Assignment of caroteneS* state features to the vibrationally hot ground electronic state

Abstract

The so-called S* state has been suggested to play an important role in the photophysics of β-carotene and other carotenoids in solution and photosynthetic light-harvesting complexes, yet its origin has remained elusive. The present experiments employing temperature-dependent steady-state absorption spectroscopy and ultrafast pump-supercontinuum probe (PSCP) transient absorption measurements of β-carotene in solution demonstrate that the spectral features of S* are due to vibrationally excited molecules in the ground electronic state S₀. Characteristic spectral signatures, such as a highly structured bleach below 500 nm and absorption in the range 500–660 nm result from the superposition of hot S₀ absorption (“S₀*”) on top of the ground-state bleach of room-temperature molecules. Appearance and disappearance of the S₀* molecules can be completely described by a global kinetic analysis employing time-dependent species-associated spectra without the need to invoke the population of an intermediate electronically excited state.