[molpro-user] simetry error

Werner Gyorffy gyorffy at theochem.uni-stuttgart.de
Fri Jul 5 12:24:26 BST 2013


Dear Diana,

The geometry of the formaldehyde molecule you defined has Cs symmetry. 
The program stops since the molecule is trying to leave the symmetry 
plane during the geometry optimization. It may sound strange, but it is 
rather a consequence of the default setting you used.

There are two ways of fixing your input:

1, You can force the geometry to be planar by fixing the D1 dihedral 
angel to be 180 degrees. This can be done by making D1 to be inactive by 
writing

{optg,numerical;inactive,d1}

or simply write 180 instead of the D1 in your geometry definition:

geometry={
           h1;
           c1,1,r1;
           h2,2,r2,1,a1;
           o1,2,r3,3,a2,1,180}

2, The other way of curing the problem is to use symmetric displacements 
in the numerical gradient calculation invoked by

{optg,numerical,displace=sym}



Some furthermore notes: The equilibrium geometry of formaldehyde has 
actually C2v symmetry. You can easily define it, for example, as

geometry={
  c
  o    1 r3
  h    1 r1         2 a2
  h    1 r1         2 a2          3 180.0
}
r1= 1.108 ang
r3= 1.197 ang
a2= 121.7 degree

The formaldehyde molecule has a closed-shell ground state, so the 
closed-shell CCSD method can be used rather than RCCSD. In closed-shell 
CCSD, gradients can be computed analytically which is much faster than 
computing gradients numerically. To use that, you can simply write

hf
ccsd
optg

Regards,

Werner Gyorffy.

