Abstract
We report on an experimental approach that reveals crucial details of the composition of singlet-triplet mixed eigenstates in acetylene. Intersystem crossing in this prototypical polyatomic molecule embodies the mixing of the lowest excited singlet state ( S 1 ) with 3 triplet states ( T 1 , T 2 , and T 3 ). Using high-energy (157-nm) photons from an F 2 laser to record excited-state photoelectron spectra, we have decomposed the mixed eigenstates into their S 1 , T 3 , T 2 , and T 1 constituent parts. One example of the interpretive power that ensues from the selective sensitivity of the experiment to the individual electronic state characters is the discovery and examination of destructive interference between two doorway-mediated intersystem crossing pathways. This observation of an interference effect in nonradiative decay opens up possibilities for rational coherent control over molecular excited state dynamics.
Keywords
Intersystem crossingExcited stateSinglet fissionSinglet statePolyatomic ionAtomic physicsAcetyleneTriplet statePhysicsChemistryInternal conversionMoleculePhotochemistrySpectral lineMolecular physicsQuantum mechanics
Affiliated Institutions
Related Publications
Spin−Orbit Coupling and Intersystem Crossing in Conjugated Polymers: A Configuration Interaction Description
Configuration−interaction calculations are performed to describe the singlet and triplet excited states of oligothiophene and oligo(phenylene ethynylene) conjugated chains. Inte...
Optimization of high-sensitivity fluorescence detection
We present general expressions for the number of photons emitted by a fluorescent chromophore as a function of the intensity and the duration of illumination. The aim is to find...
Ultrafast Excited-State Dynamics of Rhenium(I) Photosensitizers [Re(Cl)(CO)_(3)(N,N)] and [Re(imidazole)(CO)_(3)(N,N)]^+: Diimine Effects
Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)_(3)(N,N)]^n (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were invest...
Submillisecond detection of single rhodamine molecules in water
Using a modified confocal fluorescence microscope and a CW argon laser, we have measured fluorescence bursts from diffusing single Rh6G molecules that clearly exceed the backgro...
Efficient up-conversion of triplet excitons into a singlet state and its application for organic light emitting diodes
A material possessing a very small energy gap between its singlet and triplet excited states, ΔE1−3, which allows efficient up-conversion of triplet excitons into a singlet stat...
Publication Info
- Year
- 2009
- Type
- article
- Volume
- 106
- Issue
- 8
- Pages
- 2510-2514
- Citations
- 8
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
8
OpenAlex
Cite This
Mattijs de Groot,
Robert W. Field,
Wybren Jan Buma
(2009).
Interference in acetylene intersystem crossing acts as the molecular analog of Young's double-slit experiment.
Proceedings of the National Academy of Sciences
, 106
(8)
, 2510-2514.
https://doi.org/10.1073/pnas.0809159106
Identifiers
- DOI
- 10.1073/pnas.0809159106