Indirect Intersystem Crossing (S1 → T3/T2 → T1) Promoted by the Jahn–Teller Effect in Cycloparaphenylenes

Vibronic-coupling effects play a key role for excited-state charge- and energy-transfer processes in organic molecular systems. Here, we demonstrate how the Jahn–Teller effect in triplet excited states of highly symmetric cycloparaphenylenes triggers an indirect intersystem crossing deactivation pat...

Full description

Saved in:
Bibliographic Details
Published in:Journal of chemical theory and computation 2017-10, Vol.13 (10), p.4944-4949
Main Authors: Reddy, Vennapusa Sivaranjana, Irle, S
Format: Article
Language:English
Subjects:
Charge transfer
Coupling (molecular)
Deactivation
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Internal conversion
Intersystem crossing
Molecular chains
optical spectrum
Organic chemistry
relaxation dynamics
vibronic coupling
wavepacket propagation
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Vibronic-coupling effects play a key role for excited-state charge- and energy-transfer processes in organic molecular systems. Here, we demonstrate how the Jahn–Teller effect in triplet excited states of highly symmetric cycloparaphenylenes triggers an indirect intersystem crossing deactivation pathway. Strong Jahn–Teller distortion in the doubly degenerate second excited triplet state (T2) brings the molecular system energetically close to the lowest triplet state (T1), thereby opening the possibility for an extremely rapid internal conversion. Quantum dynamics simulations reveal an initial T2 → T1 population decay within 50 fs. Experimental observation of size-dependent intersystem crossing rates of cycloparaphenylenes is explained based on the proposed S1 → T3/T2 → T1 mechanism.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.7b00166