Toward an understanding of electronic excitation energies beyond the molecular orbital picture

Physical Chemistry Chemical Physics : PCCP
Patrick Kimber, Felix Plasser

Abstract

Tuning the energies of molecular excited states is a central research theme in modern chemistry with high relevance for optoelectronic applications and chemical synthesis. Whereas frontier orbitals have proven to be an intuitive and simple model in many cases, they can only provide a very rough approximation of the underlying wavefunctions. The purpose of this Perspective is to explore how our qualitative understanding of electronic excitation processes can be promoted beyond the molecular orbital picture by exploiting methods and insights from modern quantum chemistry. For this purpose, the physics of a correlated electron-hole pair is analysed in detail to show the origin of exchange repulsion and a dynamic Coulomb attraction, which determine its energy aside from the orbital energies. Furthermore, we identify and discuss the two additional effects of secondary orbital relaxation and de-excitations. Rules for reconstructing these four contributions from general excited-state computations are presented and their use is exemplified in three case studies concerned with the relative ordering of the singlet and triplet ππ* and nπ* states of uracil, the large energetic differences between the first singlet and triplet states of the...Continue Reading

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Citations

Jul 3, 2020·The Journal of Chemical Physics·Kaushik D Nanda, Anna I Krylov
Sep 3, 2020·The Journal of Chemical Physics·Anna I Krylov
Aug 31, 2020·Chemical Science·Pedro A Sánchez-MurciaLeticia González
Dec 17, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·G RicciJ C Sancho-García
Feb 18, 2021·Journal of Computational Chemistry·Marvin Hoffmann, Andreas Dreuw
Mar 2, 2021·Physical Chemistry Chemical Physics : PCCP·Pau Besalú-SalaMiquel Solà
Jul 10, 2021·The Journal of Chemical Physics·Kaushik D Nanda, Anna I Krylov
Jul 1, 2021·Journal of Chemical Theory and Computation·Maristella Alessio, Anna I Krylov
Jun 6, 2020·Journal of Chemical Theory and Computation·Balázs KozmaPéter G Szalay
Sep 3, 2021·The Journal of Chemical Physics·Evgeny EpifanovskyAnna I Krylov
Oct 8, 2021·The Journal of Physical Chemistry Letters·Vladimir PomogaevCheol Ho Choi

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Software Mentioned

TDDFT
pymol
feynman
TheoDORE
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libwfa
OpenMolcas
CASSCF
orbkit
qc

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