Detailed wavefunction analysis for multireference methods: Implementation in the Molcas program package and applications to tetracene
Stefanie A. Mewes
Heidelberg University
Andreas Dreuw
Heidelberg University
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High-level multireference computations on electronically excited and charged states of tetracene are performed, and the results are analyzed using an extensive wavefunction analysis toolbox that has been newly implemented in the Molcas program package. Aside from verifying the strong effect of dynamic correlation, this study reveals an unexpected critical influence of the atomic orbital basis set. It is shown that different polarized double-ζ basis sets produce significantly different results for energies, densities and overall wavefunctions, with the best performance obtained for the atomic natural orbital (ANO) basis set by Pierloot et al. Strikingly, the ANO basis set does not only reproduce the energies but also performs exceptionally well in terms of describing the diffuseness of the different states and of their attachment/detachment densities. This study, thus, underlines the fact that diffuse basis functions are needed for an accurate description of the electronic wavefunctions but also shows that, at least for the present example, it is enough to include them implicitly in the contraction scheme.
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English [eng]
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Journal of Chemical Theory and Computation
American Chemical Society (ACS)
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