CCL:G: TD-DFT opt failing in G09

 Sent to CCL by: Jamin Krinsky [jamink-,-berkeley.edu]
 Dear Zhou,
 Thank you very much for your detailed response. I had suggested to
 that user that he try using a smaller optimization step size (not
 really thinking it would help) and just got an email saying that it
 fixed the problem. So your suggestion of decreasing "maxstep" is
 indeed a good one!
 Best regards,
 Jamin
 On Sat, Apr 3, 2010 at 12:43 AM, Zhou Panwang pwzhou ~ gmail.com
 <owner-chemistry^^ccl.net> wrote:
 > I have consulted this question with Gaussian Technique Support, and
 > following are their answers. Please notice the last paragraph.
 > Also, you can try use the last structure to restart the optimization or add
 > the direct options to TDDFT.
 >
 > In the case of "No map to state **, you need to resolve more
 vectors"
 > messages, this is usually an indication that one did not include enough
 > excited states in the TD or CIS calculation. The "States=N"
 option to the
 > "TD" or "CIS" keywords tells how many excited states to
 include in an
 > excited state energy calculation. If this is not specified, the default
 > value will be "States=3". The recommended value is to include a
 minimum of 2
 > or 3 more states than the state of interest. Thus, if you want to perform a
 > geometry optimization for excited state 5, for example, I would recommend
 at
 > least using "States=7" or "States=8". The geometry
 optimization will be done
 > for one excited state M, selected with "Root=M", and one has to
 make sure
 > that enough states are included in the CIS or TD expansion by having
 > "States=N" where N is larger than M.
 >
 > It is possible that, at some point during an optimization of an excited
 > state, the order of the excited states changes and the CIS or TD expansion
 > might need to include more states in order to be able to follow correctly
 > the state of interest. This is essentially what that message about
 including
 > more vectors mean, that is that at that point, the number of states that
 you
 > originally specified with "States=N" was not enough in order to
 solve for
 > the state of interest, so a larger number "N" will need to be
 used for
 > "States=N".
 >
 > Other times, the problem is that the ground state wavefunction becomes
 > unstable, that is one of the states that was an excited at the initial
 > geometry now becomes lower in energy than the state that was the ground
 > state at the initial geometry. This kind of situation, unfortunately,
 cannot
 > be modeled properly with single determinant expansions such as CIS or TD,
 > and one would need to use CAS in order to be able to deal with the conical
 > intersection or avoided crossing of states.
 >
 > Another thing to note is that one should be much more careful with geometry
 > optimizations on excited states than for the ground state. Typically the
 > energy differences among excited states are smaller than between the ground
 > state and the first excited state. Thus, one can afford to perform larger
 > geometry optimization steps when optimizing the ground state than in the
 > case of optimizing an excited state.
 >
 > A "bad" geometry optimization step in the optimization of the
 ground state,
 > may take you a bit off track but in following steps the optimization might
 > find the way back and approach the converged structure. In the case of an
 > optimization of an excited state, a "bad" geometry optimization
 step will
 > also take you off track but, since other electronic states are close in
 > energy, it is possible that at the new geometry the order of the excited
 > states change and now the geometry optimization follows a different
 > electronic state.
 >
 > This is not only a problem because the optimization could be pursuing a
 > different state than the one you were interested in, but also because, if
 > several of these changes occur during a geometry optimization, it may even
 > be hopeless to continue with the optimization because the gradient
 > information and the estimated hessian could be useless (since not all the
 > previous points in the geometry optimization where points from the same
 > potential energy surface).
 >
 > As a first measure to increase the reliability of the geometry optimization
 > of excited states, I recommend to reduce the maximum allowed step size
 > during geometry optimizations. Try "Opt=(MaxStep=10)" to set this
 value to
 > 0.10 Bohr, or a smaller value if you still have problems. The default value
 > is typically 0.30 Bohr. Reducing the maximum allowed step size will result
 > in the geometry optimization taking more steps to reach convergence than
 > with the default value. This will be true obviously for well-behaved
 > geometry optimizations, but for problematic cases it will be the other way
 > around, i.e. it will take fewer steps (and may even be impossible with the
 > default step size) because it will be easier for the optimizer to follow a
 > particular electronic state if the changes from step to step are not very
 > drastic.
 >
 > 2010/4/1 Jamin Krinsky jamink_-_berkeley.edu <owner-chemistry ..
 ccl.net>
 >>
 >> Sent to CCL by: Jamin Krinsky [jamink(~)berkeley.edu]
 >> Dear forum,
 >>
 >> I have a user who is getting a mysterious failure message while
 >> attempting TD-DFT optimizations in G09. It's related to link 914 but
 >> it doesn't make sense. Here is the route section:
 >>
 >> #p opt td=(singlets,nstates=6,root=1) rb3lyp/6-31+g(d) nosymm
 >> int=ultrafine scf(xqc,maxconventionalcycles=60)
 >>
 >> The calculation runs for 6 geometry steps but the first excited state
 >> energy is quite oscillatory. At the 7th step, it quits with the
 >> following error:
 >>
 >> No map to state      1
 >> You need to solve for more vectors in order to follow this state.
 >> Error termination via Lnk1e in
 /usr/software/gaussian/g09.revA02/l914.exe
 >>
 >> If he's following the 1st excited state then he shouldn't need more
 >> states (increasing "nstates" to 20 does not help). I've never
 seen
 >> this although my experience with this algorithm is minimal, and
 >> although that error has come up a couple of times in these threads I
 >> haven't seen a conclusive explanation. Any help with this would be
 >> appreciated.
 >>
 >> Regards,
 >> Jamin
 >>
 >> --
 >> Jamin L Krinsky, Ph.D.
 >> Molecular Graphics and Computation Facility
 >> 175 Tan Hall, University of California, Berkeley, CA 94720
 >> jamink~~berkeley.edu, 510-643-0616
 >> http://glab.cchem.berkeley.edu
 >>
 >>
 >>
 >> -= This is automatically added to each message by the mailing script =-
 >> E-mail to subscribers: CHEMISTRY .. ccl.net or use:
 >>      http://www.ccl.net/cgi-bin/ccl/send_ccl_message
 >>
 >> E-mail to administrators: CHEMISTRY-REQUEST .. ccl.net or use
 >>      http://www.ccl.net/cgi-bin/ccl/send_ccl_message>>;
      http://www.ccl.net/chemistry/sub_unsub.shtml>>;  
    http://www.ccl.net/spammers.txt>>;
 >>
 >
 >
 >
 > --
 > ========================================
 > Panwang Zhou
 > State Key Laboratory of Molecular Reaction Dynamics
 > Dalian Institute of Chemical Physics
 > Chinese Academy of Sciences.
 > Tel: 0411-84379195 Fax: 0411-84675584
 > ========================================
 >
 >
 --
 Jamin L Krinsky, Ph.D.
 Molecular Graphics and Computation Facility
 175 Tan Hall, University of California, Berkeley, CA 94720
 jamink^^berkeley.edu, 510-643-0616
 http://glab.cchem.berkeley.edu