Implementation of transition moments between excited states in the approximate coupled-cluster singles and doubles model.
An implementation of transition moments between excited states for the approximate coupled-cluster singles and doubles model (CC2) using the resolution of the identity (RI) approximation is reported. The accuracy of the RI approximation is analyzed for a testset of 7 molecules and 76 transitions. The RI error is found to be very small for both transition moments and oscillator strengths. Furthermore, the performance of the CC2 model in comparison with coupled-cluster singles and doubles (CCSD) is studied for 40 transitions of the same testset, yielding deviations of about 12% for the transition moments and 24% for the oscillator strengths. In addition, for 13 transitions of the testset the behavior of the transition moments with respect to seven different basis sets (Dunnings xaug-cc-pVXZ, with x=0,1,2 for X=D,T and x=2 for X=5) is analyzed, showing a strong dependence on the degree of augmentation x and a rather small effect of the cardinal number X. First applications are presented for the triplet-triplet transition moments of benzene and polyacenes (naphthalene to pentacene), showing good agreement with experimental and theoretical results for transitions between single excitation dominated states. Somewhat problematic is the insufficient description of double-excitation dominated states by the CC2 model. As transitions to such states may be strongly allowed, unlike for excitations out of the ground state, important features of transient spectra may be missed. For triplet-triplet excitations the problem is less evident as the lowest doubly excited triplet states are expected at higher energies.
Pabst
Mathias
M
Institut für Physikalische Chemie, Universität Mainz, Jakob Welder-Weg 11, D-55099 Mainz, Germany. pabst@uni-mainz.de
Köhn
Andreas
A