[molpro-user] Matrop: V matrix with ECP not correct?

Łukasz Rajchel lrajchel1981 at gmail.com
Thu Jul 2 21:20:14 BST 2015


Dear Molpro Users,

with Matrop one can save H0 and V matrices. V is a part of H0, and for an AB dimer in dimer-centred basis sets (DCBS),

(1)     VAB = VA + VB
(2)     VA = H0AB - H0B
(3)     VB = H0AB - H0A

since kinetic parts are identical for AB, A and B in DCBS.

Now, if I use Matrop to save H0 and V matrices using an all-electron basis set for a dimer and monomers, the V matrices from Matrop and (2) / (3) are identical, as shown in the ArKr_VDZ.{inp,out} files.

This is not the case when ECPs are used, Matrop-saved VA and VB matrices are not the same as (2) and (3). From other calculations I verified that only the latter ones are correct. This is shown in ArKr_ECP.{inp,out_last} files (I trimmed the outputs to Matrop parts only, for VDZ only first row is shown for the sake of brevity - all other rows are zeros as well).

I'd be really grateful for some clarification on the issue.

Best wishes,

-- 
=====================================================================
Łukasz Rajchel
Faculty of Chemistry
University of Duisburg-Essen
Universitätsstraße 5
45117 Essen
Germany
=====================================================================
-------------- next part --------------
***, ArKr

basis = {
	Ar = ECP1
	Kr = ECP1
}

symmetry,nosym
geometry = {
	Ar
	Kr, Ar, R
}

R = 4 ANG

! dimer AB
dummy
{rhf}
data,copy,1200.1,1210.2

! monomer A
dummy,Kr
{rhf}
data,copy,1200.1,1211.2
{matrop
	load,Epot
	save,Epot,3601.2,triang
}

! monomer B
dummy,Ar
{rhf}
data,copy,1200.1,1212.2
{matrop
	load,Epot
	save,Epot,3602.2,triang
}

{matrop
	load,H0AB,triang,1210.2
	load,H0A,triang,1211.2
	load,H0B,triang,1212.2
	! VA = H0AB - H0B
	! VB = H0AB - H0A
	add,VA,1.0,H0AB,-1.0,H0B
	add,VB,1.0,H0AB,-1.0,H0A
	! VA and VB saved by matrop
	load,VAmatrop,triang,3601.2
	load,VBmatrop,triang,3602.2
	! compute and print differencies
	add,VAdiff,1.0,VA,-1.0,VAmatrop
	add,VBdiff,1.0,VB,-1.0,VBmatrop
	print,VAdiff
	print,VBdiff
}
-------------- next part --------------
 PROGRAM * MATROP


 Operator V loaded to EPOT

  Matrix EPOT saved in record 3602.2


 **********************************************************************************************************************************
 DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
              1      20        7.51       500      610      700      900      950      970     1000      129      960     1100   
                                          VAR    BASINP    GEOM    SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S 
                                         1400     1410     1420     1200     1210     1080     1600     1650     1300     1700   
                                           T        V       ECP      H0       H01     AOSYM     SMH    MOLCAS    ERIS     OPER   

              2      11        0.60       700     1000      520     2100     1210     2101     1211     3601     2102     1212   
                                         GEOM     BASIS   MCVARS     RHF      H0       RHF      H0      EPOT      RHF      H0  
                                         3602   
                                         EPOT   

 PROGRAMS   *        TOTAL    MATROP      DATA       RHF       INT    MATROP      DATA       RHF       INT      DATA       RHF
 CPU TIMES  *         0.78      0.06      0.00      0.06      0.05      0.05      0.00      0.06      0.06      0.00      0.05
 REAL TIME  *         0.89 SEC
 DISK USED  *        12.26 MB      
 **********************************************************************************************************************************


 PROGRAM * MATROP


 Matrix H0AB loaded from record   1210.2

 Matrix H0A loaded from record   1211.2

 Matrix H0B loaded from record   1212.2

 VA = H0AB - H0B

 VB = H0AB - H0A

 Matrix VAMATROP loaded from record   3601.2

 Matrix VBMATROP loaded from record   3602.2

 VADIFF = VA - VAMATROP

 VBDIFF = VB - VBMATROP

 MATRIX VADIFF          

 SYMMETRY BLOCK 1.1
    0.77126468   0.00000000   0.00000000  -0.00000000   0.00000560   0.00000000   0.00000000  -0.00031685
    0.00000000   0.38516967   0.00000000   0.00000000   0.00000000   0.00000860   0.00000000   0.00000000
    0.00000000   0.00000000   0.38516967   0.00000000   0.00000000   0.00000000   0.00000860   0.00000000
   -0.00000000   0.00000000   0.00000000   0.38516967   0.00000346   0.00000000   0.00000000  -0.00014426
    0.00000560   0.00000000   0.00000000   0.00000346   0.00000000   0.00000000   0.00000000  -0.00000000
    0.00000000   0.00000860   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000
    0.00000000   0.00000000   0.00000860   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000
   -0.00031685   0.00000000   0.00000000  -0.00014426  -0.00000000   0.00000000   0.00000000   0.00000022

