Matrix elements of lx,ly,lz
Girts Barinovs
girts at kfi.lu.lv
Fri Mar 7 12:11:28 GMT 2003
Dear all!
I am calculating matrix elements of the angular momentum
operators lx, ly, lz. Strangely, the results at CI level
change if I calculate or do not calculate the matrix
elements at CASSCF level before doing CI calculations.
I would like to have some control of this behavior,
could anybody help me to understand what is happening
in my calculations. Thanks.
Girts
****************************************************************************
***,CH2+
geometry={X;noorient; !z-axis goes through C and mass center
C, -1,0.00000000, 0.00000000, 1.150513890; !yz-molecule plane, Cs symmetry
H1,-1,0.00000000, 0.315000000,-7.395082115; !0,0,0 -center of mass
H2,-1,0.00000000,-0.315000000,-6.303890106;}!Jacobi R=8,r=1.26,theta=30
basis
H=VTZ
C=VQZ
end
hf;occ,4,0;wf,7,1,1
multi;occ,4,1;core,1,0;wf,7,1,1;wf,7,2,1;
!tran,lx,ly,lz; !<====!!! Different CI results if comment or uncomment this line
ci;occ,5,2;core,1,0;wf,7,1,1;save,7001.1;
ci;occ,5,2;core,1,0;wf,7,2,1;save,7002.1;
ci;trans,7002.1,7001.1,lx,ly,lz;
table,r1(1),rhq(i),trlz(1),trly(1),sqrt(trlz(1)**2+trly(1)**2)
!Square root of the sum above is expected to be equal to 1 approximately.
****************************************************************************
Output of
tran,lx,ly,lz;
...
ci;trans,7002.1,7001.1,lx,ly,lz;
R1(1) RHQ(I) TRLZ(1) TRLY(1) SQRT(TRLZ(1)**2+TRLY(1)**2)
R1(1) RHQ(I) 0.85721515 -0.51487382 0.99995643
MRCI MRCI MULTI MULTI HF-SCF
-38.54145104 -38.54145010 -38.44314750 -38.44316943 -38.42124983
****************************************************************************
Output of
ci;trans,7002.1,7001.1,lx,ly,lz;
R1(1) RHQ(I) TRLZ(1) TRLY(1) SQRT(TRLZ(1)**2+TRLY(1)**2)
R1(1) RHQ(I) 2.54906962D-05 0.17017114 0.17017114
MRCI MRCI MULTI MULTI HF-SCF
-38.54145104 -38.54145010 -38.44314750 -38.44316943 -38.42124983
****************************************************************************
I am using molpro2000.1
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