title: Two-Dimensional Electronic Spectroscopy of Benzene, Phenol, and Their Dimer: An Efficient First-Principles Simulation Protocol.
abstract: First-principles simulations of two-dimensional electronic spectroscopy in the ultraviolet region (2DUV) require computationally demanding multiconfigurational approaches that can resolve doubly excited and charge transfer states, the spectroscopic fingerprints of coupled UV-active chromophores. Here, we propose an efficient approach to reduce the computational cost of accurate simulations of 2DUV spectra of benzene, phenol, and their dimer (i.e., the minimal models for studying electronic coupling of UV-chromophores in proteins). We first establish the multiconfigurational recipe with the highest accuracy by comparison with experimental data, providing reference gas-phase transition energies and dipole moments that can be used to construct exciton Hamiltonians involving high-lying excited states. We show that by reducing the active spaces and the number of configuration state functions within restricted active space schemes, the computational cost can be significantly decreased without loss of accuracy in predicting 2DUV spectra. The proposed recipe has been successfully tested on a realistic model proteic system in water. Accounting for line broadening due to thermal and solvent-induced fluctuations allows for direct comparison with experiments.
authors.affiliation: Dipartimento di Chimica "G. Ciamician", Università di Bologna , Via F. Selmi 2, 40126 Bologna, Italy.
authors.forename: Artur
authors.initials: A
authors.lastname: Nenov
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697-2025, United States.
authors.forename: Shaul
authors.initials: S
authors.lastname: Mukamel
authors.affiliation: Dipartimento di Chimica "G. Ciamician", Università di Bologna , Via F. Selmi 2, 40126 Bologna, Italy.|Université de Lyon , CNRS, Laboratoire de Chimie, École Normale Supérieure de Lyon, UMR 5182, 46 Allée d'Italie, 69364 Lyon, Cedex 07, France.
authors.forename: Marco
authors.initials: M
authors.lastname: Garavelli
authors.affiliation: Université de Lyon , CNRS, Laboratoire de Chimie, École Normale Supérieure de Lyon, UMR 5182, 46 Allée d'Italie, 69364 Lyon, Cedex 07, France.
authors.forename: Ivan
authors.initials: I
authors.lastname: Rivalta
mesh_terms: D001554:Benzene / Q000737:chemistry*; D003198:Computer Simulation; D019281:Dimerization; D005740:Gases / Q000737:chemistry; D008958:Models, Molecular; D009842:Oligopeptides / Q000737:chemistry / Q000378:metabolism; D019800:Phenol / Q000737:chemistry*; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet
chemical_list: D005740:Gases; D009842:Oligopeptides; D019800:Phenol; D001554:Benzene