -0.0137378    -0.0185907
         5    -0.0403045    -0.5310268    -0.4574345     0.4820536
         6     0.0000000     0.0000000     0.0000000     0.0000000
         7     0.5578448    -0.0582505    -0.4740840    -0.4939493
         8     0.0339628     0.2013777    -0.0262342    -0.0003055
         9     0.0000000     0.0000000     0.0000000     0.0000000
        10    -0.4326822    -0.1951103     0.0155828    -0.0156247
        11    -0.0058305    -0.4337242     0.5540191    -0.4848048
        12     0.0000000     0.0000000     0.0000000     0.0000000
        13    -0.0761959    -0.0070383    -0.0847331     0.0334338
        14    -0.0009231     0.0399734    -0.0039054     0.0002263
        15     0.0000000     0.0000000     0.0000000     0.0000000
        16    -0.0208649     0.0213034    -0.0020420    -0.0006072
        17    -0.0008114     0.0578238     0.0700463     0.0365538
        18     0.0000000     0.0000000     0.0000000     0.0000000
        19    -0.0659839     0.0089881     0.0775949    -0.0361642
        20     0.0021626    -0.0024964    -0.0001997     0.0000253
        21     0.0000000     0.0000000     0.0000000     0.0000000
        22    -0.0180250    -0.0206939     0.0015708    -0.0003950
        23     0.0060357     0.0430049    -0.0797609    -0.0364456
        24     0.0000000     0.0000000     0.0000000     0.0000000

 Doing optimization in  12 symmetrical displacement coordinates
 
 Computing numerical gradient for displacement coordinate   1
----- End of Example 3

----- Example 4
This Molpro2002.3 job is running on host:
op22th10
---------------
---------------

 MPP nodes  nproc
 op22th10     1
 ga_uses_ma=true, calling ma_init with heap size        8010000 determined by size of -G / nprocs

 Primary working directories:    /usr/scratch/dima/c3nh4-start2.9830.scratch
 Secondary working directories:  /usr/scratch/dima/c3nh4-start2.9830.scratch
 
 blaslib=atlas           

 MPP tuning parameters: Latency=  1000 Microseconds,   Broadcast speed=   20 MB/sec
 default implementation of scratch files=df  

 ***,
 Including file /ds20th/san/users/dima/MY-EXECS/molpro2002-opterons/molpro-mpp-Linux-i686-i4-2002.6/molproi.rc
 ***,comment
 memory,100,m
 basis,vdz
  
 geomtyp=xyz
 geometry={
 8
 text
 N1,0.864500,0.002760,0.0
 C2,-0.038260,1.010090,0.0
 C3,-1.035690,-0.002950,0.0
 C4,-0.032200,-1.020300,0.0
 H5,1.984500,0.105530,0.0
 H6,-0.141150,2.100190,0.0
 H7,-2.235880,-0.005930,0.0
 H8,-0.129280,-2.100600,0.0
 }
  
 hf
 wf,28,1,2
 occ,12,3
 closed,12,1
  
  
 multi
 occ,12,4
 closed,12,0
 pspace,5.0
 maxiter,200
  
                                                                                 ! --- 1A ---
  
 wf,28,1,0
 state,7
  
                                                                                 ! --- 3A ---
  
 wf,28,1,2
 state,5
  
                                                                                 ! --- 5A ---
  
 wf,28,1,4
 state,1
  
  
 geomvar=energy(12)
  
 opt,startcmd=multi,numerical
 variable,geomvar
 coord,,bmat

 Variables initialized (303), CPU time= 0.00 sec
 Default parameters read. Elapsed time= 0.32 sec
 Checking input...
 Passed
1


                                         ***  PROGRAM SYSTEM MOLPRO  ***
                                      Copyright, University of Birmingham, 1997

                                    Version 2002.6 linked 7 Nov 2003 10:22:41 


 **********************************************************************************************************************************
 LABEL *   COMMENT                                                                       
 Linux-2.6.5-7.108-smp/op22th10(x86_64) 32 bit mpp version                               DATE:  24-Oct-04         TIME: 07:16:40  
 **********************************************************************************************************************************

