Search

Two-dimensional infrared (2DIR) spectroscopy has become an established method for generating vibrational spectra in condensed phase samples composed of mixtures that yield heavily congested infrared and Raman spectra. These condensed phase 2DIR spectrometers can provide very high temporal resolution (<1 ps), but the spectral resolution is generally insufficient for resolving rotational peaks in gas phase spectra. Conventional (1D) rovibrational spectra of gas phase molecules are often plagued by severe spectral congestion, even when the sample is not a mixture. Spectral congestion can obscure the patterns in rovibrational spectra that are needed to assign peaks in the spectra. A method for generating high resolution 2DIR spectra of gas phase molecules has now been developed and tested using methane as the sample. The 2D rovibrational patterns that are recorded resemble an asterisk with a center position that provides the frequencies of both of the two coupled vibrational levels. The ability to generate easily recognizable 2D rovibrational patterns, regardless of temperature, should make the technique useful for a wide range of applications that are otherwise difficult or impossible when using conventional 1D rovibrational spectroscopy.

High resolution coherent multidimensional spectroscopy has the ability to reduce congestion and automatically sort peaks by species and quantum numbers, even for simple mixtures and molecules that are extensively perturbed. The two-dimensional version is relatively simple to carry out, and the results are easy to interpret, but its ability to deal with severe spectral congestion is limited. Three-dimensional spectroscopy is considerably more complicated and time-consuming than two-dimensional spectroscopy, but it provides the spectral resolution needed for more challenging systems. This paper describes how to design high resolution coherent 3D spectroscopy experiments so that a small number of strategically positioned 2D scans may be used instead of recording all the data required for a 3D plot. This faster and simpler approach uses new pattern recognition methods to interpret the results. Key factors that affect the resulting patterns include the scanning strategy and the four wave mixing process. Optimum four wave mixing (FWM) processes and scanning strategies have been identified, and methods for identifying the FWM process from the observed patterns have been developed. Experiments based on nonparametric FWM processes provide significant pattern recognition and efficiency advantages over those based on parametric processes. Alternative scanning strategies that use synchronous scanning and asynchronous scanning to create new kinds of patterns have also been identified. Rotating the resulting patterns in 3D space leads to an insight into similarities in the patterns produced by different FWM processes.

Expansion from coherent 2D spectroscopy to coherent 3D spectroscopy can provide significant advantages when studying molecules that have heavily perturbed energy levels. This paper illustrates such advantages by demonstrating how high resolution coherent 3D (HRC3D) spectroscopy can be used to study a portion of the visible spectrum of nitrogen dioxide. High resolution coherent 2D spectra usually contain rotational and vibrational patterns that are easy to analyze, but severe congestion and complexity preclude its effective use for many parts of the NO2 spectrum. HRC3D spectroscopy appears to be much more effective; multidimensional rotational and vibrational patterns produced by this new technique are easy to identify even in the presence of strong perturbations. A method for assigning peaks, which is based upon analyzing the resulting multidimensional patterns, has been developed. The higher level of multidimensionality is useful for reducing uncertainty in peak assignments, improving spectral resolution, providing simultaneous information on multiple levels and states, and predicting, verifying, and categorizing peaks.