Generation and Implementation of Continuum Infrared Pulses for Broadband Detection in 2D IR Spectroscopy.

In recent years, new methods of generating continuum mid-infrared pulses through filamentation in gases have been developed for ultrafast time-resolved infrared vibrational spectroscopy. The generated infrared pulses can have thousands of wavenumbers of bandwidth, spanning the entire mid-IR region while retaining pulse length below 100 fs. This technology has had a significant impact on problems involving ultrafast structural dynamics in congested spectra with broad features, such as those found in aqueous solutions and molecules with strong intermolecular interactions.

Molecular Tuning of Reactivity of Zeolite Protons in HZSM-5.

In acidic HZSM-5 zeolite, the reactivity of a methanol molecule interacting with the zeolite proton is amenable to modification via coadsorbing a stochiometric amount of an electron density donor to form the [()(CHOH)(HZ)] complex. The rate of the methanol in this complex undergoing dehydration to dimethyl ether was determined for a series of with proton affinity (PA) ranging from 659 kJ mol for CF to 825 kJ mol for CHO and was found to follow the expression: Ln(Rate) - Ln(Rate) = β(PA - PA), where = N is the reference and β and γ are constants. This trend is probably due to the increased stability of the solvated proton in the [()(CHOH)(HZ)] complex with increasing PA.

Strong H-bonding from Zeolite Bro̷nsted Acid Site to Water: Origin of the Broad IR Doublet.

Hydrogen bonding between water molecules and zeolite Bro̷nsted acid sites (BAS) has received much attention due to the significant influence of water on the adsorption and catalytic properties of these widely used porous materials. When a single water molecule is adsorbed at the BAS, the zeolite O-H stretch vibration decreases in frequency and splits into two extraordinarily broad bands peaked near 2500 and 2900 cm in the infrared (IR) spectrum. This broad doublet feature is the predominant IR signature used to identify and interpret water-BAS H-bonding at low hydration levels, but the origin of the band splitting is not well understood.

Amplification of mid-IR continuum for broadband 2D IR spectroscopy.

We report the generation and characterization of microjoule level, broad bandwidth femtosecond pulses in the mid-infrared (MIR) using optical parametric amplification of continuum MIR seed pulses in GaSe. The signal (3 μm) and idler (6 μm) pulses have energies of 6 μJ and 3 μJ with bandwidths of ∼950 cm and 650 cm FWHM and pulse lengths of 34 fs and 80 fs. Broadband 2D IR spectra of O-H and N-H transitions are acquired with the signal beam demonstrating the capabilities of this source for cross peak and line shape measurements.

Advanced Materials for Energy-Water Systems: The Central Role of Water/Solid Interfaces in Adsorption, Reactivity, and Transport.

The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the water-and often the water molecules themselves-to detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena.

Structural Characterization of Protonated Water Clusters Confined in HZSM-5 Zeolites.

A molecular description of the structure and behavior of water confined in aluminosilicate zeolite pores is a crucial component for understanding zeolite acid chemistry under hydrous conditions. In this study, we use a combination of ultrafast two-dimensional infrared (2D IR) spectroscopy and molecular dynamics (AIMD) to study HO confined in the pores of highly hydrated zeolite HZSM-5 (∼13 and ∼6 equivalents of HO per Al atom). The 2D IR spectrum reveals correlations between the vibrations of both terminal and H-bonded O-H groups and the continuum absorption of the excess proton.

Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations.

The aqueous proton is a common and long-studied species in chemistry, yet there is currently intense interest devoted to understanding its hydration structure and transport dynamics. Typically described in terms of two limiting structures observed in gas-phase clusters, the Zundel HO and Eigen HO ions, the aqueous structure is less clear due to the heterogeneity of hydrogen bonding environments and room-temperature structural fluctuations in water. The linear infrared (IR) spectrum, which reports on structural configurations, is challenging to interpret because it appears as a continuum of absorption, and the underlying vibrational modes are strongly anharmonically coupled to each other.

Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects.

Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states.

Gastric distension.

A woman, 82 years of age, presented to the emergency department with an 8 day history of worsening generalised abdominal pain, nonfaecal emesis and abdominal distension associated with a background history of 20 kg weight loss over the past few months.

Matched comparison of GP and consultant rating of electronic discharge summaries.

Queensland Health is implementing a state-wide system to electronically generate and distribute discharge summaries. Previously, general practitioners (GPs) have indicated that the quality of the discharge summary does not support clinical handover. While the electronic system will address some issues (e.