title: Resolving molecular vibronic structure using high-sensitivity two-dimensional electronic spectroscopy.
abstract: Coherent multidimensional optical spectroscopy is an emerging technique for resolving structure and ultrafast dynamics of molecules, proteins, semiconductors, and other materials. A current challenge is the quality of kinetics that are examined as a function of waiting time. Inspired by noise-suppression methods of transient absorption, here we incorporate shot-by-shot acquisitions and balanced detection into coherent multidimensional optical spectroscopy. We demonstrate that implementing noise-suppression methods in two-dimensional electronic spectroscopy not only improves the quality of features in individual spectra but also increases the sensitivity to ultrafast time-dependent changes in the spectral features. Measurements on cresyl violet perchlorate are consistent with the vibronic pattern predicted by theoretical models of a highly displaced harmonic oscillator. The noise-suppression methods should benefit research into coherent electronic dynamics, and they can be adapted to multidimensional spectroscopies across the infrared and ultraviolet frequency ranges.
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA.
authors.forename: Laurie A
authors.initials: LA
authors.lastname: Bizimana
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA.
authors.forename: Johanna
authors.initials: J
authors.lastname: Brazard
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA.
authors.forename: William P
authors.initials: WP
authors.lastname: Carbery
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA.
authors.forename: Tobias
authors.initials: T
authors.lastname: Gellen
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA.
authors.forename: Daniel B
authors.initials: DB
authors.lastname: Turner