From owner-chemistry@ccl.net Fri Jul  6 04:26:01 2007
From: "Arvydas Tamulis tamulis]*[mserv.itpa.lt" <owner-chemistry_+_server.ccl.net>
To: CCL
Subject: CCL:G: Problems with oscillator strengths in TDDFT
Message-Id: <-34674-070706035451-12371-LnQr5Pgk1qXtSiQI0Y5rVQ_+_server.ccl.net>
X-Original-From: Arvydas Tamulis <tamulis:+:mserv.itpa.lt>
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Date: Fri, 6 Jul 2007 10:54:30 +0300 (EEST)
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Sent to CCL by: Arvydas Tamulis [tamulis() mserv.itpa.lt]
Good morning,

The same reversible oscillator strengths for those two singlet transitions
we obtaining not only for D3 symmetry Ru(bpy)32+ but also for 
[Ru(bpy)2(4-4'-Me2-2,2'-bpy)]2+ derivative where is breaking the D3 
symmetry. While those two singlet transitions are from Ru to ligand
in all two cases.

Best regards,
Arvydas

On Thu, 5 Jul 2007, Sue Lam chsue2004#,#yahoo.com wrote:

> Hi. Is the calculated oscillator strengths for those two singlet transitions the same, if you break down the symmetry of the [Ru(bpy)3]2+ molecule?
>
>  Best regards,
>  Sue
>
>
> "Arvydas Tamulis tamulis_._mserv.itpa.lt" <owner-chemistry!A!ccl.net> wrote:
>
> Sent to CCL by: Arvydas Tamulis [tamulis.:.mserv.itpa.lt]
>
> Dear Colleagues,
>
> We have calculated spectrum and oscillator strengths of D3 symmetry
> complex [Ru(bpy)3]2+ using TDDFT B3LYP with the LanL2DZ
> basis set and IEFPCM or COSMO water solvent shell models in
> Gaussian03 or ORCA program packages. We have received two
> singlet-E lines: 456.18 nm (0.0140 oscillator strength) and
> 435.61 nm (0.1373 oscillator strength).
> Experiment of [Ru(bpy)3]2+ derivatives gives two peaks:
> one at about 450 nm (intensity 1.0 arbitrary units) and the
> other near 430 nm (intensity 0.6 arbitrary units)
> therefore the values of our calculated intensities are reversible in
> comparison with experiment.
> Oscillator strength calculations done by G03 and
> ORCA are exactly the same wrong calculating with PBEPBE potential
> using 6-311G* basis set.
> My impression is that it is something wrong in B3LYP, PBEPBE potentials
> when calculating oscillator strengths by Gaussian03 and ORCA programs
> of the D3 symmetry complexes and their derivatives
> while the values of spectral lines are exactly good.
> It is interesting that even ZINDO gives the right intensities in
> comparison with experiment but the values of spectral lines are
> shifted strongly. Maybe you can advise some good program with DFT
> potential/basis set for the calculations of right oscillator strengths of
> the D3 symmetry complexes and their derivatives?
>
> In the case if you are far from the field of calculations of oscillator
> strengths in G03 or ORCA, would you please to forward my question to
> developers of program packages who are working on subroutine
> of calculations of oscillator strengths in G03, ORCA or people who
> possesses the good subroutine.
>
> For regular organic compounds the oscillator strengths obtained by
> TDDFT in G03 and ORCA are good.
> More about our research you can see in our website
> www.itpa.lt/~tamulis/ and press on button
> For PACE project WEBsite
>
> With best regards,
> Arvydas Tamulishttp://www.ccl.net/cgi-bin/ccl/send_ccl_messagehttp://www.ccl.net/chemistry/sub_unsub.shtmlhttp://www.ccl.net/spammers.txt---------------------------------
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