caa a22 4500 605488096 CHVBK 20210128100453.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s00214-015-1697-4 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1697-4 Part and whole in wavefunction/DFT embedding [Elektronische Daten] [Thomas Dresselhaus, Johannes Neugebauer] Density functional theory (DFT)-based subsystem and embedding methods have found a widespread use in Quantum Chemistry. The combination of correlated wavefunction (WF) methods and density-based embedding methods is particularly promising for accurate descriptions of complex systems. Here, we address some conceptual issues in such WF/DFT methods concerning (1) the interpretation of wavefunctions and densities in these frameworks, (2) the interpretation of subsystem and supersystem density changes as a polarization of the electronic system, and (3) non-orthogonality effects between wavefunctions of ground and excited states in WF/DFT embedding making use of state-specific embedding potentials. Illustrative examples are provided to analyze the significance of these issues in practical calculations. We find that physically reasonable subsystem densities and subsystem dipole moments can often be obtained from subsystem calculations making use of typical setups in practice, in spite of formal issues that are in principle in conflict with such interpretations. For excited-state WF/DFT calculations, we demonstrate that orthogonality violations due to state-specific embedding potentials are usually small. Springer-Verlag Berlin Heidelberg, 2015 Density-based embedding nationallicence Hybrid methods nationallicence Wavefunction/DFT embedding nationallicence Dresselhaus Thomas Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany aut Neugebauer Johannes Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-15 1432-881X 134:8<1 2015 134 214 https://doi.org/10.1007/s00214-015-1697-4 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1697-4 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Dresselhaus Thomas Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany aut NATIONALLICENCE 700 1- Neugebauer Johannes Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-15 1432-881X 134:8<1 2015 134 214