[molpro-user] symmetric vibrational displacement coordinates
H. -J. Werner
werner at theochem.uni-stuttgart.de
Sun Oct 24 19:58:57 BST 2004
The "symmetric vibrational displacements" are what the name says: they are
symmetry adapted. This means that there are no displacements which change the
initial symmetry, since the exact analytical gradient would be zero in
the dicection of such displacements. Take a simple example, H2O in C2v: the only totally
symmetric displacements are those corresponding to the symmetric stretch
and the bending modes. Thus, there are only 2, rather than 3 displacements.
This saves a lot of computer time if the molecule has high symmetry, and
is NO approximation! If you want a geometry optimization without any constraints,
you must start with an unsymmetric geometry. The same would be true if
analytical energy gradients are used.
Joachim werner
On So, 24 Okt 2004, Dima Khoroshun wrote:
>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
--
Prof. Hans-Joachim Werner
Institute for Theoretical Chemistry
University of Stuttgart
Pfaffenwaldring 55
D-70569 Stuttgart, Germany
Tel.: (0049) 711 / 685 4400
Fax.: (0049) 711 / 685 4442
e-mail: werner at theochem.uni-stuttgart.de
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