Superatom state-resolved dynamics of the Au25(SC8H9)18- monolayer-protected cluster (MPC) were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The electronic ground state of the Au25(SC8H9)18- MPC is described by an eight-electron P-like superatom orbital. Hot electron relaxation (200 ± 15 fs) within the superatom D manifold of lowest-unoccupied molecular orbitals was resolved from hot hole relaxation (290 ± 20 fs) in the superatom P states by using 2DES in a partially collinear pump-probe geometry. Electronic relaxation dynamics mediated by specific superatom states were distinguished by examining the time-dependent cross-peak amplitudes for specific excitation and detection photon energy combinations. Quantification of the time-dependent amplitudes and energy positions of cross peaks in the 2.21/1.85 eV (excitation/detection) region confirmed that an apparent energetic blue shift observed for transient bleach signals results from rapid hot electron relaxation in the superatom D states. The combination of structurally precise MPCs and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices.

Superatom State-Resolved Dynamics of the Au25(SC8H9)18- Cluster from Two-Dimensional Electronic Spectroscopy

RÉHAULT, JULIEN EMIL ANDRE;ORIANA, AURELIO;CERULLO, GIULIO NICOLA;
2016-01-01

Abstract

Superatom state-resolved dynamics of the Au25(SC8H9)18- monolayer-protected cluster (MPC) were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The electronic ground state of the Au25(SC8H9)18- MPC is described by an eight-electron P-like superatom orbital. Hot electron relaxation (200 ± 15 fs) within the superatom D manifold of lowest-unoccupied molecular orbitals was resolved from hot hole relaxation (290 ± 20 fs) in the superatom P states by using 2DES in a partially collinear pump-probe geometry. Electronic relaxation dynamics mediated by specific superatom states were distinguished by examining the time-dependent cross-peak amplitudes for specific excitation and detection photon energy combinations. Quantification of the time-dependent amplitudes and energy positions of cross peaks in the 2.21/1.85 eV (excitation/detection) region confirmed that an apparent energetic blue shift observed for transient bleach signals results from rapid hot electron relaxation in the superatom D states. The combination of structurally precise MPCs and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices.
2016
Chemistry (all); Catalysis; Biochemistry; Colloid and Surface Chemistry
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11311/1015433
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 68
  • ???jsp.display-item.citation.isi??? 67
social impact