Spin adapted implementation of EOM-CCSD for triplet excited states: Probing intersystem crossings of acetylacetone at the carbon and oxygen K-edges

Abstract

 Users may download and print one copy of any publication from the public portal for the purpose of private study or research.  You may not further distribute the material or use it for any profit-making activity or commercial gain  You may freely distribute the URL identifying the publication in the public portal If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.

Probing competing relaxation pathways in malonaldehyde with transient X-ray absorption spectroscopy

“…The neglect of scalar relativistic effects is expected to be associated with a red-shi of $0.3-0.4 eV. 96 Similar close agreement in shape was recently reported by Faber et al for acetylacetone at the CVS-EOM-CCSD level of theory, 55 although the overall shi is smaller in the present study. The methyl substituents in AcAc lead to a blue-shi of both pre-edge peaks of $0.2 eV compared to malonaldehyde.…”

“…42 Increasing effort is being devoted towards enabling theoretical support for transient X-ray spectroscopies both in terms of accurate calculations of valenceto-core-excited state spectroscopic signals and inclusion of coupled electron-nuclear dynamics. Currently available methods for simulating TRXAS include density functional theory (DFT), 10,[43][44][45][46] restricted active space self-consistent eld without (RASSCF) 47,48 and with second-order perturbation correction (RASPT2), 46,49 algebraic-diagrammatic construction (ADC), [50][51][52] coupled cluster 13,[53][54][55] and combined DFT/ multireference conguration interaction. 56 Effects of nuclear dynamics, and in particular non-adiabatic transitions, have been treated at varying degrees of complexity and accuracy using full-dimensionality trajectory- 10,48 and Gaussian wavepacket-based 46,51,57 dynamics as well as reduced-dimensionality quantum dynamics.…”

XABOOM: An X-Ray Absorption Benchmark of Organic Molecules Based on Carbon, Nitrogen, and Oxygen 1s → π ∗ Transitions

“…The modeling of transient X-ray spectroscopy is a relatively new field, with one of the first systematic studies of transient X-ray absorption and emission spectroscopy from as late as 2015. 18 Nonetheless, the field has experienced rapid growth, encompassing applications ranging from photodissociation 19,20 and ring-opening reactions, 21,22 to excited state dynamics, 23,24 intersystem crossings, 25,26 and many more. 2,3,27,28 In order to interpret and understand these advanced measurements, an interplay between experiment and computational chemistry is required.…”

Probing Competing Relaxation Pathways in Malonaldehyde with Transient X-Ray Absorption Spectroscopy

“…42 Increasing effort is being devoted towards enabling theoretical support for transient X-ray spectroscopies both in terms of accurate calculations of valence-to-core-excited state spectroscopic signals and inclusion of coupled electron-nuclear dynamics. Currently available methods for simulating TRXAS include density functional theory (DFT), 10,[43][44][45][46] restricted active space self-consistent field without (RASSCF) 47,48 and with second-order perturbation correction (RASPT2), 46,49 algebraicdiagrammatic construction (ADC), 50-52 coupled cluster 13,[53][54][55] and combined DFT/multireference configuration interaction. 56 Effects of nuclear dynamics, and in particular non-adiabatic transitions, have been treated at varying degrees of complexity and accuracy using fulldimensionality trajectory- 10,48 and Gaussian wavepacket-based 46,51,57 dynamics as well as reduced-dimensionality quantum dynamics.…”