2011
DOI: 10.1021/jp2037894
|View full text |Cite
|
Sign up to set email alerts
|

Spectral Signatures of Inter-System Crossing Mediated by Energetically Distant Doorway Levels: Examples from the Acetylene S1 State

Abstract: We review recent research on the acetylene S(1) state that illustrates how mechanistic rather than phenomenological information about intersystem crossing (ISC) may be obtained directly from frequency-domain spectra. The focus is on the dynamically rich "doorway-mediated" ISC domain that lies between isolated spectroscopic spin-orbit perturbations and statistical-limit interactions between one singlet "bright state" and a quasi-continuum of triplet "dark states". New and improved experimental and data processi… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1
1

Citation Types

1
5
0

Year Published

2012
2012
2017
2017

Publication Types

Select...
5

Relationship

0
5

Authors

Journals

citations
Cited by 5 publications
(6 citation statements)
references
References 70 publications
1
5
0
Order By: Relevance
“…This picture agrees with many ab initio calculations 13,21,22 , which suggest that after intersystem crossing there would have to be a sequential energy transfer along several modes involving large molecular contortions that would make such a mechanism slow 13 . This agrees with the observed µs metastable state lifetimes of the excited acetylene upon irradiation 23,24 and a lower limit for a predissociation lifetime has been suggested of at least tens of picoseconds 25 .…”
Section: Singlet Excited State Landscapesupporting
confidence: 91%
“…This picture agrees with many ab initio calculations 13,21,22 , which suggest that after intersystem crossing there would have to be a sequential energy transfer along several modes involving large molecular contortions that would make such a mechanism slow 13 . This agrees with the observed µs metastable state lifetimes of the excited acetylene upon irradiation 23,24 and a lower limit for a predissociation lifetime has been suggested of at least tens of picoseconds 25 .…”
Section: Singlet Excited State Landscapesupporting
confidence: 91%
“…30,31 In many cases, vibrational coupling significantly influences the rate of ISC. [32][33][34][35] Temperature-dependent absorption measurements indicate electron-phonon coupling is strong for Au 25 nanoclusters, which may help to mediate an intersystem crossing event. 36 ISC is only one possible explanation that can reconcile the current data.…”
Section: Resultsmentioning
confidence: 99%
“…The collision complex of two ultracold reactants is like the highly excited molecular states that are well-studied in chemistry 316 under paradigms such as internal relaxation, 317,318 unimolecular decomposition, 319−321 transition state theory, 322 or semiclassical or chaotic dynamics. 323,324 Although the lowenergy entrance channel is undoubtedly highly quantum mechanical in its long-range collision dynamics, once it is coupled to the high-energy scale of the collision complex the conventional chemical dynamics from these familiar fields takes over.…”
Section: Perspectives For Ultracold Chemistrymentioning
confidence: 99%