Intermediate state representation approach to physical properties of molecular electron-detached states - I. Theory and implementation
The third-order non-Dyson algebraic-diagrammatic construction approach to the electron propagator [IP-ADC(3)] is extended using the intermediate state representation (ISR) formalism, allowing the wave functions and properties of molecular states with detached electron to be studied. The second-order...
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| Main Authors: | , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
10 January 2020
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| In: |
The journal of chemical physics
Year: 2020, Volume: 152, Issue: 2 |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.5137792 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1063/1.5137792 Verlag, lizenzpflichtig, Volltext: https://aip.scitation.org/doi/10.1063/1.5137792 
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| Author Notes: | Adrian L. Dempwolff, Alexander C. Paul, Alexandra M. Belogolova, Alexander B. Trofimov, and Andreas Dreuw |
| Summary: | The third-order non-Dyson algebraic-diagrammatic construction approach to the electron propagator [IP-ADC(3)] is extended using the intermediate state representation (ISR) formalism, allowing the wave functions and properties of molecular states with detached electron to be studied. The second-order ISR equations [ISR(2)] for the one-particle (transition) density matrix have been derived and implemented in the Q-CHEM program. The approach is completely general and enables evaluation of arbitrary one-particle operators and interpretation of electron detachment processes in terms of density-based quantities. The IP-ADC(3)/ISR(2) equations were implemented for ŜzŜz<math display="inline" overflow="scroll" altimg="eq-00001.gif"><msub><mrow><mi>Ŝ</mi></mrow><mrow><mi>z</mi></mrow></msub></math>-adapted intermediate states, allowing open-shell molecules to be studied using unrestricted Hartree-Fock references. As a first test for computations of ground state properties, dipole moments of various closed- and open-shell molecules have been computed by means of electron detachment from the corresponding anions. The results are in good agreement with experimental data. The potential of IP-ADC(3)/ISR(2) for the interpretation of photoelectron spectra is demonstrated for the galvinoxyl free radical. |
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| Item Description: | Gesehen am 14.04.2020 |
| Physical Description: | Online Resource |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.5137792 |