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The coherent anti-Stokes Raman scattering (CARS) and photoacoustic Raman spectroscopy (PARS) spectra of gaseous CHF2Cl and CH3CF2Cl in the 3000 cm-1 region were investigated. Several vibrational bands were observed to be related to C-H stretch fundamentals of CHF2Cl isotopomers, and to CH3 stretches and the first overtone of CH3 deformation of CH3CF2Cl. The simultaneous detection of CARS/PARS signals aided the assignment of the isotopomer bands. Both methods were found to be appropriate for detection of these compounds and can be applied in chemical dynamics studies.

Noncovalent interactions and their careful variation can be crucial in understanding molecular structures, conformational topographies, and properties. Here, we examine the fluorination impact on the structure and conformational behavior of 2-(2-fluorophenyl)ethyl alcohol (2-FPEAL) by monitoring the first individual ionization-loss-stimulated Raman spectra of the jet-cooled molecule. The comparison of two different broad-range spectra and predicted equivalents discloses two distinct structures. One possesses a folded side chain ( gauche ) and the other an extended chain ( anti ) with the terminal hydrogen atom pointing opposite or toward the fluorine side, indicating the improper previous tentative assignment of the latter. These conformers resemble and differ from the nonfluorinated analogue structures. Theoretical analyses reveal interconversion pathways of 2-FPEAL conformers during expansion and the delicate balance between attractive (C-H···F and O-H···π) and repulsive interactions. These findings show the achievements of our integrated approach, suggesting its potential for overcoming future structural challenges.

We report a new spectroscopic detection scheme for molecular oxygen that achieves roughly two orders of magnitude higher sensitivity for fully rotationally resolved spectra than the current state of the art. Two-color (2 + 1') resonance-enhanced multiphoton ionization (REMPI) via the 3 d Rydberg complex yields state-selective spectra with signal comparable to the intense but diffuse C 3 s σ 3 Π g ← X 3 Σ g - (2 + 1) REMPI bands without significant saturation or broadening. The resulting increase in sensitivity permitted observation of the very weak 3 d π 1 Δ 2 ← X 3 Σ g - transitions and is independent of the intermediate state. This advance in ionization efficiency and quantum state-selective sensitivity for O 2 promises to aid physical and chemical studies across a wide variety of fields.

Even apparently simple, obtaining and analyzing observations on molecules and clusters and unambiguously assigning their structures is challenging. We report here the first ionization-loss Raman spectra compared to quantum chemical predictions for establishing the structural preferences of hydrates of the neurotransmitters hydroxy analogue, 2-phenylethyl alcohol (PEAL). The spectra encode two monohydrates and two previously unnoticed dihydrates, consequences of water insertion and sidewise attachment to the O-H group of gauche PEALs, in PEAL-H 2 O and PEAL-(H 2 O) 2 , or the higher-energy gauche - trans PEAL in the latter. The electronic structures retain the stable PEAL or flip its O-H to convert the gauche - trans PEAL conformer to the global minimum-energy dihydrate. We disclose conventional and bifurcated hydrogen bonds and electron steric repulsions by noncovalent interaction analysis and correlations between the experimental O-H stretching vibrational frequencies and the O-H and H···X bond lengths and electron densities, pointing to implications on hydrate forms and our approach virtue.

The highly successful velocity map imaging (VMI) technique plays a central role in revealing light-matter interactions. Here we demonstrate the related but distinct kinetic energy-broadened spatial map imaging (KESMI) option for recovering KE and angular recoil information on photophysical processes using a VMI system operating in different out-of-focus modes. The characteristic single or double stripes and related steps in the vertical intensity profiles of KESMIs of photoelectrons (PEs) from Ar ionization allow breakthrough developments of a potent global model that enables an understanding and analysis of these patterns. These signatures reflect the relationship between the observed features and predicted convolved discrete KEs and angular distributions. The derivation of the velocity distribution of the PEs ensuing from the ionization of a single H 2 O quantum state based on the measured and simulated KESMI provides another rigorous test demonstrating and realizing the feasibility of this new approach, which holds future promise on its own or combined with VMI.

Fluorine-containing medicinal compounds frequently allow modulation of physical-chemical properties. Here, we address the effect of fluorine, near the ethylamino side chain, on conformational flexibility and noncovalent interactions (NCIs) of the selected jet-cooled monohydrated cluster of 2-(2-fluoro-phenyl)-ethylamine (2-FPEA) by mass-selected resonance-enhanced two-photon ionization and ionization-loss stimulated Raman spectroscopies. Our results show that Raman spectral signatures of the 2-FPEA-H 2 O cluster match the scaled harmonic vibrational Raman frequencies, resulting from density functional theory calculations of the most stable 2-FPEA gauche conformer hydrogen-bonded (HB) to water, confirming the three-dimensional cluster structure. This predicted electronic structure, together with NCI analysis, allows visualization and assessment of the attractive and repulsive interactions. The comparison of the NCIs and revealed red (O-H and N-H stretches) and blue shifts (C-H stretches and CH 2 out-of-plane bends) of the cluster to other class members confirm O-H···N, N-H···π, C-H···O, and C-H···F HB formation and their contribution to structure stabilization, uncovering the potential of the approach.

