Ultrafast Quantum Interference in the Charge Migration of Tryptophan

J Phys Chem Lett. 2020 Feb 6;11(3):891-899. doi: 10.1021/acs.jpclett.9b03517. Epub 2020 Jan 22.

Abstract

Extreme-ultraviolet-induced charge migration in biorelevant molecules is a fundamental step in the complex path leading to photodamage. In this work we propose a simple interpretation of the charge migration recently observed in an attosecond pump-probe experiment on the amino acid tryptophan. We find that the decay of the prominent low-frequency spectral structure with increasing pump-probe delay is due to a quantum beating between two geometrically distinct, almost degenerate charge oscillations. Quantum beating is ubiquitous in these systems, and at least on the few-to-tens of femtosecond time scales, it may dominate over decoherence the line intensities of time-resolved spectra. We also address the experimentally observed phase shift in the charge oscillations of two different amino acids, tryptophan and phenylalanine. Our results indicate that a beyond mean-field treatment of the electron dynamics is necessary to reproduce the correct behavior.

MeSH terms

  • Density Functional Theory*
  • Phenylalanine / chemistry
  • Tryptophan / chemistry*

Substances

  • Phenylalanine
  • Tryptophan