On 07/05/2013 04:14 AM, Diana Rodríguez wrote:
>
> Dear molpro user/developers:
>
> I received a message of error when optimizing, at CCSD/cc-pVDZ level,
> some molecules. In all cases, at the begining of the optimization the
> following error ocurred:
>
>
>
>   PROGRAM * OPT (Geometry optimization)     Authors: F. Eckert and H.-J.
> Werner
>
>
>   BFGS update of hessian
>
>   *** Long output written to logfile
> /home_nfs/unila/fis/juan.garrido/2clmp-oh/och2-1-CCSD-DZ.log ***
>
>
>   Geometry optimization using default procedure for command RCCSD
>
>   Geometry written to block  1 of record 700
>   Starting numerical gradient for RCCSD
>   The request for symmetry elements Y, cannot be honoured
>   ? Error
>   ? Symmetry problem
>   ? The problem occurs in zmatrix.f:zmat_orient
>
>   ERROR EXIT
>   CURRENT STACK:      MAIN
>
>
>   **********************************************************************************************************************************
>   The request for symmetry elements Y, cannot be honoured
>
>   Prototype coordinates
>                     1             2             3             4
>           1     1.7795890     0.0000265    -1.7813729     0.0000925
>           2    -0.0116832     0.0029144    -0.0116715    -0.0007166
>           3     2.2345163     1.1313336     2.2315477    -1.1306657
>   ? Error
>   ? Symmetry problem
>   ? The problem occurs in zmatrix.f:zmat_orient
>   Attempt to include non-existent symmetry Y
>   This should not happen .. please report as a bug
>   User-specified symmetry elements: Y
>   Symmetry elements:
>   ? Error
>   ? Symmetry error
>   ? The problem occurs in zmatrix.f:zmat_evaluate
>   DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>                1      21        3.43       500      610      700
> 900      950      970     1000      129      960     1100
>                                            VAR    BASINP    GEOM
> SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S
>                                           1400     1410     1200
> 1210     1080     1600     1650     1300     1700     2100
>                                             T        V       H0
> H01     AOSYM     SMH    MOLCAS    ERIS     OPER      RHF
>                                            701
>                                           GEOM
>
>                2       5        0.34       700     1000     2100
> 5600      701
>                                           GEOM     BASIS     RHF
> GINFO    GEOM
>
>   PROGRAMS   *        TOTAL    FEHLER     RCCSD       RHF       INT
>   CPU TIMES  *        12.64      1.01      0.88      0.00      0.14
>   REAL TIME  *        25.91 SEC
>   DISK USED  *        10.79 MB
>   **********************************************************************************************************************************
>      <stm:metadataList displaced="true">
>       <stm:metadata displaced="true" name="dc:date"
> content="2013-07-04T23:01:29-03:00"/>
>       <stm:metadata displaced="true" name="dc:creator"
> content="juan.garrido"/>
>       <stm:metadata displaced="true" name="cmlm:insilico" content="Molpro">
>        <version displaced="true" major="2010" minor="1"
> integer_bits="64" parallelism="serial">
>         2010.1
>         <date displaced="true" year="2013" month="7" day="4" hour="23"
> minute="1" second="3">
>          2013-07-04T23:01:03
>         </date>
>        </version>
>        <licence displaced="true" id="brito"/>
>        <parallel displaced="true" processes="1" nodes="1"
> all_processes="1" openmp="1"/>
>        <machine displaced="true" hostname="lattes13" architecture="x86_64">
>         Linux-2.6.18-128.1.6.el5.Bull.7/lattes13(x86_64) 64 bit serial
> version
>         <sysinfo displaced="true" name="cpu MHz" content="2666.813"/>
>         <sysinfo displaced="true" name="MemTotal" content="24544556 kB"/>
>         <sysinfo displaced="true" name="vendor_id" content="GenuineIntel"/>
>         <sysinfo displaced="true" name="cpu family" content="6"/>
>         <sysinfo displaced="true" name="model name"
>           content="Intel(R) Xeon(R) CPU           X5650  @ 2.67GHz"/>
>         <sysinfo displaced="true" name="flags"
>           content="fpu vme de pse tsc msr pae mce cx8 apic sep mtrr pge
> mca cmov pat pse36 clflush dts acpi mmx fxsr sse sse2 ss ht tm syscall
> nx pdpe1gb rdtscp lm constant_tsc nonstop_tsc pni monitor ds_cpl vmx smx
> est tm2 cx16 xtpr popcnt lahf_lm"/>
>         <sysinfo displaced="true" name="MemTotal" content="24544556 kB"/>
>         <sysinfo displaced="true" name="cache size" content="12288 KB"/>
>         <sysinfo displaced="true" name="ncpu" content="12"/>
>        </machine>
>       </stm:metadata>
>      </stm:metadataList>
>    <input>
>
> <p>
> ! opt a partir de la geo opt BHandHLYP/6-31+* </p>
>     <p> ***, </p>
>     <p> memory,1000,M </p>
>     <p> R1= 1.108 ang, </p>
>     <p> R2= 1.108 ang, </p>
>     <p> R3= 1.197 ang, </p>
>     <p> A1= 116.5 degree, </p>
>     <p> A2= 121.7 degree, </p>
>     <p> D1= 180.0 degree, </p>
>     <p> geometry={ </p>
>     <p>           H1; </p>
>     <p>           C1,1,R1; </p>
>     <p>           H2,2,R2,1,A1; </p>
>     <p>           O1,2,R3,3,A2,1,D1} </p>
>     <p> GTHRESH,ENERGY=1.d-5, </p>
>
> <p>
> !GDIRECT </p>
>     <p> basis=cc-pVDZ </p>
>     <p> rhf,maxit=800,ENERGY=1.d-5 </p>
>
> <p>
> !multi </p>
>
> <p>
> !rs2 </p>
>     <p> rccsd,maxit=800; </p>
>     <p> {optg,method=qsd,root=1} </p>
>     <p> frequencies </p>
>     <p> put,molden,och2-DZ-ccsd.molden,new </p>
>    </input>
>      <!--
>
> I hope you can help me,
>
> Best regards,
>
> Diana
>
>
>
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