The structural and dynamical characteristics of isolated molecules are essential, yet obtaining this information is difficult. We demonstrate laser-desorption jet-cooling/ionization-loss stimulated Raman spectroscopy to obtain Raman spectral signatures of nonvolatile molecules in the gas phase. The vibrational features of a test substance, the most abundant conformer of tryptamine, are compared and found to match those resulting from the scaled harmonic Raman spectrum obtained by density functional theory calculations. The vibrational signatures serve to identify the most prominent gauche conformer and evaluate its predicted electronic structure. These findings, together with noncovalent interaction (NCI) analysis, provide new insights into electron densities and reduced density gradients, assessing the hydrogen bonds (N-H···π and C-H···H-C) and interplay between attractive and repulsive NCIs affecting the structure. This approach accesses vibrational signatures of isolated nonvolatile molecules by tabletop lasers at uniform resolution and in a broad frequency range, promising great benefit to future studies.

The room-temperature photoacoustic Raman and jet-cooled H action spectra, measured in the region of the fundamental CD3 stretches and the almost isoenergetic overtones or combinations of CD3 deformations in the methylamine-d3 (CD3NH2) isotopologue, show different relative intensities of the vibrational bands. The observed difference and the vibrational assignment point to favored ultraviolet excitation due to larger Franck-Condon (FC) factors from the deformation modes, leading to more effective N-H bond cleavage in CD3NH2 predissociation. The comparable measured two-color reduced-Doppler ion images and total kinetic energy distributions resulting from the predissociation of molecules promoted from vibrationally excited and vibrationless ground states confirmed that the FC factors and not the ensuing dynamics are the main reason for the mode specificity in this molecule.

Nonadiabatic processes, dominated by dynamic passage of reactive fluxes through conical intersections (CIs), are considered to be appealing means for manipulating reaction paths, particularly via initial vibrational preparation. Nevertheless, obtaining direct experimental evidence of whether specific-mode excitation affects the passage at the CI is challenging, requiring well-resolved time- or frequency-domain experiments. Here promotion of methylamine-d2 (CH3ND2) molecules to spectral-resolved rovibronic states on the excited S1 potential energy surface, coupled to sensitive D photofragment probing, allowed us to follow the N-D bond fission dynamics. The branching ratios between slow and fast D photofragments and the internal energies of the CH3ND(X̃) photofragments confirm correlated anomalies for predissociation initiated from specific rovibronic states. These anomalies reflect the existence of a dynamic resonance that strongly depends on the energy of the initially excited rovibronic states, the evolving vibrational mode on the repulsive S1 part during N-D bond elongation, and the manipulated passage through the CI that leads to CH3ND radicals excited with C-N-D bending. This resonance plays an important role in the bifurcation dynamics at the CI and can be foreseen to exist in other photoinitiated processes and to control their outcome.

The rapid increase in graphene-based applications has been accompanied by novel top-down manufacturing methods for graphene and its derivatives (e.g., graphene nanoplatelets (GnPs)). The characterization of the bulk properties of these materials by imaging and surface techniques (e.g., electron microscopy and Raman spectroscopy) is only possible through laborious and time-consuming statistical analysis, which precludes simple and efficient quality control during GnP production. We report that thermogravimetry (TG) may be utilized, beyond its conventional applications (e.g., quantification of impurities or surfactants, or labile functional groups) to characterize bulk GnP properties. We characterize the structural parameters of GnP (i.e., defect density, mean lateral dimension, and polydispersity) by imaging and surface techniques, on one hand, and by a systematic TG, on the other. The combined data demonstrate that the combustion temperature of commercially available and laboratory-prepared GnPs is correlated with their mean lateral dimension and defect density, while the combustion temperature range is proportional to their polydispersity index. Mapping all these parameters allows one to evaluate the GnPs' structure following a simple thermogravimetric experiment (without necessitating further statistical analysis). Finally, TG is also used to detect and quantify different GnP constituents in powder and to conduct rapid quality-control tests during GnP production.

Photoacoustic Raman spectra of gaseous pyrrole in the 3504-3535 and 3068-3152 cm(-1) energetic windows were measured, to obtain new information about the hot bands in the vicinity of the N-H(ν1) and C-H(ν2) stretch fundamentals, respectively. The observed vibrational patterns are characterized by sharp Q-branches, where the strong bands reflect the fundamentals and the weaker ones, as established from their temperature dependence, are hot bands. From the simulation of the observed spectra, the band origins and nondiagonal anharmonicities were determined. Comparison of the latter values to the anharmonicities, x(ij) (i = 1, 2 and j = 16, 15, 14, 12, 11) obtained from anharmonic calculations at the B3LYP/6-311++G(d,p), B3LYP/cc-pVQZ and MP2/cc-pVTZ levels, aided the tentative assignment of the hot bands. The retrieved parameters add new data to the extensive set of already known vibrational constants of pyrrole.

