A new diagnostic for open-shell coupled-cluster theory

We present a new diagnostic for open-shell coupled-cluster theory, readily computed from the single substitution amplitudes in the CCSD wavefunction. The new diagnostic, D-1(ROCCSD), is designed to be comparable to the previo usly proposed D-1(CCSD) diagnostic. Unlike other approaches, the D-1 diagno stics are independent of system size and have the same invariance propertie s as the energy with respect to orbital rotations. Calibration of the D-1(R OCCSD) diagnostic on 34 molecular systems indicates that for Values of D-1( ROCCSD) of 0.025 or below the quality of the CCSD results are, in general, excellent, whereas values larger than 0.025 signal inadequacies in the CCSD approach. (C) 2000 Elsevier Science B.V. All rights reserved.