Charge-transfer (CT) orbitals for the one-electron description of CT excitations in a wide range of donor-acceptor separations

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• 作者：O.V. Gritsenko ^{o.gritsenko@vu.nl}
• 刊名：Chemical Physics Letters
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：667
• 期：Complete
• 页码：51-54
• 全文大小：360 K
• 卷排序：667

文摘

A transformation of the virtual KS orbitals is proposed to a set of charge-transfer orbitals (CTOs) adapted to description of CT excitations. The CTO scheme offers a simple estimate of the CT excitation energy with an orbital energy difference. This estimate reproduces well the reference values of the configuration interaction (CI) method in a wide range of donor-acceptor separations in the paradigmatic He-BeHe-Be complex. CTO-based orbital energy and shape indices are proposed to assess the suitability of the CT description with virtual orbitals of a given basis set. Both indices yield correct trends for the KS and HF orbitals.