Subject: Re: CCL:TDDFT on G03: negative transition energies

From: "S.I.Gorelsky" <gorelsky /a\ stanford.edu>
Date: Thu, 2 Jun 2005 10:09:54 -0700 (PDT)

> 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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From: "T. Daniel Crawford" <crawdad!at!exchange.vt.edu>
Date: Thu, 02 Jun 2005 16:59:21 -0400

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!at!stanford.edu> wrote:

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T. Daniel Crawford                           Department of Chemistry
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From: John McKelvey <jmmckel :: attglobal.net>
Date: Thu, 02 Jun 2005 17:17:58 -0500

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:

>On 6/2/05 1:09 PM, "S.I.Gorelsky" <gorelsky :: stanford.edu> wrote:
>
>  
>
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