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Communication: Configuration interaction singles has a large systematic bias against charge-transfer states
4. M. Casida, in Recent Advances in Density Functional Methods, edited by D. P. Chong (World Scientific, Singapore, 1995), Vol. 1, pp. 155–192.
12. A. Savin, in Recent Advances in Density Functional Methods, edited by D. P. Chong (World Scientific, Singapore, 1995), pp. 129–154.
31. J. W. Ponder
–Software Tools for Molecular Design, version 5.0, Washington University School of Medicine, Saint Louis, MO, 2009, http://dasher.wustl.edu/tinker
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We show that standard configuration interaction singles (CIS) has a systematic bias against charge-transfer(CT) states, wherein the computed vertical excitation energies for CT states are disproportionately too high (by >1 eV) as compared with non-CT states. We demonstrate this bias empirically for a set of chemical problems with both inter- and intra-molecular electron transfer, and then, for a small analytical model, we prove that this large difference in accuracy stems from the massive changes in electronic structure that must accompany long-range charge transfer. Thus far, the conclusion from this research is that, even in the context of wave functiontheory,CIS alone is insufficient for offering a balanced description of excited state surfaces (both CT and non-CT) and explicit electron-electron correlation must be included additionally (e.g., via CIS(D)) for charge-transfer applications.
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