CCL:G: Problems with oscillator strengths in TDDFT

 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---------------------------------
 Take the Internet to Go: Yahoo!Go puts the Internet in your pocket: mail, news,
 photos & more.