Ultrafast intersystem crossing in xanthone from wavepacket dynamics simulations

التفاصيل البيبلوغرافية
العنوان: Ultrafast intersystem crossing in xanthone from wavepacket dynamics simulations
المؤلفون: Marc Alías Rodríguez, Miquel Huix-Rotllant, Coen de Graaf
بيانات النشر: Cambridge University Press (CUP), 2021.
سنة النشر: 2021
مصطلحات موضوعية: Physics, chemistry.chemical_compound, Intersystem crossing, chemistry, Wave packet, Excited state, Picosecond, Xanthone, Quantum yield, Singlet state, Internal conversion (chemistry), Molecular physics
الوصف: Most aromatic ketones containing first-row elements undergo unexpectedly fast intersystem crossing in few tens of picosecond and a quantum yield close to unity. Among them, xanthone (9H-xanthen-9-one) possesses one of the fastest intersystem crossing rates of ~1.5 ps, despite containing only first-row elements. The exact mechanism of this unusually fast singlet-triplet transition is still under debate. Here, we perform a complete wavepacket dynamics simulation of the internal conversion and intersystem crossing reactions of xanthone in the gas phase. We show that xanthone follows El-Sayed's rule for intersystem crossing. From the second singlet excited state, the mechanism is sequential: (i) an internal conversion between singlets 1pipi*-1npi* (~0.14 fs), (ii) an intersystem crossing 1npi*-3pipi* (~1.8 ps), and (iii) an internal conversion between triplets 3pipi*-3npi* (~27 ps). Each transfer finds its origin in a barrierless access to electronic state intersections. These intersections are close to minimum energy structures, allowing for an efficient radiationless transition from 1pipi* to 3npi*.
DOI: 10.33774/chemrxiv-2021-k6hqt-v2
URL الوصول: https://explore.openaire.eu/search/publication?articleId=doi_________::396671a0f21f87aad0255a3cac5fc8db
https://doi.org/10.33774/chemrxiv-2021-k6hqt-v2
Rights: OPEN
رقم الانضمام: edsair.doi...........396671a0f21f87aad0255a3cac5fc8db
قاعدة البيانات: OpenAIRE
الوصف
DOI:10.33774/chemrxiv-2021-k6hqt-v2