A pair natural orbital implementation of the coupled cluster model CC2 for excitation energies

Benjamin Helmicha and Christof Hättiga
a Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44801 Bochum, Germany

J. Chem. Phys. 139, 084114 (2013)
(Received 20 JUN 2013; accepted 08 AUG 2011)

We demonstrate how to extend the pair natural orbital (PNO) methodology for excited states, presented in a previous work for CIS(D), to iterative coupled cluster methods like the approximate singles and doubles model CC2. The original O(N5) scaling of the PNO construction is reduced by using orbital-specific virtuals (OSVs) as an intermediate step without spoiling the initial accuracy of the PNO method. Furthermore, a slower error convergence for charge-transfer states is analyzed and resolved by a numerical Laplace transformation during the PNO construction, so that an equally accurate treatment of local and charge-transfer excitations is achieved. With state-specific truncated PNO expansions, the eigenvalue problem is solved by combining the Davidson algorithm with deflation to project out roots that have already been determined and an automated refresh with a generation of new PNOs to achieve self-consistency of the PNO space. For a large test set, we found that truncation errors for PNO-CC2 excitation energies are only slightly larger than for PNO-CIS(D). The computational efficiency of PNO-CC2 is demonstrated for a large organic dye where a reduction of the doubles space by a factor of more than 1000 is obtained compared to the canonical calculation. A compression of the doubles space by a factor 30 is achieved by a unified OSV space only. Moreover, calculations with the still preliminary PNO-CC2 implementation on a series of glycine oligomers revealed an early break even point with a canonical RI-CC2 implementation between 100 and 300 basis functions.

View Article:     PDF   (access restricted to domain theochem.rub.de)

Back to the list of Publications by the Quantum Chemistry (Hättig) Group