 MATRIX VBDIFF          

 SYMMETRY BLOCK 1.1
    0.00000000   0.00000000   0.00000000   0.00000000   0.00000863   0.00000000   0.00000000  -0.00000689
    0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000176   0.00000000   0.00000000
    0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000176   0.00000000
    0.00000000   0.00000000   0.00000000   0.00000001   0.00004747   0.00000000   0.00000000  -0.00003737
    0.00000863   0.00000000   0.00000000   0.00004747   0.61364593   0.00000000   0.00000000  -0.00000000
    0.00000000   0.00000176   0.00000000   0.00000000   0.00000000   0.32324744   0.00000000   0.00000000
    0.00000000   0.00000000   0.00000176   0.00000000   0.00000000   0.00000000   0.32324744   0.00000000
   -0.00000689   0.00000000   0.00000000  -0.00003737  -0.00000000   0.00000000   0.00000000   0.32324744


 **********************************************************************************************************************************
 DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
              1      20        7.51       500      610      700      900      950      970     1000      129      960     1100   
                                          VAR    BASINP    GEOM    SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S 
                                         1400     1410     1420     1200     1210     1080     1600     1650     1300     1700   
                                           T        V       ECP      H0       H01     AOSYM     SMH    MOLCAS    ERIS     OPER   

              2      11        0.60       700     1000      520     2100     1210     2101     1211     3601     2102     1212   
                                         GEOM     BASIS   MCVARS     RHF      H0       RHF      H0      EPOT      RHF      H0  
                                         3602   
                                         EPOT   

 PROGRAMS   *        TOTAL    MATROP    MATROP      DATA       RHF       INT    MATROP      DATA       RHF       INT      DATA
 CPU TIMES  *         0.83      0.05      0.06      0.00      0.06      0.05      0.05      0.00      0.06      0.06      0.00
 REAL TIME  *         0.95 SEC
 DISK USED  *        12.26 MB      
 **********************************************************************************************************************************

 MATROP/AR=ECP1,KR=ECP1 energy=      0.000000000000

        RHF-SCF         RHF-SCF         RHF-SCF 
    -17.86553478    -20.67323640    -38.53843575
 **********************************************************************************************************************************
 Variable memory released
-------------- next part --------------
***, ArKr

basis = VDZ

symmetry,nosym
geometry = {
	Ar
	Kr, Ar, R
}

R = 4 ANG

! dimer AB
dummy
{rhf}
data,copy,1200.1,1210.2

! monomer A
dummy,Kr
{rhf}
data,copy,1200.1,1211.2
{matrop
	load,Epot
	save,Epot,3601.2,triang
}

! monomer B
dummy,Ar
{rhf}
data,copy,1200.1,1212.2
{matrop
	load,Epot
	save,Epot,3602.2,triang
}

{matrop
	load,H0AB,triang,1210.2
	load,H0A,triang,1211.2
	load,H0B,triang,1212.2
	! VA = H0AB - H0B
	! VB = H0AB - H0A
	add,VA,1.0,H0AB,-1.0,H0B
	add,VB,1.0,H0AB,-1.0,H0A
	! VA and VB saved by matrop
	load,VAmatrop,triang,3601.2
	load,VBmatrop,triang,3602.2
	! compute and print differencies
	add,VAdiff,1.0,VA,-1.0,VAmatrop
	add,VBdiff,1.0,VB,-1.0,VBmatrop
	print,VAdiff
	print,VBdiff
}
-------------- next part --------------
 PROGRAM * MATROP


 Matrix H0AB loaded from record   1210.2

 Matrix H0A loaded from record   1211.2

 Matrix H0B loaded from record   1212.2

 VA = H0AB - H0B

 VB = H0AB - H0A

 Matrix VAMATROP loaded from record   3601.2

 Matrix VBMATROP loaded from record   3602.2

 VADIFF = VA - VAMATROP

 VBDIFF = VB - VBMATROP

 MATRIX VADIFF          

 SYMMETRY BLOCK 1.1

   -0.00000000   0.00000000   0.00000000  -0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000  -0.00000000
    0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000
   -0.00000000  -0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000  -0.00000000   0.00000000
    0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000   0.00000000
    0.00000000   0.00000000   0.00000000   0.00000000   0.00000000


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