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Dear Molpro mailing list,<br>
<br>
<br>
<br>
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.<br>
<br>
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.<br>
<br>
My input is as follows:<br>
<br>
***,Calculating spin-orbit coupling of CH2<br>
memory,148,M<br>
angstrom<br>
gthresh,orbital=1.d-8,energy=1.d-8,step=1.d-5,gradient=1.d-5<br>
nosym<br>
geom={<br>
C<br>
H1 C rCH<br>
H2 C rCH H1 aHCH<br>
}<br>
RCH= 1.12276332 ANGSTROM<br>
AHCH= 102.15789308 DEGREE<br>
basis=dzp<br>
{uhf;occ,5;wf,8,0,2 ! UHF of triplet ground state<br>
orbital,4400.1<br>
}<br>
{multi;occ,10;wf,nelec=8,spin=2;wf,nelec=8,spin=0}<br>
<br>
{ci;wf,nelec=8,spin=2;save,4500.1} ! triplet wavefunction<br>
{ci;wf,nelec=8,spin=0;save,4600.1} ! singlet wavefunction<br>
<br>
{ci;tranls,4500.1,4600.1} ! calculate matrix element<br>
<br>
<br>
Which, at the end of the output gives me:<br>
<br>
Spin-orbit matrix elements for mean field operator:<br>
<br>
!MRCI expec <1.1|LSZ|1.1> 0.000000000000i au =
0.000000006576i cm-1<br>
<br>
If I'm interpreting this correctly, this is supposed to be my matrix
element for these two states?<br>
The previously calculated values lie around ~12 cm-1 or so, so what
unbelievably stupid mistake am I making?<br>
<br>
Any form of help would be greatly appreciated.<br>
<br>
<br>
<br>
<br>
Thank you,<br>
<br>
<br>
Kelvin<br>
<br>
<br>
<div class="moz-signature">-- <br><span><pre wrap=""><span><span><pre wrap="">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 | <span __postbox-detected-content="__postbox-detected-date" class="__postbox-detected-content __postbox-detected-date" style="display: inline; font-size: inherit; padding: 0pt;"><span __postbox-detected-content="__postbox-detected-date" class="__postbox-detected-content __postbox-detected-date" style="display: inline; font-size: inherit; padding: 0pt;">2052
T <span __postbox-detected-content="__postbox-detected-date" class="__postbox-detected-content __postbox-detected-date" style="display: inline; font-size: inherit; padding: 0pt;"><span __postbox-detected-content="__postbox-detected-date" class="__postbox-detected-content __postbox-detected-date" style="display: inline; font-size: inherit; padding: 0pt;"><span __postbox-detected-content="__postbox-detected-date" class="__postbox-detected-content __postbox-detected-date" style="display: inline; font-size: inherit; padding: 0pt;"><span __postbox-detected-content="__postbox-detected-date" class="__postbox-detected-content __postbox-detected-date" style="display: inline; font-size: inherit; padding: 0pt;"></span></span></span></span></span></span>9385-0457 |
E <a class="moz-txt-link-abbreviated" href="mailto:k.lee@chem.usyd.edu.au">kin.lee@unsw.edu.au</a> |</pre></span></span>
</pre> </span></div>
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