Conformational Mapping, Interactions, and Fluorine Impact by Combined Spectroscopic Approaches and Quantum Chemical Calculations.

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.

Significantly Improved Detection of Molecular Oxygen by Two-Color Resonance-Enhanced Multiphoton Ionization.

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 3d Rydberg complex yields state-selective spectra with signal comparable to the intense but diffuse C 3sσ 3Πg ← X 3Σg- (2 + 1) REMPI bands without significant saturation or broadening. The resulting increase in sensitivity permitted observation of the very weak 3dπ 1Δ2 ← X 3Σg- transitions and is independent of the intermediate state. This advance in ionization efficiency and quantum state-selective sensitivity for O2 promises to aid physical and chemical studies across a wide variety of fields.

Synergistic Spectroscopic and Computational Characterization Evidencing the Preservation or Flipping of the Hydroxyl Group of 2-Phenylethyl Alcohol upon Single and Double Hydration.

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-H2O and PEAL-(H2O)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.

Ionization energies and ionization-induced structural changes in 2-phenylethylamine and its monohydrate.

We report the resonance-enhanced two-photon ionization combined with various detection approaches and quantum chemical calculations of biologically relevant neurotransmitter prototypes, the most stable conformer of 2-phenylethylamine (PEA), and its monohydrate, PEA-H2O, to reveal the possible interactions between the phenyl ring and amino group in the neutral and ionic species. Extracting the ionization energies (IEs) and appearance energy was achieved by measuring the photoionization and photodissociation efficiency curves of the PEA parent and photofragment ions, together with velocity and kinetic energy-broadened spatial map images of photoelectrons. We obtained coinciding upper bounds for the IEs for PEA and PEA-H2O of 8.63 ± 0.03 and 8.62 ± 0.04 eV, within the range predicted by quantum calculations. The computed electrostatic potential maps show charge separation, corresponding to a negative charge on phenyl and a positive charge on the ethylamino side chain in the neutral PEA and its monohydrate; in the cations, the charge distributions naturally become positive. The significant changes in geometries upon ionization include switching of the amino group orientation from pyramidal to nearly planar in the monomer but not in the monohydrate, lengthening of the N-H⋯π hydrogen bond (HB) in both species, Cα-Cß bond in the side chain of the PEA+ monomer, and the intermolecular O-H⋯N HB in PEA-H2O cations, leading to distinct exit channels.

Kinetic Energy-Broadened Spatial Map Imaging for Recovering Dynamical Information.

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 H2O 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.

Experimental/Computational Study on the Impact of Fluorine on the Structure and Noncovalent Interactions in the Monohydrated Cluster of ortho-Fluorinated 2-Phenylethylamine.

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-H2O 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 CH2 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.

Revealing the Structure and Noncovalent Interactions of Isolated Molecules by Laser-Desorption/Ionization-Loss Stimulated Raman Spectroscopy and Quantum Calculations.

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.

Maximal kinetic energy and angular distribution analysis of spatial map imaging: Application to photoelectrons from a single quantum state of H2O.

Dynamical or spatial properties of charged species can be obtained using electrostatic lenses by velocity map imaging (VMI) or spatial map imaging (SMI), respectively. Here, we report an approach for extracting dynamical and spatial information from patterns in SMI images that map the initial coordinates, velocity vectors, and angular distributions of charged particles onto the detector, using the same apparatus as in VMI. Deciphering these patterns required analysis and modeling, involving both their predictions from convolved spatial and velocity distributions and fitting observed images to kinetic energies (KEs) and anisotropy parameters (ßs). As the first demonstration of this capability of SMI, the ensuing photoelectrons resulting from (2 + 1) resonant ionization of water in a selected rotational state were chosen to provide a rigorous basis for comparison to VMI. Operation with low acceleration voltages led to a measured SMI pattern with a unique vertical intensity profile that could be least-squares fitted to yield KE and ß, in good agreement with VMI measurement. Due to the potential for improved resolution and the extended KE range achievable by this new technique, we expect that it might augment VMI in applications that require the analysis of charged particles and particularly in processes with high KE release.

