Hi all,

I have encountered some problems using egrad.

Short background: I attempt to propagate a

*nuclear* wave packet on the potential energy surface (PES) of the first excited electronic state,

*S*_{1}, of CH

_{2}O using a semiclassical approximation. Therefore, I have to run a bunch of classical trajectories on the excited state PES, and calculate the Hessian (by calling NumForce) along these trajectories. The Hessian is used in the equation-of-motion for the so-called monodromy matrix. Hence, instead of using frog to run the trajectories, I have written a few python scripts, which make the necessary calls to the TURBOMOLE executable modules. For the initial tests of the trajectory calculations, I have turned off the Hessian calculation.

The TURBOMOLE (V6.0, 2009) modules are called with the following setup of the control file:

*C*_{1} symmetry, and Cartesian coordinates- def2-TZVP basis set
- SCF convergence criterion is 10
^{-9} - TD-DFT in conjunction with the RI approximation
- BP86 (default) functional and m5 grid size
- rpas is turned on with the irrep option "a 3"
- The keyword "$exopt 1" is added

The trajectories are represented in a 12-dimensional phase space corresponding to the normal modes of

*S*_{1}. At each time step, the normal mode coordinates are transformed to Cartesian coordinates. Then, the ridft, and subsequently, the egrad modules are called. The Cartesian coordinate representation of the gradient is transformed to the normal mode representation, and Hamilton's equations-of-motion are integrated one time step. This procedure works fine as long as the vibrational energy of the trajectory is rather small, in this case less than ~7000 cm

^{-1} (the energy of the vibrational ground state of

*S*_{1} is

*E*_{g} ~ 5000 cm

^{-1}). If the energy is larger (not more than 2*

*E*_{g}), some trajectories are terminated before reaching the final time (500 fs in these calculations). At the configuration of termination, the ridft ends normally, and I get one of two error messages from egrad:

**abnormal termination**. These are the last few lines of the output written by egrad:

232 -------------------

233 excitation vector

234 -------------------

235

236

237 dimension of super-tensorspace: 1

238

239 IRREP tensor space dimension number of roots

240

241 a 528 3

242

243 Aufbau principle violation encountered. Check occupancies!

I don't know how to solve this problem during the trajectory calculation.**missing or faulty SCF orbitals**. These are the last few lines of the output written by egrad:

210 MOs are in ASCII format !

211

212

213 reading orbital data $scfmo from file mos .

214

215 orbital characterization : scfdump=100

216

217

218 self consistent orbitals required

Here I have used "$scfiterlimit 100". The same problem occurs with "$scfiterlimit 200", where the output reads "scfdump=200". Should I relax the SCF convergence criterion? I have chosen 10^{-9} to get a well conserved total energy along the trajectories.

In order to understand these problems, I have run similar trajectory calculations in the ground electronic state,

*S*_{0}, of CH

_{2}O. Here, the gradient (rdgrad), and Hessian (aoforce), calculations along the trajectories can be carried out even for "large" energies (~7*

*E*_{g}).

Regards,

Jakob