[molpro-user] Rotating orbitals in RMP2

Grant Hill Grant.Hill at glasgow.ac.uk
Tue Sep 3 10:52:41 BST 2013

```Dear All,

I'm trying to localize a subset of HF orbitals, then rotate them to force specific orbitals to be frozen in an RMP2 calculation.

The following does what I want with df-rmp2 (or df-rmp2-f12):

{rhf;accu,14;wf,49,1,1;print,orbs}
{locali;group,8.1,9.1,10.1,11.1,12.1,13.1,14.1,15.1;print,orbitals}
{df-rmp2,df_basis=dfmp;orbit,local,ignore_error;rotate,8.1,13.1,0;rotate,9.1,14.1,0;rotate,10.1,15.1,0}

But the analogous rmp2 seems to ignore the rotation (or reads the wrong set of orbitals), a snipped output is copied below. Does anyone know how I might use localized rotated orbitals in conventional RMP2 calculations?

Best regards,

Grant

**********************************************************************************************************************************
1PROGRAM * RMP2 (Restricted open-shell)     Authors: U. Schumann, H.-J. Werner, 2001

Convergence thresholds:  THRVAR = 1.00D-08  THRDEN = 1.00D-10

Number of core orbitals:          12 (  12 )
Number of closed-shell orbitals:  12 (  12 )
Number of active  orbitals:        1 (   1 )
Number of external orbitals:     208 ( 208 )

Reading UHF information from record   2100.2

TOTAL       A-A         B-B         A-B
Pair energies:            -0.74602403 -0.11875703 -0.10154183 -0.52572517
Singles energies:         -0.00098992 -0.00049146 -0.00049846

Reference energy                    -511.876166078673
Correlation energy                    -0.747013952219
!RMP2 STATE 1.1 Energy              -512.623180030893
**********************************************************************************************************************************
1PROGRAM * RMP2 (Restricted open-shell)     Authors: U. Schumann, H.-J. Werner, 2001

Convergence thresholds:  THRVAR = 1.00D-08  THRDEN = 1.00D-10

Number of core orbitals:          12 (  12 )
Number of closed-shell orbitals:  12 (  12 )
Number of active  orbitals:        1 (   1 )
Number of external orbitals:     208 ( 208 )

Number of N-1 electron functions:              25
Number of N-2 electron functions:             300
Number of singly external CSFs:              5225
Number of doubly external CSFs:           9944220
Total number of CSFs:                     9949445

Molecular orbitals read from record     2100.2  Type=RHF/LOCAL(BOYS) (state 1.1)

?Warning: invalid orbital type for MPn or triples: LOCAL(BOYS)
ROTATION OF ORBITALS   8.1   13.1       90.00 DEGREES
ROTATION OF ORBITALS   9.1   14.1       90.00 DEGREES
ROTATION OF ORBITALS  10.1   15.1       90.00 DEGREES

Fock operators(AO) taken from dump record.

CPU time for singles                             0.05 sec

AO(A)-basis ORBITAL           loaded. Number of functions:     233
DF-basis DFMP                 loaded. Number of functions:     633

Screening thresholds:   THRAO=  1.00D-10  THRMO=  1.00D-09  THRPROD=  1.00D-09
THRSW=  1.00D-05  THROV=  1.00D-12  THRF12=   1.00D-08

Using semi-canonical formulas. This will break singlet/triplet splittings.

TOTAL          ALPHA          BETA
Singles Contributions MO        -0.000837827   -0.000421012   -0.000416815

DF-RMP2 doubles energies:
- - - - - - - - - - - - -
Approx.                             TOTAL           A-B            A-A            B-B
RMP2                            -0.913867738   -0.673267708   -0.120862678   -0.119737352

Reference energy                   -511.876166078673
DF-RMP2 singles (MO) energy          -0.000837826985
DF-RMP2 pair energy                  -0.913867737514
DF-RMP2 correlation energy           -0.914705564500
!DF-RMP2 energy                     -512.790871643173

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