Abstract

This paper introduces a new approach to analysis of spectra called asynchronous orthogonal sample design (AOSD). Specifically designed concentration series are selected according to mathematical analysis of orthogonal vectors. Based on the AOSD approach, the interfering portion of the spectra arising strictly from the concentration effect can be completely removed from the asynchronous spectra. Thus, two-dimensional (2D) asynchronous spectra can be used as an effective tool to characterize intermolecular interactions that lead to apparent deviations from the Beer–Lambert law, even if the characteristic peaks of two compounds are substantially overlapped. A model solution with two solutes is used to investigate the behavior of the 2D asynchronous spectra under different extents of overlap of the characteristic peaks. Simulation results demonstrate that the resulting spectral patterns can reflect subtle spectral variations in bandwidths, peak positions, and absorptivities brought about by intermolecular interaction, which are barely visualized in the conventional one-dimensional (1D) spectra. Intermolecular interactions between butanone and dimethyl formamide (DMF) in CCl₄ solutions were investigated using the proposed AOSD approach to prove the applicability of the AOSD method in real chemical systems.

Fluorescence spectral correlation spectroscopy (FSCS) for probes with highly overlapping emission spectra

Aleš Benda, Peter Kapusta, Martin Hof, and Katharina Gaus
Opt. Express 22(3) 2973-2988 (2014)

Polarization shaping in the mid-IR and polarization-based balanced heterodyne detection with application to 2D IR spectroscopy

Chris T. Middleton, David B. Strasfeld, and Martin T. Zanni
Opt. Express 17(17) 14526-14533 (2009)

Ultrafast 2D IR microscopy

Carlos R. Baiz, Denise Schach, and Andrei Tokmakoff
Opt. Express 22(15) 18724-18735 (2014)

High-resolution infrared spectroscopy of formamide and deuterated formamide in a molecular beam

Christopher L. Brummel, Meihua Shen, Kevin B. Hewett, and Laura A. Philips
J. Opt. Soc. Am. B 11(1) 176-183 (1994)

Experimental implementations of 2D IR spectroscopy through a horizontal pulse shaper design and a focal plane array detector

Ayanjeet Ghosh, Arnaldo L. Serrano, Tracey A. Oudenhoven, Joshua S. Ostrander, Elliot C. Eklund, Alexander F. Blair, and Martin T. Zanni
Opt. Lett. 41(3) 524-527 (2016)