P. Parneix

Formation and destruction of polycyclic aromatic hydrocarbon clusters in the interstellar medium

Aims. The competition between the formation and destruction of coronene clusters under interstellar conditions is investigated theoretically. Methods. The unimolecular nucleation of neutra! clusters is simulated with an atomic model combining an explicit classical force field and a quantum tight-binding approach. Evaporation rates are calculated in the framework of the phase space theory and are inserted in an infrared emission model and compared with the growth rate constants. Results. It is found that, in interstellar conditions, most collisions lead to cluster growth. The time evolution of small clusters (containing up to 312 carbon atoms) was specifically investigated under the physical conditions of the northern photodissociation region of NGC 7023. These clusters are found to be thermally photoevaporated much faster than they are reformed, thus providing an interpretation for the lowest limit of the interstellar cluster size distribution inferred from observations. The effects of ionizing the clusters and density heterogeneities are also considered. Based on our results, the possibility that PAH clusters could be formed in PDRs is critically discussed.

Quantum anharmonic densities of states using the Wang–Landau method

The Wang-Landau sampling method is adapted to the calculation of quantum densities of states for fully coupled anharmonic systems. The accuracy of the method is illustrated against exact counting for two molecules with separable oscillators, namely, the Zundel complex H(5)O(2) (+) and the Na(11) cluster. Application to the fully coupled naphthalene molecule (C(10)H(8)) reveals significant deviations in the finite temperature thermodynamical properties that are not captured by simple perturbation theory. There are no limitations in the size of the molecules that can be treated with this method.

Resonant two-photon two-color photoionization (R2P2CI) spectra of aniline-Ar n clusters: Isomer strutures and solvent shifts

We present resonant two-photon two-color photoionization (R2P2CI) spectra of a series of Aniline-Arn complexes (n=1−6). An apparently anomalous blue shifted spectra for An-Ar3 is explained by a modified spectral shift additivity rule which assigns different shifts to different relative positions of the Ar with respect to aniline. Evidence is presented for the existence of several isomers of clusters withn≧2. It is shown that, by changing the nucleation conditions, it is possible to control the relative populations of the various isomers.

Quantum calculation of vibrational states in the aniline-argon Van der Waals cluster

Theoretical calculations of vibrational intermolecular states of the aniline–argon van der Waals complex for J=0 are reported. A fully‐quantum method (LCHOP) was used in order to describe the van der Waals cluster. Results in the first two electronic states S0 (X 1A1) and S1 (A 1B2) are presented; in the S1 state a comparison with available experimental data is made. We introduce an additive repulsive interaction between N and Ar in the S1 state in order to account for the spectral features observed in larger clusters. Several parametrizations of this term in the potential are discussed with a view to applications to semiclassical simulation of the spectra of the larger An–Arn clusters.

Accurate modeling of infrared multiple photon dissociation spectra: the dynamical role of anharmonicities.

The dynamical response of a molecular system to a macropulse typically produced by a free-electron laser is theoretically modeled over experimentally long times, within a realistic kinetic Monte Carlo framework that incorporates absorption, stimulated emission, spontaneous emission, and dissociation events. The simulation relies on an anharmonic potential energy surface obtained from quantum chemistry calculations. Application to cationic naphthalene yields a better agreement with measurements than the anharmonic linear absorption spectrum, thus emphasizing the importance of specific dynamical effects on the spectral properties.

Far-infrared spectroscopy of small polycyclic aromatic hydrocarbons

Both experimental and theoretical spectroscopic studies on small gas phase polycyclic aromatic hydrocarbons in the far-infrared spectral region are reported. The experimental set-up based on thermal emission and Fourier transform far infrared analysis led to the detection of relatively broad vibrational bands, unresolved in rotation, representative of each molecule. Detailed theoretical investigations were performed, including both ab initio calculations and spectral simulations. For the majority of the samples, this study provides the first detection of the vibrational modes associated with the skeleton motions.

Temperature and Anharmonic Effects on the Infrared Absorption Spectrum from a Quantum Statistical Approach: Application to Naphthalene

A method is developed to calculate the finite-temperature infrared absorption spectrum of polyatomic molecules with energy levels described by a second-order Dunham expansion. The anharmonic couplings are fully incorporated in the calculation of the quantum density of states, achieved using a Wang-Landau Monte Carlo procedure, as well as in the determination of transition energies. Additional multicanonical simulations provide the microcanonical absorption intensity as a function of both the absorption wavelength and the internal energy of the molecule. The finite-temperature spectrum is finally obtained by Laplace transformation of this microcanonical histogram. The present scheme is applied to the infrared spectrum of naphthalene, for which we quantify the shifting, broadening, and third-order effects as a continuous function of temperature. The influence of anharmonicity and couplings is manifested on the nontrivial variations of these features with increasing temperature.

Photoinduced products from cold coronene clusters : A route to hydrocarbonated nanograins?

Free cold pure coronene clusters have been formed in a gas aggregation source and irradiated with excimer laser pulses. Analysis of the photoproducts thanks to a reflectron time-of-flight mass spectrometer showed that new ionic compounds are formed. These species may include Polycyclic Aromatic Hydrocarbons (PAHs) larger than coronene, PAH-coronene clusters, as well as coronene clusters branched with unsaturated aliphatic chains. The relevance of these results in the context of interstellar medium chemistry, and in particular the carriers of the so-called aromatic infrared emission bands (AIBs), is discussed.

Statistical evaporation of rotating clusters. I. Kinetic energy released

Unimolecular evaporation in rotating atomic clusters is investigated using phase space theory (PST) and molecular dynamics simulations. The rotational densities of states are calculated in the sphere+atom approximation, and analytical expressions are given for a radial interaction potential with the form −C/rp. The vibrational densities of states are calculated using Monte Carlo simulations, and the average radial potential at finite temperature is obtained using a recent extension of the multiple range random-walk algorithm. These ideas are tested on simple argon clusters modeled with the Lennard-Jones interaction potential, at several excitation energies and angular momenta of the parent cluster. Our results show that PST successfully reproduces the simulation data, not only the average KER but its probability distribution, for dissociations from LJ14, for which the product cluster can effectively be considered as spherical. Even for dissociations from the nonspherical LJ8, simulation results remain ver...

Finite-Temperature IR Spectroscopy of Polyatomic Molecules: A Theoretical Assessment of Scaling Factors

With a recently developed simulation method (Basire, M.; et al. J. Phys. Chem. A 2009, 113, 6947), the infrared vibrational spectra of several polyatomic molecules are calculated over a broad range of temperature, taking into account quantum, anharmonic, and couplings effects. Anharmonic force fields, generated from static first-principle calculations, are sampled in the microcanonical ensemble to provide energy-resolved absorption intensities and their finite temperature analogues after Laplace transformation. Effective anharmonic frequencies are characterized as a continuous function of temperature for vinyl fluoride, the N-acetyl-Phe-NH(2) peptide, and protonated naphthalene. These frequencies generally deviate increasingly from the harmonic value with increasing temperature, although the overestimation due to the harmonic approximation is particularly salient for high-frequency modes. Anharmonicities may also be sufficient to alter structural assignment of experimental spectra with respect to empirically scaled harmonic bands. These results emphasize some possible limitations and inaccuracies inherent to using such static scaling factors for correcting harmonic IR spectra.