Embedded equation-of-motion coupled-cluster theory for electronic excitation, ionisation, electron attachment, and electronic resonances
| Autor: | Valentina Parravicini, Thomas-C. Jagau |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
equation-of-motion coupled-cluster theory
Biophysics FOS: Physical sciences OPEN-SHELL Physics Atomic Molecular & Chemical 010402 general chemistry 01 natural sciences Projection (linear algebra) ENERGY DENSITY-FUNCTIONAL-THEORY RYDBERG STATES Ionization Physics - Chemical Physics 0103 physical sciences electronic resonances Physical and Theoretical Chemistry Physics::Chemical Physics WAVE-FUNCTION METHODS Molecular Biology Quantum excited states BASIS-SETS Physics AB-INITIO Chemical Physics (physics.chem-ph) Science & Technology 010304 chemical physics Chemistry Physical RANGE QUANTUM-CHEMISTRY Equations of motion Condensed Matter Physics 0104 chemical sciences Chemistry Coupled cluster EXCITED-STATES Excited state Physical Sciences Embedding coupled-cluster theory Atomic physics Quantum embedding Excitation |
| Zdroj: | Molecular Physics |
| DOI: | 10.6084/m9.figshare.14830981 |
| Popis: | The projection-based quantum embedding method is applied to electronically excited states of valence, Rydberg, and charge-transfer character, valence- and core-ionized states, as well as bound and temporary radical anions. We embed different variants of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) theory in density functional theory and investigate the performance of the resulting methods using small organic molecules microsolvated by a varying number of water molecules as test cases. States that are unstable towards electron loss are treated by means of a complex-absorbing potential. Besides transition energies, we also present Dyson orbitals and natural transition orbitals for embedded EOM-CCSD. Our results illustrate that embedded EOM-CCSD describes ionization and valence excitation very well and that these transitions are quite insensitive towards technical details of the embedding procedure. On the contrary, more care is required when dealing with Rydberg excitations or electron attachment. For the latter type of transition in particular, the use of long-range corrected density functionals is mandatory and truncation of the virtual orbital space -- which is indispensable for the application of projection-based embedding to large systems -- proves to be difficult. 21 pages, 3 figures, 9 tables. Final version before typesetting |
| Databáze: | OpenAIRE |
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