Re: CCL:TDDFT on G03: negative transition energies



This comment is strongly tied to the Thouless instability condition [see copious work by Paldus and Cizek in the 60's.] Negative eigenvalues were discussed as a direction in which to improve the reference wavefunction, usually the ground state. Rolf Seeger et. al. placed such code in Gxy for HF wave functions, I believe...
 John McKelvey
 T. Daniel Crawford wrote:
 
 It should be noted that, in the TD-DFT framework (which is closely related
 to RPA), the response matrix cannot technically have negative eigenvalues.
 I would speculate that the eigenvalues reported by the code as negative are
 actually pure imaginary.  This does indicate an "instability" in the
 response matrix, which you could perhaps interpret as a lower-energy state.
 -Daniel
 On 6/2/05 1:09 PM, "S.I.Gorelsky" <gorelsky :: stanford.edu>
 wrote:
 
 I have done some B3lyp TDDFT calculations on some
 transition metal complexes and I have obtained some
 negative excitation energies . Does it make sense or
 it is an error of the code? Has anyone come across the
 same problem?
 
 This means that what you have got as a reference state in your calculation
 is THE EXCITED STATE, and there is at least one lower-energy electronic
 state (the TRUE ground state) at the given level of theory.
 Regards,
 S. Gorelsky
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 Dr S.I. Gorelsky, Department of Chemistry, Stanford University
 Box 155, 333 Campus Drive, Stanford, CA 94305-5080 USA
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