Michael Epshtein

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.

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.

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.

Revealing the hot bands in the regions of the N-H and C-H stretch fundamentals of pyrrole.

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.

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.

Vibrational overtone spectroscopy and intramolecular dynamics of C–H stretches in pyrrole

Room-temperature photoacoustic spectra and jet-cooled action spectra of the regions of the first and second C-H stretch overtones of pyrrole were measured with the goal of gaining new insight on the vibrational patterns and the intramolecular energy flow out of the initially excited vibrational states. The rotational cooling of the action spectra helped in observing hitherto unresolved features, assisting determination of the existing multiple bands and their positions in each region. These bands were analyzed by building vibrational Hamiltonian matrices related to a simplified joint local-mode∕normal-mode (LM∕NM) model, accounting for two types of C-H stretches and their Fermi resonances with the CCH deformation modes. The diagonalization of the LM∕NM vibrational Hamiltonians and the fitting of the eigenvalues to the band positions revealed model parameters, enabling assignment of the observed bands. The time dependences of the survival probabilities of the C-H stretches in the region of the first and second overtones, deduced from the vibrational Hamiltonian, show quantum beats due to the couplings to the deformations and decays driven by weaker interactions to the bath states. The C-H stretches, although somewhat lower in energy, show stronger coupling than the N-H stretches.