[molpro-user] CaF ground state HF and UHF calculation problems with Molpro2015.1.8

[侯世林]

Dear all:

 

I have some troubles when calculating CaF with HF and UHF method, and this will consequently influence the results of the related post-HF approaches. I use the version of Molpro 2015.1.8.

Both HF and UHF can do optimization successfully and give reasonable results. However, when a set of internuclear separations R are given, the UHF can finish calculations with no computational errors but the final results are wrong, because the obtained potential curve is repulsive for CaF ground state.

With HF method, reasonable results can be obtained only for the first R, and then the following error message present:

 

' Molecular orbitals read from record     2100.2  Type=RHF/CANONICAL (state 1.1)

 Incorrect occupation. noc=  15  ncl=  15  nelec=  29  ms2= 1

 ICLOS

   1-  8     9     3     3     0     0     0     0     0

 NOCC

   1-  8     9     3     3     0     0     0     0     0

'

The input file for HF calculation reads

                                                                               

   r=[25.0 18.0 ... ]                                                                           

   geometry={F;Ca,F,$r(l)}

    basis=v5z; F=av5z

do l=1,#r

     HF

 

    e(1) = energy

    method(1) = program

    dip(1) = dmz

    bond(1) = $r(l)

 

   table,method,bond,e,dip

enddo

 

 

For UHF, the 'HF' is just replaced with 'UHF', the output data in units a.u. are:  .

 METHOD     BOND        E            DIP

 UHF-SCF   25.00   -775.9654195   -0.00017432

 UHF-SCF   18.00   -775.9653928   -0.00069340

 UHF-SCF   12.00   -775.9652089   -0.00390148

 UHF-SCF   11.50   -775.9651646   -0.00469214

 UHF-SCF   11.00   -775.9651097   -0.00568491

 UHF-SCF   10.50   -775.9650412   -0.00694651

 UHF-SCF   10.00   -775.9649553   -0.00857887

 UHF-SCF    9.50   -775.9648472   -0.01069510

 UHF-SCF    9.00   -775.9647107   -0.01349033

 UHF-SCF    8.50   -775.9645376   -0.01720938

 UHF-SCF    8.00   -775.9643176   -0.02216390

 UHF-SCF    7.50   -775.9640366   -0.02871871

 UHF-SCF    7.00   -775.9636746   -0.03732960

 UHF-SCF    6.50   -775.9632006   -0.04848223

 UHF-SCF    6.00   -775.9625529   -0.06287766

 UHF-SCF    5.80   -775.9622145   -0.06969148

 UHF-SCF    5.60   -775.9618031   -0.07716052

 UHF-SCF    5.00   -775.9596775   -0.10355852

 UHF-SCF    4.50   -775.9551436   -0.12986174

 UHF-SCF    4.20   -775.9491519   -0.14710620

 UHF-SCF    4.00   -775.9423734   -0.15892108

 UHF-SCF    3.90   -775.9376989   -0.16481988

 UHF-SCF    3.80   -775.9318805   -0.17064276

 UHF-SCF    3.75   -775.9284576   -0.17349700

 UHF-SCF    3.70   -775.9246395   -0.17630598

 UHF-SCF    3.60   -775.9156343   -0.18171688

 UHF-SCF    3.50   -775.9044483   -0.18673182

 UHF-SCF    3.40   -775.8905774   -0.19116755

 UHF-SCF    3.20   -775.8522514   -0.19723968

 UHF-SCF    3.00   -775.7944646   -0.19696011

 

The UHF optimization result is:

      R               E1          DIP1

    3.73815213   -776.3297329   1.07225773

 

The HF optimization result is:

 METHOD     BOND            E           DIP

 HF-SCF   3.73818011   -776.3296065   1.06723713

 

How to solve such problems?

 

Thank you!

 

Dr. Shilin HOU

 

Department of Physics,

Ocean University of China

238 Songling Road, Qingdao,

Shandong, 266100
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