Infrared multiphoton dissociation spectra of protonated p-aminobenzoic acid generated by electrospray ionization (ESI) from aqueous methanol and acetonitrile solutions were recorded in the gas phase from 2800-4000 cm(-1). The O-protonated ion is more stable than the N-protonated structure in the gas phase, whereas the opposite is true in both solutions. When CH(3)OH/H(2)O was used as the ESI solvent, only the O-protonated ion was observed. In contrast, a 70:30 mixture of the O- and N-protonated species were produced from CH(3)CN/H(2)O. These structural assignments are based on an assortment of experimental data (action spectra, photofragments, photofragmentation kinetics, and H/D exchange) and are fully supported by extensive computations. This work shows that ESI can lead to isomerization and that the ionization site may be varied by changing the solvent from which the substrate is analyzed.

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Two-dimensional infrared spectroscopy (2D-IR) was used to investigate the sensitivity of a vibrational mode to spectral diffusion on the nanometer length scale. A confined volume within a porous silica nanoparticle was used as the model system. Utilizing a novel grafting technique, silane probes were covalently secured to the pore surface for a series of templated mesoporous silica nanoparticles with variable pore sizes. 2D-IR measurements determined that isopropanol exhibited two dominant time scales of ultrafast motions within the pores with time scales of a few picoseconds and tens of picoseconds. The unique perspective of the probe on a surface revealed that the vibrational dynamics of the reporting mode were perturbed by molecules up to ∼5 nm away. The data were modeled well by a 1/d 2 distance dependence for the coupling of solvent dynamics to frequency fluctuations and a logistic radial distribution of fast and slow dynamic populations.

Fourier transform infrared and two-dimensional IR (2D-IR) spectroscopies were applied to two different silanes in three different solvents. The selected solutes exhibit different degrees of vibrational solvatochromism for the Si-H vibration. Density functional theory calculations confirm that this difference in sensitivity is the result of higher mode polarization with more electron withdrawing ligands. This mode sensitivity also affects the extent of spectral diffusion experienced by the silane vibration, offering a potential route to simultaneously optimize the sensitivity of vibrational probes in both steady-state and time-resolved measurements. Frequency-frequency correlation functions obtained by 2D-IR show that both solutes experience dynamics on similar time scales and are consistent with a picture in which weakly interacting solvents produce faster, more homogeneous fluctuations. Molecular dynamics simulations confirm that the frequency-frequency correlation function obtained by 2D-IR is sensitive to the presence of hydrogen bonding dynamics in the surrounding solvation shell.

Two-dimensional infrared (2D-IR) spectroscopy was performed on Vaska's complex (VC) and its oxygen adduct (V C-O2) in binary solvent mixtures of chloroform or benzyl alcohol in d6-benzene. The second order rate constants for oxygenation were also measured in these solvent mixtures. The rate constant in chloroform mixtures is linear with mole fraction within the error of the measurements but changes nonlinearly in benzyl alcohol mixtures, displaying a preference for the alcohol over benzene. The rate constants were compared with FTIR spectra of the carbonyl ligand and the frequency-frequency correlation function of this mode determined by 2D-IR. The line shape broadening mechanisms of the linear spectra of the CO bound to VC and V C-O2 are similar to those previously reported for V C-I2. There is a particularly strong correlation between rate constants and homogeneous linewidths of the carbonyl vibration on the V C-O2 product state. Concurrently, the FTIR spectra and spectral diffusion observed by 2D-IR corroborate an increase in solvent heterogeneity around the product. We interpret these results in the context of the potential role of solvent dynamics in facilitating chemical reactivity.