 Installed patches: cidps_orthp configure_xeon darwin_conf dft_orbital_hi enest_dummy fujitsu-ssl2
                    fujitsu_conf ga_conflict2 ia64root_check merge_orbdom mkl60 modelopt
                    molden_orbital_normalization mpputil mxm_fujitsu nec_parse opteron2 patcher_printf
                    posinp pseudo_libmol2 readop_multipole_nps sun_forte8
 **********************************************************************************************************************************
 SETTING BASIS          =    VDZ
 SETTING GEOMTYP        =    XYZ

 Variable memory set to  100000000 words,  buffer space   230000 words
 


 Using spherical harmonics

 Library entry N      S cc-pVDZ              selected for orbital group  1
 Library entry N      P cc-pVDZ              selected for orbital group  1
 Library entry N      D cc-pVDZ              selected for orbital group  1
 Library entry C      S cc-pVDZ              selected for orbital group  2
 Library entry C      P cc-pVDZ              selected for orbital group  2
 Library entry C      D cc-pVDZ              selected for orbital group  2
 Library entry H      S cc-pVDZ              selected for orbital group  3
 Library entry H      P cc-pVDZ              selected for orbital group  3

1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets)     Author: Roland Lindh, 1990

 Geometry written to block  1 of record 700


 Point group  Cs  



 ATOMIC COORDINATES

 NR  ATOM    CHARGE       X              Y              Z

   1  N1      7.00    1.633668117    0.005215644    0.000000000
   2  C2      6.00   -0.072300916    1.908793324    0.000000000
   3  C3      6.00   -1.957170309   -0.005574692    0.000000000
   4  C4      6.00   -0.060849177   -1.928087426    0.000000000
   5  H5      1.00    3.750161224    0.199422784    0.000000000
   6  H6      1.00   -0.266734823    3.968783624    0.000000000
   7  H7      1.00   -4.225200543   -0.011206075    0.000000000
   8  H8      1.00   -0.244303776   -3.969558412    0.000000000

 Bond lengths in Bohr (Angstrom)

  1--2  2.556156945   1--3  3.590854638   1--4  2.570807192   1--5  2.125384550   2--3  2.686547511
       (1.352660100)       (1.900198579)       (1.360412678)       (1.124705149)       (1.421659821)

  2--4  3.836897840   2--6  2.069145858   3--4  2.700386834   3--7  2.268037225   4--8  2.049697386
       (2.030399043)       (1.094944913)       (1.428983276)       (1.200193700)       (1.084653224)

 Bond angles

  1--2--3   86.42155122   1--2--4   41.69539973   1--2--6  143.52552926   1--3--2   45.27268459

  1--3--4   45.56513005   1--3--7  179.97009054   1--4--2   41.40518938   1--4--3   85.84122324

  1--4--8  143.90084854   2--1--3   48.30576419   2--1--4   96.89941089   2--1--5  126.62368878

  2--3--4   90.83781465   2--3--7  134.69740595   2--4--3   44.43603386   2--4--8  174.69396208

  3--1--4   48.59364670   3--1--5  174.92945297   3--2--4   44.72615149   3--2--6  130.05291952

  3--4--8  130.25792821   4--1--5  136.47690033   4--2--6  174.77907101   4--3--7  134.46477940

 NUCLEAR CHARGE:                   29
 NUMBER OF PRIMITIVE AOS:         136
 NUMBER OF SYMMETRY AOS:          132
 NUMBER OF CONTRACTIONS:           76   (  56A'  +  20A"  )
 NUMBER OF CORE ORBITALS:           4   (   4A'  +   0A"  )
 NUMBER OF VALENCE ORBITALS:       20   (  16A'  +   4A"  )


 NUCLEAR REPULSION ENERGY  108.98080422

<------------------------ skipped ---------------------------->

 **********************************************************************************************************************************
 SETTING GEOMVAR        =      -169.65270818  HARTREE

