Re: CCL:Defining orbitals

David,

You interpreted my question correctly. Without going into the experiment in detail ... we generate Li-(H2O)n clusters and record their infrared spectrum. The source of Li- can potentially create Li- anions in more than the lowest energy singlet state. It appears that the symmetry of the clusters is not the same for different e spin states on the Li- ... an excellent way to differentiate species in vibrational spectroscopy. It would be nice to characterise the different triplet states comprehensively.

Cheers,
Chris

On 14/06/2005, at 3:40 AM, Shobe, David wrote:

<x-tad-smaller>Yes, but...I think he wants to study what would more correctly be called a particular state of Li anion triplet. </x-tad-smaller>
 
<x-tad-smaller>I don't remember how Gaussian treats the degeneracy of the three p orbitals.  If Gaussian just arbitrarily picks one of the three p orbitals, no special manipulation is needed; but if the HOMO is a mixture of px, py, and pz it's a different story...</x-tad-smaller>
 

<x-tad-smaller>--David Shobe, Ph.D., M.L.S.</x-tad-smaller>
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<x-tad-smaller>From:</x-tad-smaller><x-tad-smaller> Computational Chemistry List [mailto:chemistry-request ^^^ ccl.net] </x-tad-smaller><x-tad-smaller>On Behalf Of </x-tad-smaller><x-tad-smaller>Wayne Steinmetz</x-tad-smaller>
<x-tad-smaller>Sent:</x-tad-smaller><x-tad-smaller> Friday, June 10, 2005 4:46 PM</x-tad-smaller>
<x-tad-smaller>To:</x-tad-smaller><x-tad-smaller> chemistry ^^^ ccl.net</x-tad-smaller>
<x-tad-smaller>Subject:</x-tad-smaller><x-tad-smaller> CCL:Defining orbitals</x-tad-smaller>
<x-tad-smaller>The electrons belong to the entire atom and are not constrained to any orbital.  One uses orbitals to construct the wave function.  One must be sure that the set of orbitals, i.e. the basis set, is sufficiently flexible to describe completely the molecular species.  You are dealing with an atomic species so a polarization basis set is probably not needed.</x-tad-smaller>
 
<x-tad-smaller>Wayne E. Steinmetz</x-tad-smaller>
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<x-tad-smaller>-----Original Message-----</x-tad-smaller>
<x-tad-smaller>From:</x-tad-smaller><x-tad-smaller> Computational Chemistry List [mailto:chemistry-request ^^^ ccl.net] </x-tad-smaller><x-tad-smaller>On Behalf Of </x-tad-smaller><x-tad-smaller>Christopher Thompson</x-tad-smaller>
<x-tad-smaller>Sent:</x-tad-smaller><x-tad-smaller> Thursday, June 09, 2005 6:09 PM</x-tad-smaller>
<x-tad-smaller>To:</x-tad-smaller><x-tad-smaller> chemistry ^^^ ccl.net</x-tad-smaller>
<x-tad-smaller>Subject:</x-tad-smaller><x-tad-smaller> CCL:Defining orbitals</x-tad-smaller>
 
Gday,
 
I would like to do an MP2 calc on a Li- species in triplet state.
 
With one electron in the s orbital and one in a p orbital,
how can you constrain the electron to say the px orbital?
 
Cheers,
cdth ## unimelb.edu.au
 
<x-tad-smaller>Christopher Thompson</x-tad-smaller>
<x-tad-smaller>Laser Spectroscopy Group</x-tad-smaller>
<x-tad-smaller>School of Chemistry</x-tad-smaller>
<x-tad-smaller>University of Melbourne</x-tad-smaller>

Dr Christopher Thompson
Laser Spectroscopy Group
School of Chemistry
University of Melbourne
VIC, Australia, 3010.
Ph. +61 3 8344 8163
Fax. +61 3 9347 5180