Excited state pes

Yes, there are EOM CCSD gradients for both ROHF and UHF approaches. The “follow_root” keyword is intended for CC3 computations where only a single excited state is solved, and one needs the CC3 state to correspond with the previously determined EOM CCSD state. By default, the gradients or properties for EOM CCSD are computed for the last state (irrep and highest energy) obtained. This can be controlled with PROP_ROOT and PROP_SYM. Sometimes it is necessary to carry out the Davidson algorithm for 3 excited states, for example, when it is the 2nd one that one wants to converge and further investigate. The EOM_GUESS (defaulting to the lowest-energy eigenvectors of the Hbar singles block) should allow you to specify other initial-guess states. We seem not to have a test case for this, and if anyone has used it recently, it may be someone in the Crawford group. I read a paper on seeking conical intersections and was very interested, but never got around to implementing it.