CCL: Energy convergence around conical intersection
- From: Seth Olsen <s.olsen1[A]uq.edu.au>
- Subject: CCL: Energy convergence around conical intersection
- Date: Mon, 11 Sep 2006 10:49:49 +1000
Sent to CCL by: Seth Olsen [s.olsen1|a|uq.edu.au]
Hi Sherin,
Changing the weighting of the states in a state-averaged CAS calculation
will give you convergence problems if the states are close together just
because it doesn't take much variation in the energy of either state in
order to flip the roots. I'm a bit confused as to what your objective
is, though, since any weighting scheme other than 0.5/0.5 would be
expected to overbias one state or the other. This would change the
energy and the position of the intersection, and it's not clear to me
that this would happen in a regular fashion. The question of what
weighting is 'right' to describe the intersection (in the sense of
getting the 'right answer for the right reason') does not seem to be
very relevant because the 'right' weighting will probably vary depending
on the state and the system. In this case, even if the 'right' answer
is achieved, the weighting has become just a tuning parameter and its
not clear that the it is 'right for the right reason'. When you vary
the weighting, are you then comparing to something more trustworthy
(like evenly-weighted MCQDPT or MRCI)?
I've often thought that there isn't that information about
state-averaging in the literature, given that it is the currently the
most popular method for computational photochemical modeling. The rate
of change of weighting of a state averaged CAS solution has been
suggested as a diagnostic for the quality of the wavefunction (Stalring
et al, Mol. Phys. v.2 pp.103-114 (2001)). In this work it is also
pointed out that only for an evenly-weighted wave function is the final
solution invariant to projections within the state-averaged subspace (in
addition to the usual CASSCF orbital rotation invariance). This in turn
has implications for the Lagrangian used to determine analytic gradients
w/ respect to geometry.
Good luck. :-)
Cheers,
Seth
Sherin Alfalah shireen.alfalah^yahoo.com wrote:
Sent to CCL by: "Sherin Alfalah" [shireen.alfalah-*-yahoo.com]
Dear CCL users,
We are trying to run energy calculations for some points around a
conical intersection. I am facing some problems in convergence for the excited
state. To reach MCSCF convergence, we try to read some molecular orbitals of
other close points or to run the energy calculations for the excited state with
more weight of the ground state for example "0.1 or 0.2". In the
conical intersection region, reading different vectors may lead to different
stationary points with different energies. I am a bit confused about the most
proper way to have convergence. Shall it be the choice of method that gave the
lowest energy or what? How can I know that I am not over shooting the minimum?
We are using GAMESS, I am wondering if the results we have are due to
chemical reasons or some artificial results of GAMESS software.
I think that having more weights of the ground state, is reasonable
since the points are within the conical intersection area?
I am wondering about the most proper way to obtain convergence? and also if some
one has any experience or know some tricks that may be useful to obtain
convergence? Also, any information or discussion for this issue would be highly
appreciated.
Thanks in advance.
**************************************
Sherin Alfalah
PhD Student
Theoretical Chemist
Chemistry Department
AlQuds University
**************************************>