The binding of block copolymer Pluronic F-127 in aqueous dispersions of single- (SWCNT) and multiwalled (MWCNT) carbon nanotubes has been studied by pulsed-field-gradient (PFG) (1)H NMR spectroscopy. We show that a major fraction of polymers exist as a free species while a minor fraction is bound to the carbon nanotubes (CNT). The polymers exchange between these two states with residence times on the nanotube surface of 24 ± 5 ms for SWCNT and of 54 ± 11 ms for MWCNT. The CNT concentration in the solution was determined by improved thermal gravimetric analysis (TGA) indicating that the concentration of SWCNT dispersed by F-127 was significantly higher than that for MWCNT. For SWCNT, the area per adsorbed Pluronic F-127 molecule is estimated to be about 40 nm(2).

A key first step toward probing structures and interactions of individual conformers of isolated flexible molecules is uncovering their characteristic spectral signatures. Here, conformation-specific ionization-detected stimulated Raman (IDSR) and visible-visible-ultraviolet hole-burning spectra were measured simultaneously to determine the unique signatures of the two most stable conformers of tryptamine in the gas phase. These signatures together with the comparison of the IDSR spectra to the computationally predicted Raman spectra assisted in their characterization and structural identification. This new approach offers high selectivity and is foreseen to be an improved diagnostic tool for dissection of conformers of flexible molecules.

The anharmonic vibrational spectra of α-D-glucose, β-D-glucose, and sucrose are computed by the vibrational self-consistent field (VSCF) method, using potential energy surfaces from electronic structure theory, for the lowest energy conformers that correspond to the gas phase and to the crystalline phase, respectively. The results are compared with ultraviolet-infrared (UV-IR) spectra of phenyl β-D-glucopyranoside in a molecular beam, with literature results for sugars in matrices and with new experimental data for the crystalline state. Car-Parrinello dynamics simulations are also used to study temperature effects on the spectra of α-D-glucose and β-D-glucose and to predict their vibrational spectra at 50, 150, and 300 K. The effects of temperature on the spectral features are analyzed and compared with results of the VSCF calculations conducted at 0 K. The main results include: (i) new potential surfaces, constructed from Hartree-Fock, adjusted to fit harmonic frequencies from Møller-Plesset (MP2) calculations, that give very good agreement with gas phase, matrix, and solid state spectra; (ii) computed infrared spectra of the crystalline solid of α-glucose, which are substantially improved by including mimic groups that represent the effect of the solid environment on the sugar; and (iii) identification of a small number of combination-mode transitions, which are predicted to be strong enough for experimental observation. The results are used to assess the role of anharmonic effects in the spectra of the sugars in isolation and in the solid state and to discuss the spectroscopic accuracy of potentials from different electronic structure methods., (© 2011 American Chemical Society)

The probability of hydrogen atom release, following photoexcitation of methylamine, CH(3)NH(2), is found to increase extensively as higher vibrational states on the first excited electronic state are accessed. This behavior is consistent with theoretical calculations, based on the probability of H atom tunneling through an energy barrier on the excited potential energy surface, implying that N-H bond breaking is dominated by quantum tunneling.

Molecularly imprinted polymer (MIP) droplets were printed using a pipet or a nano fountain pen on surface-enhanced Raman scattering (SERS)-active surfaces, to directly monitor the uptake and release of a template molecule, the beta-blocking drug propranolol, by SERS. The monitored SERS bands can be related to the template, allowing for its detection but also identification in the MIP. This is an advantage if the technique is to be used during the development phase of MIPs as microstructures, but equally for the readout of MIP-based biochips.

The first through fourth C-H stretching overtone regions of ethene were measured by photoacoustic spectroscopy of room-temperature molecules and action spectroscopy of jet-cooled molecules. The rotational cooling led to improved resolution in the action spectra, turning these spectra into key players in determining the multiple band appearance in each region, their types, and origins. These manifolds arise from strong couplings of the C-H stretches to doorway states and were analyzed in terms of a simplified joint local-mode/normal-mode (LM)/(NM) model and an equivalent NM model, accounting for principal resonances. The diagonalization of the LM/NM and NM vibrational Hamiltonians and the least-square fittings revealed model parameters, enabling assignment of A- and B-type bands. These bands behave differently through the V = 2-4 manifolds, showing coupling to doorway states for the former but not for the latter. The energy flow out of the fourth C-H overtone is governed by the interaction with bath states due to the increase in the density of states.