Journal Article

FZJ-2017-00323

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Energy Ordering of Molecular Orbitals

Puschnig, P. (Corresponding author) ; Boese, A. D. ; Willenbockel, M. ; Meyer, M. ; Lüftner, D. ; Reinisch, E. M. ; Ules, T. ; Koller, G. ; Soubatch, S. ; Ramsey, M. G. ; Tautz, F. S.FZJ*

2016
ACS Washington, DC

This record in other databases:      

Please use a persistent id in citations: http://hdl.handle.net/2128/13423  doi:10.1021/acs.jpclett.6b02517

Abstract: Orbitals are invaluable in providing a model of bonding in molecules or between molecules and surfaces. Most present-day methods in computational chemistry begin by calculating the molecular orbitals of the system. To what extent have these mathematical objects analogues in the real world? To shed light on this intriguing question, we employ a photoemission tomography study on monolayers of 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) grown on three Ag surfaces. The characteristic photoelectron angular distribution enables us to assign individual molecular orbitals to the emission features. When comparing the resulting energy positions to density functional calculations, we observe deviations in the energy ordering. By performing complete active space calculations (CASSCF), we can explain the experimentally observed orbital ordering, suggesting the importance of static electron correlation beyond a (semi)local approximation. On the other hand, our results also show reality and robustness of the orbital concept, thereby making molecular orbitals accessible to experimental observations.

---

Contributing Institute(s):

1. Funktionale Nanostrukturen an Oberflächen (PGI-3)

Research Program(s):

1. 142 - Controlling Spin-Based Phenomena (POF3-142) (POF3-142)

Appears in the scientific report 2016

---

Database coverage:
; ; Current Contents - Physical, Chemical and Earth Sciences ; Free to read ; IF >= 5 ; JCR ; NCBI Molecular Biology Database ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

---