High-resolution coherent multidimensional spectroscopy provides an alternative to conventional methods for generating rotationally resolved electronic spectra of gas phase molecules. In addition to revealing information such as the relationships among peaks, it can provide clearly recognizable patterns for spectra that otherwise appear patternless due to rotational congestion. Despite this improvement, high-resolution coherent 2D spectroscopy can still exhibit congestion problems; expansion to the second dimension is often not sufficient to prevent overlapping of peaks from different patterns. A new 3D version of the technique that provides improved resolution and selectivity to help address cases with severe congestion was recently demonstrated. The experimental design and interpretation of data for the 3D technique are significantly more complicated than that for the 2D version. The purpose of this paper is to provide important information needed to plan, run, and interpret results from high-resolution coherent 3D spectroscopy experiments.
In the past, high-resolution spectroscopy has been limited to small, simple molecules that yield relatively uncongested spectra. Larger and more complex molecules have a higher density of peaks and are susceptible to complications (e.g., effects from conical intersections) that can obscure the patterns needed to resolve and assign peaks. Recently, high-resolution coherent two-dimensional (2D) spectroscopy has been used to resolve and sort peaks into easily identifiable patterns for molecules where pattern-recognition has been difficult. For very highly congested spectra, however, the ability to resolve peaks using coherent 2D spectroscopy is limited by the bandwidth of instrumentation. In this article, we introduce and investigate high-resolution coherent three-dimensional spectroscopy (HRC3D) as a method for dealing with heavily congested systems. The resulting patterns are unlike those in high-resolution coherent 2D spectra. Analysis of HRC3D spectra could provide a means for exploring the spectroscopy of large and complex molecules that have previously been considered too difficult to study.
Velocity-mapped imaging and theoretical calculations have been used to study the angular distribution of the products of NO predissociation following its excitation to the 11s, 10p, 11p, and 9f Rydberg levels based on the NO(+) (X (2)Σ(+)) core. The Rydberg states were reached from the NO (A (2)Σ(+), v = 0, N = 2, J = 1.5) level prepared with strong alignment by excitation with linear polarization from NO (X (2)Π, v = 0, N = 1, J = 0.5). Ion dip spectra of the Rydberg states were recorded along with velocity-mapped images at the major peaks. The results are compared to calculations based on a previous theoretical approach modified to include transitions to states of Hund's case (d) coupling. The reasonable agreement shows the predictive value of the theory. The theory has also been used to reassess and explain previous results and to understand variations in the rate of photodissociation with components of the 10p and 11p Rydberg states.
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