Peter C. Chen

Two-Dimensional Coherent Double Resonance Electronic Spectroscopy

A new form of coherent 2D spectroscopy involving a pair of electronic resonances appears to provide several advantages over more established techniques. It can resolve congested peaks and sort them by vibrational quantum number, rotational quantum number, and isotopomer. The high degree of symmetry in the resulting spectra facilitates the ability to assign the quantum numbers and isotopomer for each peak. Quantitative results are demonstrated using an isotopomeric mixture of bromine.

High Resolution Coherent 2D Spectroscopy

The purpose of this article is to describe recent progress on the use of coherent two-dimensional spectroscopy for investigating the electronic spectroscopy of gas phase molecules. Unlike conventional high resolution spectra where peaks are distributed along a single axis, high resolution coherent 2D spectra reveal informative patterns along two orthogonal frequency domains. The technique can successfully produce these patterns in situations where one-dimensional spectra appear patternless due to complexity and congestion. Molecular spectra that are difficult to analyze because of strongly perturbing effects (e.g., conical intersections) may be studied using this new technique. Several innovations, such as the ability to graphically separate rotational and vibrational information by clustering peaks and the ability to use multiple clusters to overcome spectral congestion help provide high resolution coherent 2D spectroscopy with the ability to analyze spectra that have previously resisted analysis.

MULTIPLEX COHERENT ANTI-STOKES RAMAN SPECTROSCOPY BY USE OF A NEARLY DEGENERATE BROADBAND OPTICAL PARAMETRIC OSCILLATOR

Optical parametric oscillators (OPOs) provide low-maintenance solid-state alternatives to dye lasers. We present results from use of a nearly degenerate broadband OPO for multiplex coherent anti-Stokes Raman spectroscopy. The system described is capable of generating spectra that cover a range of approximately 1000 cm(-1).

High-resolution coherent three-dimensional spectroscopy of Br2.

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.

Analysis of polyatomic molecules using high resolution coherent two-dimensional spectroscopy: Application to nitrogen dioxide

The peak-sorting capabilities of high resolution coherent two-dimensional (2D) spectroscopy provide a new way of dealing with severe rotational congestion. This paper describes the application of this technique to the polyatomic molecule, NO(2). NO(2) is a primary component of photochemical smog and has a notoriously complex and congested spectrum that extends from the infrared to the ultraviolet regions. This spectrum is infamous for having an unusually high density of peaks and very few regular patterns. However, the coherent 2D spectrum of NO(2) shows a network consisting of numerous X-shaped patterns that mark the locations of vibronic origins. This paper describes how peak sorting leads to the formation of such patterns and how peak coupling can be used to conduct a rotational analysis of congested areas in the visible spectrum of NO(2).

Rejection of Background Light Using Single-Wavelength Detection in Nonlinear Raman Spectroscopy

A new method for single-wavelength detection (SWD) spectroscopy has been developed with the use of synchronous scanning of an optical parametric oscillator (OPO). With the combination of SWD with spatial and temporal discrimination, a high level of background light rejection is achieved. Results show sufficient ambient room light rejection for obtaining complete gas-phase nonlinear Raman spectra with no detectable signs of interference.

High resolution coherent three dimensional spectroscopy of NO2

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.

Spectral diffusion within the porous silicon emission wavelength range on the nanosecond to millisecond time scale

The emission spectrum from porous silicon (PS) at room temperature was recorded after different delay times ranging from 30 ns to 2.0 ms after pulsed laser excitation by using a gated charge-coupled device camera. In agreement with previous studies, the photoluminescence of porous silicon was found to redshift with delay time in the ns to 100 μs time scale. However, a study of the normalized band shape of the redshifted emission reveals that the emission spectrum retains its band shape rather than giving a distorted band shape that increases in intensity on the longer wavelength side. This behavior suggests that the redshift in the emission spectrum of porous silicon is a result of spectral diffusion resulting from energy transfer among emitters within the inhomogeneously broadened absorption spectrum. Furthermore, on the longer time scale (0.8–2 ms), the much weaker, long wavelength emission spectrum is found to blueshift as the delay time is increased. Two peaks were resolved in the photoluminescence sp...

Rotational and vibrational pattern interpretation for high-resolution coherent 3D spectroscopy.

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.

High-Speed Gas Chromatography—Multiplex Coherent Raman Analysis of BTEX

Gas chromatography–multiplex coherent Raman (GC-MCR) is a new tandem technique that can be used for the high-speed analysis of volatile mixtures. BTEX serves as a useful and challenging test sample because of the similarity in boiling point and spectroscopic properties of its constituents. The ability to spectroscopically resolve isomers (e.g., m-xylene and p-xylene) allows GC-MCR to sacrifice chromatographic resolution for speed. The result is the analysis of BTEX in less than 5 min, which is relatively fast compared with other tandem GC techniques.