jz0c00482_si_001.pdf (231.85 kB)
Ultrafast Intersystem Crossing in Isolated Ag29(BDT)123– Probed by Time-Resolved Pump–Probe Photoelectron Spectroscopy
journal contribution
posted on 2020-03-23, 12:48 authored by Aron P. Veenstra, Laurenz Monzel, Ananya Baksi, Joseph Czekner, Sergei Lebedkin, Erik K. Schneider, Thalappil Pradeep, Andreas-Neil Unterreiner, Manfred M. KappesThe photophysics
of the isolated trianion Ag29(BDT)123– (BDT = benzenedithiolate), a ligand-protected
cluster comprising BDT-based ligands, terminating a shell of silver
thiolates and a core of silver atoms, was studied in the gas phase
by femtosecond time-resolved, pump–probe photoelectron spectroscopy.
UV excitation at 490 nm populates one or more singlet excited states
with significant charge transfer (CT) character in which electron
density is shifted from shell to core. These CT states relax on an
average time scale of several hundred femtoseconds by charge recombination
to yield either the vibrationally excited singlet ground state (internal
conversion) or a long-lived triplet (intersystem crossing). Our study
is the first ultrafast spectroscopic probe of a ligand-protected coinage
metal cluster in isolation. In the future, it will be interesting
to study how cluster size, overall charge state, or heteroatom doping
can be used to tune the corresponding relaxation dynamics in the absence
of solvent.
History
Usage metrics
Categories
Keywords
ligand-protected clusterheteroatom dopingelectron densityIsolated Ag 29charge transferfemtosecond time-resolvedtime scalecharge recombinationsinglet ground stateultrafast spectroscopic probetrianion Ag 29coresilver thiolatesrelaxation dynamicsgas phasecluster sizesilver atomsligand-protected coinage metal clusterBDT-based ligands490 nm populatescharge stateCT statesUltrafast IntersystemUV excitation
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC