title: First-principles simulation of amide and aromatic side chain ultraviolet spectroscopy of a cyclic dipeptide.
abstract: By combining time-dependent density functional theory (TDDFT) and molecular dynamics (MD) simulations, we calculate the ultraviolet absorption and circular dichroism (CD) of a cyclic dipeptide, cyclo(L-Pro-D-Tyr), in the 185-300 nm region. The absorption is dominated by the phenol chromophore of tyrosine. The CD spectrum shows both phenol and amide units transitions. A crude coherent two-dimensional ultraviolet spectrum (2DUV) calculated by neglecting the two-excitation states shows a cross-peak between two transitions of the phenol in the tyrosine side chain. Additional cross-peaks between the side chain and the backbone are observed when using a chirality-induced pulse polarization configuration.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697, USA.
authors.forename: Zhenyu
authors.initials: Z
authors.lastname: Li
authors.forename: Shaul
authors.initials: S
authors.lastname: Mukamel
mesh_terms: D000577:Amides / Q000737:chemistry*; D002942:Circular Dichroism; D004151:Dipeptides / Q000737:chemistry*; D008958:Models, Molecular; D010456:Peptides, Cyclic / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet / Q000379:methods*
chemical_list: D000577:Amides; D004151:Dipeptides; D010456:Peptides, Cyclic