Ionization energies in solution with the QM:QM approach. Issue 19 (3rd February 2020)

• Record Type: Journal Article
• Authors: Tóth, Zsuzsanna; Kubečka, Jakub; Muchová, Eva; Slavíček, Petr
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 19(2020)
• Page Start: 10550
• Page End: 10560
• Publication Date: 2020-02-03
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp06154a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Fragment-based QM:QM technique provides an efficient and accurate way for calculating energetics of vertical processes such as ionization. Abstract : We discuss a fragment-based QM:QM scheme as a practical way to access the energetics of vertical electronic processes in the condensed phase. In the QM:QM scheme, we decompose the large molecular system into small fragments, which interact solely electrostatically. The energies of the fragments are calculated in a self-consistent field generated by the other fragments and the total energy of the system is calculated as a sum of the fragment energies. We show on two test cases (cytosine and a sodium cation) that the method allows one to accurately simulate the shift of vertical ionization energies (VIE) while going from the gas phase to the bulk. For both examples, the predicted solvent shifts and peak widths estimated at the DFT level agree well with the experimental observations. We argue that the QM:QM approach is more suitable than either an electrostatic embedding based QM/MM approach, a full quantum description at the DFT level with a generally used functional or a combination of both. We also discuss the potential scope of the applicability for other electronic processes such as Auger decay.