Photodissociation Imaging Research Articles

Predissociation of the B Σu−3 state of S2: A coupled-channel model

A coupled-channel Schrödinger equation model of predissociation in the B Σu-3 state of S2 is developed and optimized by comparison with recent photoabsorption spectra of the B Σu-3-X Σg-3(v,0) bands for 11 ≤ v ≤ 27, covering the energy range 35 800-41 500 cm-1. All bands in this range exhibit varying degrees of diffuseness, with corresponding predissociation linewidths Γ ≈ 4-60 cm-1 full-width at half-maximum. Model comparisons with both low-temperature (T = 370 K) and high-temperature (T = 823 K) spectra indicate, for many bands, significant dependence of the linewidth on both the rotational quantum number J and the fine-structure component Fi. Just as in the analogous case of O2, the B(v)-state predissociation in S2 is caused principally by spin-orbit interaction with 3Πu, 1Πu, 5Πu, and Σu+3 states. The inner-limb crossing with B″3Πu is responsible for the predissociation of B(v = 11) and provides a significant slowly varying contribution for B(v ≥ 12). The outer crossings with the 1Πu, 5Πu, and 2 Σu+3 states are responsible for oscillatory contributions to the predissociation widths, with first peaks at v = 13, 20, and 24, respectively, and the 5Πu contribution dominant. Prior to the photodissociation imaging study of Frederix et al. [J. Phys. Chem. A 113, 14995 (2009)], which redefined the dissociation energy of S2, the prevailing paradigm was that only the 1Πu interaction was responsible for the B(v = 11-16) predissociation: this view is not supported by our model.

Toward fully quantum modelling of ultrafast photodissociation imaging experiments. Treating tunnelling in the ab initio multiple cloning approach.

We present an account of our recent effort to improve simulation of the photodissociation of small heteroaromatic molecules using the Ab Initio Multiple Cloning (AIMC) algorithm. The ultimate goal is to create a quantitative and converged technique for fully quantum simulations which treats both electrons and nuclei on a fully quantum level. We calculate and analyse the total kinetic energy release (TKER) spectra and Velocity Map Images (VMI), and compare the results directly with experimental measurements. In this work, we perform new extensive calculations using an improved AIMC algorithm that now takes into account the tunnelling of hydrogen atoms. This can play an extremely important role in photodissociation dynamics.

Nanosecond photofragment imaging of adiabatic molecular alignment

Adiabatic alignment of CH(3)I, induced by the anisotropic interaction of this symmetric top molecule with the intense field of a nonresonant infrared laser pulse, has been studied using velocity map imaging. We are using photodissociation imaging with pulsed nanosecond lasers to probe the distribution of the molecular axis in the laboratory space. In contrast to the commonly used probing with femtosecond laser pulses, this technique directly yields the degree of alignment over an extended space-time volume. This will be relevant for future reactive scattering experiments with laser-aligned molecules. The obtained degree of alignment, (cos (2)θ), measured as a function of the infrared laser intensity, agrees well with a quantum calculation for rotationally cold methyl iodide. The strong infrared laser is also found to modify the photofragmentation dynamics and open up pathways to CH(3)I(+) formation and subsequent fragmentation.

Photodissociation of theHeH+ion into excited fragments(n=2,3)by time-dependent methods

The total and partial photodissociation cross sections of the molecular ion ${\text{HeH}}^{+}$ are computed by time-dependent methods for fragmentation into the excited shells $n=1,2,3$ up to a photon energy of 40 eV. ${^{1}\ensuremath{\Sigma}}^{+}$ and $^{1}\ensuremath{\Pi}$ states are considered for parallel and perpendicular transitions for different initial rotational or vibrational excitations. Nonadiabatic radial and rotational couplings are taken into account. The results from coupled-channel equations are compared with the Born-Oppenheimer approximation. A time-dependent calculation with a femtosecond laser pulse is carried out to simulate a recent crossed beam photodissociation imaging experiment with vacuum ultraviolet free-electron laser [H. B. Pedersen et al., Phys. Rev. Lett. 98, 223202 (2007)]. The dominance of photodissociation perpendicular to the photon polarization is confirmed.

Photodissociation Imaging of Diatomic Sulfur (S2)

The photodissociation of diatomic sulfur, S(2), in the region of the first dissociation limit is studied with velocity map imaging. Correlated fine structure distributions P(J1,J2) for the two S((3)P(J)) fragments are determined at selected photolysis wavelengths. Image analysis of the speed distributions of the atomic fragments following product-state-specific detection results in a revision of the bond energy to D(0) = 35636.9 +/- 2.5 cm(-1) with respect to the lowest rovibrational level. This value arises from reinterpretation of previous spectroscopic data showing onset of predissociation in the B(3)Sigma(u)(-) state, as the measurements presented here demonstrate that the long-range correlation of the excited state invoked as causing the dissociation is S((3)P(2)) + S((3)P(2)) rather than S((3)P(2)) + S((3)P(1)). The wavelength dependence of data for the S((3)P(2)) + S((3)P(2)) channel suggests involvement of photoexcitation through the optically forbidden Herzberg continuum bands in addition to dissociation initiated via the optically allowed B(3)Sigma(u)(-)-X(3)Sigma(g)(-) and B''(3)Pi(u)-X(3)Sigma(g)(-) bands. Changes in product recoil velocity angular distributions and atomic angular momentum polarization were also measured as a function of dissociation wavelength. The results are compared with predictions from an adiabatic model for dissociation, which provides a basis for interpretation but does not explain quantitatively the experimental results.

Observing time-dependent vibrational quantum dynamics in deuterium hydride molecular ions

Few-cycle laser pulses are used to “pump and probe” image the vibrational wavepacket dynamics of a HD+ molecular ion. The quantum dephasing and revival structure of the wavepacket are mapped experimentally with time-resolved photodissociation imaging. The motion of the molecule is simulated using a quantum-mechanical model predicting the observed structure. The coherence of the wavepacket is controlled by varying the duration of the intense laser pulses. By means of a Fourier transform analysis both the periodicity and relative population of the vibrational states of the excited molecular ion have been characterized.