[molpro-user] Spin-orbit coupling between Triplet and Singlet states
Kelvin Lee
kin.lee at unsw.edu.au
Thu May 7 06:52:04 BST 2015
Dear Molpro mailing list,
I am trying to learn how to calculate the spin-orbit matrix element
between a singlet and triplet state. As a starting point, I've been
trying to calculate CH2 using CASSCF and MRCI, as there is a lot of
published data on this molecule.
I've tried following the example given in the manual on the S-atom, but
the results I'm getting on CH2 make very little sense to me, and I'd
appreciate it if anyone would extend their help.
My input is as follows:
***,Calculating spin-orbit coupling of CH2
memory,148,M
angstrom
gthresh,orbital=1.d-8,energy=1.d-8,step=1.d-5,gradient=1.d-5
nosym
geom={
C
H1 C rCH
H2 C rCH H1 aHCH
}
RCH= 1.12276332 ANGSTROM
AHCH= 102.15789308 DEGREE
basis=dzp
{uhf;occ,5;wf,8,0,2 ! UHF of triplet ground state
orbital,4400.1
}
{multi;occ,10;wf,nelec=8,spin=2;wf,nelec=8,spin=0}
{ci;wf,nelec=8,spin=2;save,4500.1} ! triplet wavefunction
{ci;wf,nelec=8,spin=0;save,4600.1} ! singlet wavefunction
{ci;tranls,4500.1,4600.1} ! calculate matrix element
Which, at the end of the output gives me:
Spin-orbit matrix elements for mean field operator:
!MRCI expec <1.1|LSZ|1.1> 0.000000000000i au = 0.000000006576i
cm-1
If I'm interpreting this correctly, this is supposed to be my matrix
element for these two states?
The previously calculated values lie around ~12 cm-1 or so, so what
unbelievably stupid mistake am I making?
Any form of help would be greatly appreciated.
Thank you,
Kelvin
--
KIN LONG KELVIN LEE | PhD Student
Molecular Photonics Group | School of Chemistry | Faculty of Science
University of New South Wales
Room 417, Chemical Sciences Building F10 | NSW | AUSTRALIA |2052
T9385-0457 |
Ekin.lee at unsw.edu.au |
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