title: Ab initio excited-state dynamics of the photoactive yellow protein chromophore.
abstract: The photoisomerization mechanism of the neutral form of the photoactive yellow protein (PYP) chromophore is investigated using ab initio quantum chemistry and first-principles nonadiabatic molecular dynamics (ab initio multiple spawning or AIMS). We identify the nature of the two lowest-lying excited states, characterize the short-time behavior of molecules excited directly to S2, and explain the origin of the experimentally observed wavelength-dependent photoisomerization quantum yield.
authors.affiliation: Department of Chemistry and The Beckman Institute, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Chaehyuk
authors.initials: C
authors.lastname: Ko
authors.forename: Benjamin
authors.initials: B
authors.lastname: Levine
authors.forename: A
authors.initials: A
authors.lastname: Toniolo
authors.forename: Leslie
authors.initials: L
authors.lastname: Manohar
authors.forename: Seth
authors.initials: S
authors.lastname: Olsen
authors.forename: Hans-Joachim
authors.initials: HJ
authors.lastname: Werner
authors.forename: Todd J
authors.initials: TJ
authors.lastname: Martínez
mesh_terms: D001426:Bacterial Proteins / Q000737:chemistry*; D003373:Coumaric Acids / Q000737:chemistry*; D007536:Isomerism; D010777:Photochemistry; D020283:Photoreceptors, Microbial / Q000737:chemistry*; D011422:Propionates; D011789:Quantum Theory; D013050:Spectrometry, Fluorescence
chemical_list: D001426:Bacterial Proteins; D003373:Coumaric Acids; D020283:Photoreceptors, Microbial; D011422:Propionates; C050162:photoactive yellow protein, Bacteria; C495469:p-coumaric acid