A new imaging-based method for alignment of multiple laser beams.

A new method for multiple laser beams alignment, useful in a wide range of spectroscopies, is proposed and demonstrated. The method, based on the coupling of spatial map imaging (SMI) with velocity map imaging (VMI), aided beams visualization, through interrogation of the ionization signal of different species in a time-of-flight mass spectrometer. This approach is very effective for alignment and for evaluating the spatial overlap of laser beams with a molecular beam. This was demonstrated by monitoring the resonant two-photon ionization spectrum of 2-phenylethylamine (PEA) monomer and its hydrated (PEA-H2O) cluster and the ionization-loss stimulated Raman spectrum of the cluster, via VMIs accumulation, as a function of the exciting laser wavelength. The former permitted immediate classification of the features in the spectrum, corresponding to the molecular ion or the cluster. The proposed methodology will be useful in other challenging multiple laser beam experiments for spectroscopic studies and is expected to improve extensively their outcome.

A simple strategy for enhanced production of nanoparticles by laser ablation in liquids.

Upgrading the productivity of nanoparticles (NPs), generated by pulsed laser ablation in liquid (PLAL), still remains challenging. Here a novel variant of PLAL was developed, where a doubled frequency Nd:YAG laser beam (532 nm, ∼5 ns, 10 Hz) at different fluences and for different times was directed into a sealed vessel, toward the interface of the meniscus of ethanol with a tilted bulk metal target. Palladium, copper and silver NPs, synthesized in the performed proof of concept experiments, were mass quantified, by inductively coupled plasma optical emission spectrometry, and characterized by ultraviolet-visible extinction spectroscopy, transmission electron microscopy and x-ray diffraction. The NPs consist of crystalline metals of a few nm size and their ablation rates and agglomeration levels depend on the employed laser fluences. The ensuing laser power-specific productivity curves for each metal, peaked at specific laser fluences, were fitted to the results of a simple model accounting for plasma absorption and heat transfer. The resulting peaked yields and concentrations were more than an order of magnitude higher than those obtained for totally immersed targets. Besides, the measured productivities showed nearly linear dependencies during time intervals up to 30 min of ablation, but became saturated at 1 h, due to accumulation of a significant number of NPs along the laser beam path, reducing the laser intensity reaching the target. The suggested approach that led to enhanced productivities and to generation of high concentrations of NPs in a single vessel could inspire future studies that will contribute to further developments of efficient generation of NPs with controlled characteristics.

Alloying copper and palladium nanoparticles by pulsed laser irradiation of colloids suspended in ethanol.

Nanoparticles (NPs) of copper, palladium and Cu0.8Pd0.2 alloy have been prepared by pulsed laser ablation/irradiation in ethanol, by the second harmonic of a pulsed Nd : YAG laser (532 nm, ∼5 ns, 10 Hz). The monometallic NPs were synthesized by laser ablation of pure bulk targets immersed in ethanol and the alloyed ones by laser irradiation of stirred mixtures of suspended monometallic colloids. The suspensions were irradiated through two distinctive configurations, including lateral collimated and top focused beams that reached the corresponding fluences for NPs vaporization and for extensive plasma formation. The generated NPs were characterized by ultraviolet-visible absorption spectrometry, low and high-resolution transmission electron microscopy, energy-dispersive spectroscopy and selected area electron diffraction. The first fluence regime afforded the synthesis of alloyed NPs in the few nm diameter range, where alloying was somewhat disturbed by agglomeration, while the second led to larger size NPs and faster alloying, due to laser scattering by the plasma. These findings were supported and interpreted by the particle heating-melting-evaporation model. The approach developed here, assisted by the model and the various characterization methods, proved to control the alloying process and the size distribution of the NPs and to give the best indication for its progress.