 PROGRAM * OPT (Geometry optimization step)     Author: F. Eckert

 Optimizing variable GEOMVAR; current value: -169.65270818 HARTREE     

 symmetric vibrational displacements
                   1             2             3             4             5             6             7             8
         1     0.2020249     0.0356615    -0.0076190    -0.0123612     0.0704400     0.1617451    -0.0019340    -0.0901650
         2    -0.0504809     0.2158324    -0.0344256     0.4344538     0.0065174    -0.0859519     0.2846251    -0.1258385
         3     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         4     0.2299744     0.0704303    -0.0963462    -0.4633279    -0.0056794     0.2694898    -0.0149123    -0.1917243
         5    -0.0428564     0.2033781    -0.0208505     0.0126843    -0.0777703    -0.0221638     0.2194281    -0.0714569
         6     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         7     0.2050057     0.0411267    -0.0111580    -0.0018902    -0.0815221     0.1394345    -0.0276700    -0.1543032
         8    -0.0625784     0.2634119     0.0081104    -0.4399521     0.0020034    -0.0668235     0.2723045    -0.1245543
         9     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        10     0.2564707     0.0306879     0.0699848     0.4637871    -0.0093546     0.2785213     0.0073641    -0.2011893
        11    -0.0522073     0.1973856    -0.0180404     0.0103857     0.0778151    -0.0762142     0.1787008    -0.1060438
        12     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        13     0.1416740     0.0676862    -0.0354203     0.0141567     0.4933810    -0.7307143    -0.2320226    -0.0081934
        14     0.1672258    -0.5602128     0.4976999    -0.2789633     0.0250782    -0.0538917     0.0337071    -0.0193613
        15     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        16    -0.5602840    -0.1176573     0.5535478     0.1775612     0.0221841     0.0471334     0.0332013    -0.0292415
        17    -0.0667806     0.1454218     0.0161105     0.0237841    -0.5023675    -0.1060619    -0.7473847    -0.1313836
        18     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        19     0.1469485     0.0342944    -0.0056563    -0.0042492    -0.5064402    -0.2283510     0.2517501     0.6851915
        20     0.1130372    -0.6235835    -0.4576864     0.2161970    -0.0028958    -0.0125536     0.0470800    -0.0169160
        21     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        22    -0.6218141    -0.1622297    -0.4673329    -0.1736765     0.0169912     0.0627410    -0.0157766    -0.0103746
        23    -0.0053593     0.1583666     0.0090821     0.0214105     0.4716195     0.4236605    -0.2884609     0.5955545
        24     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
                   9            10            11            12            13
         1    -0.3285781     0.5277451    -0.3878665     0.0155599     0.5062434
         2    -0.2237067    -0.1507483    -0.0561128    -0.6423723     0.0082385
         3     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         4    -0.1257086    -0.6116339    -0.1212689    -0.1796775    -0.0065433
         5    -0.1522569    -0.2033823     0.5041676     0.4564058     0.4941884
         6     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
         7    -0.2634672     0.3595343     0.5801929    -0.0531279    -0.4922955
         8     0.5533053     0.3561467     0.0103885    -0.1987963    -0.0016413
         9     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        10     0.6001442    -0.1201274    -0.0688367     0.2024813    -0.0075334
        11    -0.2336353    -0.0162382    -0.4618758     0.5074149    -0.5020001
        12     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        13     0.0647083    -0.0812931     0.0713588     0.0088703     0.0352743
        14    -0.0262571    -0.0301819     0.0042879    -0.0357478     0.0010529
        15     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        16    -0.0335592    -0.0433569     0.0006714    -0.0138381     0.0003345
        17     0.0184141     0.0140180    -0.0760364    -0.0381805     0.0350510
        18     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        19     0.0342165    -0.0430766    -0.0795738     0.0060064    -0.0357893
        20     0.0459916     0.0299901     0.0012480     0.0011047    -0.0000858
        21     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000
        22     0.0522442     0.0122083     0.0053227     0.0137257     0.0003093
        23     0.0181450     0.0003959     0.0739331    -0.0498285    -0.0348036
        24     0.0000000     0.0000000     0.0000000     0.0000000     0.0000000

 Doing optimization in  13 symmetrical displacement coordinates
 
 Computing numerical gradient for displacement coordinate   1
----- End of Example 4




More information about the Molpro-user mailing list