Timeline for After a unitary transformation, is Koopmans' theorem still valid?
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| Jul 24, 2017 at 20:30 | comment | added | jheindel | @levineds Thanks for the reference. I see what you're saying and what they're saying. I should have been more precise when saying total energy. I have also since cleared up my confusion about the Fock operator and Fock matrix. Things were pretty jumbled but I'm glad to straighten them out! | |
| Jul 24, 2017 at 18:46 | comment | added | levineds | No, again, the eigenvalues of the Fock matrix (which is the Fock operator in some basis) are the canonical orbital energies. Moreover, the sum of orbital energies is NOT the total system energy. Check out this paper for more info: pubs.acs.org/doi/abs/10.1021/ed200673w | |
| Jul 24, 2017 at 15:32 | vote | accept | jheindel | ||
| Jul 24, 2017 at 14:36 | answer | added | Martin - マーチン♦ | timeline score: 17 | |
| Apr 13, 2017 at 12:57 | history | edited | CommunityBot |
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| Apr 6, 2017 at 20:13 | vote | accept | jheindel | ||
| Jul 24, 2017 at 15:32 | |||||
| Apr 6, 2017 at 3:11 | history | edited | pentavalentcarbon |
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| Mar 18, 2017 at 3:09 | answer | added | Tyberius♦ | timeline score: 11 | |
| Mar 3, 2017 at 2:57 | history | tweeted | twitter.com/StackChemistry/status/837497005148614656 | ||
| Mar 1, 2017 at 3:26 | comment | added | jheindel | Ah sorry. I was confusing the Fock matrix and the Fock operator. The eigenvalues of the Fock matrix are the energy of the whole system which corresponds to the sum of eigenvalues of the Fock operator which are indeed the orbital energies. Sorry to suggest otherwise. What I'm pointing out in the question is that the set of orbitals and their eigenvalues given by the Fock operator is not the only solution we could come up with. So, I'm basically asking what is so special about the HF orbitals that Koopmans' theorem should be so simple when that doesn't seem to be the case for other orbital sets. | |
| Mar 1, 2017 at 0:52 | comment | added | Greg | They do, the Fock operator is an effective one electron operator and this is how you find the orbitals and the correspond energies. | |
| Mar 1, 2017 at 0:45 | comment | added | jheindel | I don't think that the orbital energies ever correspond to the eigenvalues of the Fock operator. Rather the eigenvalues are the sum of these orbital energies, but I'm pretty sure these orbital energies are not unique because the orbitals themselves are not unique. The second half of that sentence depends on the answer to this question which I'm not completely sure of. | |
| Mar 1, 2017 at 0:37 | comment | added | Greg | HOMO has a well defined energy only when it corresponds to an eigenvalue from HF. After such a unitary transformation the orbitals have no well defined energies any more | |
| Feb 28, 2017 at 23:46 | history | edited | jheindel | CC BY-SA 3.0 |
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| Feb 28, 2017 at 23:41 | history | asked | jheindel | CC BY-SA 3.0 |