Structural features of monohydrated 2-(4-fluorophenyl)ethylamine: a combined spectroscopic and computational study.

A jet-cooled singly hydrated 2-(4-fluorophenyl)ethylamine (4-FPEA-H2O) cluster has been studied by ionization-loss stimulated Raman spectroscopy of the 4-FPEA photofragment and density functional calculations of the parent. Comparison of the measured spectrum of the photofragment to computed scaled harmonic Raman spectra of different conformers of the 4-FPEA-H2O cluster, at the M06-2X/6-311++G(d,p) level of theory, allowed determination of the calculated spectrum that best fits the experimental one. The correlation between them was further supported by the stability of the cluster, as revealed from the calculated energies of the fully optimized geometries of the possible different clusters in the ground electronic state. The corresponding structure consists of a water molecule, which is hydrogen-bonded to the nitrogen lone pair of the folded ethylamino side chain in the most stable gauche conformer of 4-FPEA. The presence of the hydrogen bond and other bonding and non-bonding interactions was also tested by atoms in molecules and noncovalent interaction analyses. The former approach showed no critical points in electron density, while the latter revealed regional topologies of reduced density gradients, indicating the formation of this hydrogen-bond and other attractive and repulsive interactions. The monohydration of 4-FPEA provides an insight into the intra- and inter-molecular interactions that play a role in stabilizing the cluster.

The conformational landscape of 2-(4-fluoro-phenyl)-ethylamine: consequences of fluorine substitution at the para position.

Fluorination is considered as a possible means for alteration of conformational landscapes in molecules. The effect of fluorine substitution was studied here by measuring the vibronic and vibrational spectra of gas phase 2-(4-fluoro-phenyl)-ethylamine (4-FPEA) by resonant two-photon ionization (R2PI) and by ionization-loss stimulated Raman spectroscopy (ILSRS). The measurement of survey ILSR spectra of 4-FPEA in the amino group region allowed to associate the bands in the R2PI spectrum to origin and vibronic transitions of the ground (S0) to the excited (S1) electronic states of three different conformers. The presence of these conformers of 4-FPEA in the molecular beam was confirmed by measurement of distinctive ILSRS spectral signatures in the 400-1700 and 2750-3500 cm-1 broad spectral range. The interpretation of their structures was assisted by the results of quantum chemical calculations, including a torsional potential energy surface, energies of the fully optimized geometries in the S0 state and harmonic Raman spectra as well as natural bond orbital and atoms in molecule analyses. Comparison of the spectra with the results of scaled harmonic Raman spectra revealed two gauche configurations with folded ethylamino side chains and amino groups aiming to different directions together with a symmetric anti structure with an outward extended chain. The site-specific para-fluorination, at a distant position from the side chain modified the energetic ordering of the conformers, relative to the structure with the fluorine atom at the ortho position, but kept it close to that of PEA.

Control of Nonadiabatic Passage through a Conical Intersection by a Dynamic Resonance.

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.

CD3 Deformation Modes as Preferential Promoters of Methylamine-d3 to the First Electronic State.

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.

Structural motifs of 2-(2-fluoro-phenyl)-ethylamine conformers.

Vibronic and vibrational spectra of 2-(2-fluoro-phenyl)-ethylamine (2-FPEA) conformers were measured in a molecular beam by resonant two-photon ionization (R2PI), ultraviolet-ultraviolet hole burning (UV-UV HB) spectroscopy, and ionization-loss stimulated Raman spectroscopy (ILSRS). The measured ILSR spectral signatures in the survey spectra of the amino group region and in the broad spectral range revealed the presence of five different conformers, which were confirmed by the HB spectra. The determination of the structures of the conformers of 2-FPEA was assisted by quantum chemical calculations of the torsional potential energy surface and of the scaled harmonic Raman spectra. Comparison of the measured ILSR spectra with the calculated Raman spectra allowed us to identify one gauche structure with the ethylamino side chain folded toward the fluorine atom, two gauche structures with the ethylamino side chain folded to the opposite side and two anti conformers with extended tails. The effect of fluorination on the spectra and on the stability and structures of these species is discussed.

