Alexander Portnov

Identification of organic compounds in ambient air via characteristic emission following laser ablation

The potential of laser-induced breakdown spectroscopy (LIBS) as a simple and rapid method for detection of organic compounds in ambient air was investigated. Ablation of samples of aromatic hydrocarbons and nitroaromatic compounds covering various surfaces was performed using the second (532nm) or fourth (266nm) harmonic of a nanosecond pulsed Nd:YAG laser. The plasma emission following the ablation consisted mainly of spectral features related to the CN (B 2 Σ + -X 2 Σ - ) violet system and C 2 (d 3 IIg -a 3 II u )Swan system, and to some C, H, O, and N atomic lines. The CN, O and N lines include some contribution from the interaction of the ensuing plasma with background atmospheric air. There is a correlation between the intensity ratios of the products and the molecular structure, providing the possibility of identifying these compounds by LIBS.

Detection of particles of explosives via backward coherent anti-Stokes Raman spectroscopy

Coherent anti-Stokes Raman scattering spectroscopy (CARS) was used for detection of solid particles of explosives and related compounds. The CARS spectra were recorded in the fingerprint region and were shown to exhibit the strong characteristic features of spontaneous Raman spectra of the respective compounds. This study demonstrates the applicability of narrowband backward-CARS spectroscopy for detection of explosives and specifically of its preference over spontaneous Raman scattering. This method has the potential to be applied to remote sensing of hazardous materials.

Vibrational spectroscopy and intramolecular dynamics of 1-butyne

Photodissociation of jet-cooled vibrationally excited 1-butyne, C(2)H(5)C[Triple Bond]C[Single Bond]H, coupled with mass spectrometric detection of H photofragments, facilitated measurements of action spectra and Doppler profiles, expressing the yield of the ensuing fragments versus the vibrational excitation and UV probe lasers, respectively. Both the action spectra and the simultaneously measured room temperature photoacoustic spectra in the 2nu(1), 3nu(1), and 4nu(1) C[Single Bond]H acetylenic stretch regions exhibit unresolved rotational envelopes with significant narrowing of the former due to temperature-related change in the rotational structure. The narrowing of the action spectrum in the 3nu(1) region exposed a resonance splitting, implying intramolecular vibrational energy redistribution (IVR) time of approximately 1 ps. Asymmetric rotor simulation of the band contours provided the rotational constants and estimates for the homogeneous broadening arising from IVR to the bath vibrational states. The homogenous linewidth of 4nu(1) is anomalously narrower than that of 2nu(1) and 3nu(1), indicating a longer lived 4nu(1) state despite the increasing background state density, suggestive of a lack of low-order resonances or of mode-specific coupling with the bath states. The Doppler profiles indicate that the H photofragments are released with low average translational energies, pointing to an indirect dissociation process occurring after internal conversion (IC) to the ground electronic state or after IC and isomerization to butadiene.

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.

Mode-dependent enhancement and intramolecular dynamics via vibrationally mediated photodissociation

Vibrationally mediated photodissociation has been shown to control bond cleavage in molecules and probe their dynamics on the ground and excited potential energy surfaces. The application of this method to two seven-atom molecules illustrates surprising vibrational energy localization in methylamine (CH3NH2), a molecule with a torsional degree of freedom and unique information regarding intramolecular vibrational energy redistribution for the C‐H

Vibrational structure and methyl C–H dynamics in propyne

Our previous study [J. Chem. Phys. 122, 224316 (2005)] presented the photoacoustic and action spectra of the V=2, 3, 4, and 5 manifolds of the C-H methyl stretching vibrations of propyne and their analysis in terms of a simplified joint local mode/normal mode model. In the current paper the C-H transition intensities were calculated using B3LYP6-311++G(d,p) level of theory to obtain the dipole moment functions. The diagonalization of the vibrational Hamiltonian revealed new model parameters obtained by least square fitting of the eigenvalues to the action spectra band origins, while examining the correspondence between the calculated intensities and simulated band areas. The newly derived parameters predict well the band positions and the observed intensities, allowing new assignment of the features. The derived Hamiltonian was also used to obtain the overall temporal behavior of the C-H stretches as a result of the Fermi couplings and interactions with the bath states. These results indicate that any specificity attained by suitable excitation of the methyl C-H stretches is lost on picosecond time scale, primarily due to strong interactions with doorway states in the lower overtone and coupling with bath states in the region of the higher ones.

Communication: Mode-specific photodissociation of vibrationally excited pyrrole

Laser-based spectroscopies coupled with molecular beam techniques facilitated the monitoring of H fragments released in ultraviolet photodissociation of pre-excited isoenergetic vibrational levels of pyrrole. Most noticeably, there was an order of magnitude larger reactivity for an eigenstate primarily consisting of two quanta of ring deformation than for another with one quantum of symmetric C-H stretch. The dynamics, the intramolecular interactions controlling the energy flow, and the mode-selectivity within a medium-sized, ten atom molecule, is discussed.

Vibrationally mediated photodissociation of ethene isotopic variants preexcited to the fourth C-H stretch overtone.

H and D photofragments produced via vibrationally mediated photodissociation of jet-cooled normal ethene (C2H4), 1,2-trans-d2-ethene (HDCCDH), and 1,1-d2-ethene (CH2CD2), initially excited to the fourth C-H stretch overtone region, were studied for the first time. H and D vibrational action spectra and Doppler profiles were measured. The action spectra include partially resolved features due to rotational cooling, while the monitored room temperature photoacoustic spectra exhibit only a very broad feature in each species. Simulation of the spectral contours allowed determination of the band types and origins, limited precision rotational constants, and linewidths, providing time scales for energy redistribution. The H and D Doppler profiles correspond to low average translational energies and show slight preferential C-H over C-D bond cleavage in the deuterated variants. The propensities toward H photofragments emerge even though the energy flow out of the initially prepared C-H stretch is on a picosecond time scale and the photodissociation occurs following internal conversion, indicating a more effective release of the light H atoms.

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.

Overtone spectroscopy of C–H ethyl stretches of 1-butyne

Room-temperature photoacoustic (PA) spectra and jet-cooled action spectra of the first to third overtone regions of the ethyl C-H stretches in vapor phase 1-butyne, CH3CH2C[Triple Bond]C-H, were measured. Both the PA and action spectra exhibit a complex multiple peak structure being better resolved and more pronounced in the latter, due to inhomogeneous structure reduction. The observed manifolds were analyzed in terms of a simplified joint local-/normal-mode (LM/NM) model accounting for two types of C-H stretches (methyl and methylene) and for Fermi resonances between stretches and deformations. The retrieved parameters, used for calculation of the eigenstates, come from the best-fit parameters based on the diagonalization of the vibrational Hamiltonian in the LM/NM basis. The parameters were obtained by comparing the eigenvalues and the sum of the squares of the expansion coefficients of the eigenvectors of the C-H stretches of methyl and methylene to the action spectra peak positions and intensities, respectively. This approximate model vibrational Hamiltonian is proposed to explain most observed spectral features, corresponding to C-H stretch bands and to combinations of C-H stretches and deformations, indicating the importance of the Fermi resonance. The model was also applied to calculate the dynamics of the C-H stretching modes resulting from coupling with the deformations, implying rapid initial state decay on subpicosecond time scale. Decays of several picoseconds were found for complete transfer of probability from the initially prepared state of methylene and methyl to the counterpart LM states.