Femtosecond Spectroscopy of Heterogeneous Electron Transfer:  Extraction of Excited-State Population Dynamics from Pump−Probe Signals

• Published in: The journal of physical chemistry. B Vol. 107; no. 2; pp. 607 - 611
• Main Authors: Ramakrishna, S, Willig, F, May, V, Knorr, A
• Format: Journal Article
• Language: English
• Published: American Chemical Society 16.01.2003
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp027104b

Numerical calculations of pump−probe signals corresponding to excited-state absorption of the molecular state are presented. The molecular excited-state decays due to ultrafast electron injection into a continuum of electronic states (semiconductor levels) and the model calculations take into account the consequent molecular reorganization. A time-dependent Schrödinger wave equation approach is utilized to model the pump−probe dynamics. The continuum of semiconductor states, namely, its conduction-band levels, is described by an expansion in terms of orthogonal polynomials. It is shown that excited-state dynamics, including information on the modulation of population transfer due to vibrational coherences, can be unambiguously deduced from the pump−probe signals.