Evidence for quantum effects in the predissociation of methylamine isotopologues.

Non-adiabatic dynamics at conical intersections (CIs) extensively affects the photostability of biomolecules by efficiently photoinducing decay routes that dissipate harmful excess ultraviolet energy. Here the predissociation of the model test molecules, methylamine (CH3NH2) and its partially deuterated isotopologue (CD3NH2), excited to different specific vibrational modes in the electronically excited state has been experimentally investigated. The H(D) photofragments were detected by two-color reduced-Doppler ion imaging, which allows measurement of their entire velocity distributions in each laser pulse. The fast and slow H products, resulting from N-H bond cleavage, obtained via different dissociation pathways, showed anomalous distributions for some vibronic states, as indicated by dynamic resonances in the product branching ratio and in the anisotropy parameters of the fast H photofragments. This vibronic-specific control is attributed to the sensitivity of the non-adiabatic dynamics to the energy difference between the initially prepared vibrational states and the energy of the CIs and not only to the distinctive pre-excited nuclear motions. The observations in the two isotopologues reveal uniquely detailed insight into the dynamics of state-specific control.

In situ generation of superoxide anion radical in aqueous medium under ambient conditions.

In the recent decades superoxide [O(2-.) ] has become the subject of considerable interest. Nonetheless, generation of superoxide compounds is still a substantial challenge. The standard methods for synthesis of superoxide derivatives are either through the oxidation of molten alkali metals with hot air or by using electrolytic reduction of oxygen in aprotic solvent such as dimethylformamide. No methodology is available for the generation of superoxides in protic solutions and particularly not in water. We propose a new in situ method for alkali superoxide preparation by using sodium hydroxide and hydrogen peroxide at room temperature and in aqueous solution.

Enhanced sensitivity in H photofragment detection by two-color reduced-Doppler ion imaging.

Two-color reduced-Doppler (TCRD) and one-color velocity map imaging (VMI) were used for probing H atom photofragments resulting from the ~243.1 nm photodissociation of pyrrole. The velocity components of the H photofragments were probed by employing two counterpropagating beams at close and fixed wavelengths of 243.15 and 243.12 nm in TCRD and a single beam at ~243.1 nm, scanned across the Doppler profile in VMI. The TCRD imaging enabled probing of the entire velocity distribution in a single pulse, resulting in enhanced ionization efficiency, as well as improved sensitivity and signal-to-noise ratio. These advantages were utilized for studying the pyrrole photodissociation at ~243.1 and 225 nm, where the latter wavelength provided only a slight increase in the H yield over the self-signal from the probe beams. The TCRD imaging enabled obtaining high quality H(+) images, even for the low H photofragment yields formed in the 225 nm photolysis process, and allowed determining the velocity distributions and anisotropy parameters and getting insight into pyrrole photodissociation.

Computational modeling of laser-plasma interactions: pulse self-modulation and energy transfer between intersecting laser pulses.

The nonlinear interaction of intense femtosecond laser pulses with a self-induced plasma channel in air and the energy transfer between two intersecting laser pulses were simulated using the finite-difference time-domain particle-in-cell method. Implementation of a simple numerical code enabled modeling of various phenomena, including pulse self-modulation in the spatiotemporal and spectral domains, conical emission, and energy transfer between two intersecting laser beams. The mechanism for energy transfer was found to be related to a plasma waveguide array induced by Moiré patterns of the interfering electric fields. The simulation results provide a persuasive replication and explanation of previous experimental results, when carried out under comparable physical conditions, and lead to prediction of others. This approach allows us to further examine the effect of the laser and plasma parameters on the simulation results and to investigate the underlying physics.