Finite-temperature infrared spectroscopy of polycyclic aromatic hydrocarbon molecules. II. Principal mode analysis and self-consistent phonons.

Following previous work [F. Calvo et al. J. Chem. Phys. 132, 124308 (2010)], infrared spectra of several polycyclic aromatic hydrocarbon molecules are simulated with classical and quantum molecular dynamics trajectories. The interactions are modeled using a tight-binding potential energy surface and quantum delocalization is accounted for using the partially adiabatic centroid and ring-polymer molecular dynamics frameworks, both built upon the path-integral representation. The spectra obtained directly by Fourier transformation of the dipole moment autocorrelation function are here compared with several quasiharmonic approximations that provide additional information about the vibrational modes. A principal mode analysis (PMA) is carried out from the covariance matrix of atomic displacements in classical and quantum trajectories. The method systematically overestimates the line shifts due to anharmonicities, except in the power spectra of atomic displacements, and is not robust in predicting IR intensities for such large molecules. Alternatively, effective normal modes have also been determined by adapting the self-consistent phonon (SCP) theory of condensed matter physics to the present tight-binding model, in both classical and quantum mechanical descriptions. The SCP approximation turns out as semiquantitative in estimating the redshift of tight stretching modes, and performs better for classical systems. More problematic, it predicts that many low- or medium-frequency modes should be blueshifted, in contradiction with the molecular dynamics results. The sets of anharmonic normal modes extracted from the PMA and SCP approaches reveal important mixings within the tightest C-H and C-C stretching modes, which are also manifested on the corresponding power spectra.

Finite temperature infrared spectroscopy of polycyclic aromatic hydrocarbon molecules: path-integral molecular dynamics.

The vibrational spectra of the naphthalene, pyrene, and coronene molecules have been computed in the 0-3500 cm(-1) infrared range using classical and quantum molecular dynamics simulations based on a dedicated tight-binding potential energy surface. The ring-polymer molecular dynamics (RPMD) and partially adiabatic centroid molecular dynamics (CMD) methods have been employed to account for quantum nuclear effects. The contributions of quantum delocalization to the line shift and broadening are significant in the entire spectral range and of comparable magnitude as pure thermal effects. While the two methods generally produce similar results, the CMD method may converge slower at low temperature with increasing Trotter discretization number. However, and contrary to the CMD method, the RPMD approach suffers from serious resonance problems at high frequencies and low temperatures.

Fragmentation branching ratios of highly excited hydrocarbon molecules CnH and their cations CnH+ (n

We have measured fragmentation branching ratios of neutral C(n)H and C(n)H(+) cations produced in high velocity (4.5 a.u) collisions between incident C(n)H(+) cations and helium atoms. Electron capture gives rise to excited neutral species C(n)H and electronic excitation to excited cations C(n)H(+). Thanks to a dedicated setup, based on coincident detection of all fragments, the dissociations of the neutral and cationic parents were recorded separately and in a complete way. For the fragmentation of C(n)H, the H-loss channel is found to be dominant, as already observed by other authors. By contrast, the H-loss and C-loss channels equally dominate the two-fragment break up of C(n)H(+) species. For these cations, we provide the first fragmentation data (n>2). Results are also discussed in the context of astrochemistry.