Can one calculate core-excited states with MRCI ?

[Evgeniy Gromov]

Dear Sir,

I faced a problem when calculating core-excited state of H2CO with MRCI.
The ocupation of the core orbital was fixed by RESTRICT option.
The program (MOLPRO2002.1) stops after performing the calculation of the 
reference
energy and gives the error:

NO VECTOR OF INTERNAL CI OVERLAPS SUFFICIENTLY WITH REFERENCE VECTOR 1. 
INCREASE NSTATI!

OVERLAP BETWEEN INITIAL AND PRESENT VECTORS

                  1
        1     0.0012413
ovmax=  1.241277214171334E-003   ovref=  1.241277214171334E-003

ERROR EXIT


I tried to increase NSTATI, but it did not help to overcome the problem.
The reference CSFs used in MRCI are the following:

Reference CSFs
==============

CSF  Conf  Shell  Occupation      Coefficients
  1    1     2     2222+-202200      0.048612
  2    2     2     2222+-022200      0.001585
  3    3     2     2222+-002220      0.000063
  4    4     2     2222+-002202      0.001004
  5    5     2     2222+2-02200      0.998763
  6    6     2     2222+0-22200     -0.000426
  7    7     2     2222+0-02220     -0.000023
  8    8     2     2222+0-02202     -0.000345
  9    9     2     2222+20-2200      0.000200
 10   10     2     2222+02-2200      0.002189
 11   11     2     2222+00-2220      0.000000
 12   12     2     2222+00-2202      0.000004
 13   13     3     2222+-+-2200      0.007639
 14   13     3     2222++--2200     -0.006529

Optimized reference wavefunction n.  1
 222212102200                            0.99876


************************************************************

Is it possible to calculate core-excited states with MRCI in MOLPRO ?

  I shall very appreciate you for any help in solving this problem !


Best regards,
                       Evgeniy

************************************************************

My input-file is the following:


file,1,h2co.int,new;
file,2,h2co.wfu,new;
file,3,h2co.res,new;
!cartesian
basis={
! OXYGEN       (9s,5p) -> [4s,2p]
s,O 
,0.781654000E+04,0.117582000E+04,0.273188000E+03,0.811696000E+02,0.271836000E+02,0.341360000E+01,0.953220000E+01,0.939800000E+00,0.284600000E 

+00,0.04
c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
c,3.3, 0.100000000E+01
c,4.4, 0.100000000E+01
c,5.5, 0.100000000E+01
c,6.6, 0.100000000E+01
c,7.7, 0.100000000E+01
c,8.8, 0.100000000E+01
c,9.9, 0.100000000E+01
c,10.10 0.100000000E+01
p,O 
,0.351832000E+02,0.790400000E+01,0.230510000E+01,0.717100000E+00,0.213700000E+00,0.06 

c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
c,3.3, 0.100000000E+01
c,4.4, 0.100000000E+01
c,5.5, 0.100000000E+01
c,6.6, 0.100000000E+01
d,O ,2.31400000,0.64500000,0.08
c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
c,3.3, 0.100000000E+01
! CARBON       (9s,5p) -> [4s,2p]
s,C 
,0.423261000E+04,0.634882000E+03,0.146097000E+03,0.424974000E+02,0.141892000E+02,0.196660000E+01,0.514770000E+01,0.496200000E+00,0.153300000E 

+00,0.02
c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
c,3.3, 0.100000000E+01
c,4.4, 0.100000000E+01
c,5.5, 0.100000000E+01
c,6.6, 0.100000000E+01
c,7.7, 0.100000000E+01
c,8.8, 0.100000000E+01
c,9.9, 0.100000000E+01
c,10.10,  0.100000000E+01
p,C 
,0.181557000E+02,0.398640000E+01,0.114290000E+01,0.359400000E+00,0.114600000E+00,0.04 

c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
c,3.3, 0.100000000E+01
c,4.4, 0.100000000E+01
c,5.5, 0.100000000E+01
c,6.6, 0.100000000E+01
d,C ,1.09700000,0.31800000,0.06
c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
c,3.3, 0.100000000E+01
! HYDROGEN     (4s) -> [2s]
s,H ,0.192406000E+02,0.289920000E+01,0.653400000E+00,0.177600000E+00
c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
c,3.3, 0.100000000E+01
c,4.4, 0.100000000E+01
p,H 1.40700000,0.38800000
c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
}
gprint,basis
geomtyp=xyz
geometry={
4
O1s -> pi*
C ,0.0000000000   0.0000000000  -0.0910426086
O ,0.0000000000   0.0000000000   1.2393858139
H ,0.0000000000  -0.9550455960  -0.5622547956
H ,0.0000000000   0.9550455960  -0.5622547956
}
hf
occ,5,2,2
wf,16,2,2
open,1.1,2.2
orbital,2100.2
orbprint,20
!
merge
orbital,2100.2
move,2.1,5.1,1.1
move,1.1,1.1,5.1
move,6.1,52.1,6.1
move,1.2,20.2,1.2
move,1.3,26.3,1.3
move,1.4,8.4,1.4
!print,3
save,2100.2
!
ci;
occ,5,3,3,1
closed,4,0,2,0
core
orbit,2100.2
wf,16,2,0
restrict,1,1,5.1
thresh,print=0.03
maxiter,500,500
print,ref=0
print,ref=1
---