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The photochemical dynamics of the acetic acid and trifluoro-acetic acid dimers in hexane are studied using time-resolved infrared absorption spectroscopy and ab initio electronic structure calculations. The different hydrogen bond strengths of the two systems lead to changes in the character of the accessed excited states and in the timescales of the initial structural rearrangement that define the early time dynamics following UV excitation. The much stronger hydrogen bonding in the acetic acid dimer stabilizes the system against dissociation. Ground state recovery is mediated by a structural buckling around the hydrogen bond itself with no evidence for excited state proton transfer processes that are usually considered to drive ultrafast relaxation processes in hydrogen bonded systems. The buckling of the ring leads to relaxation through two conical intersections and the eventual reformation of the electronic and vibrational ground states on a few picosecond timescale. In trifluoro-acetic acid, the weaker hydrogen bonding interaction means that the dimer dissociates under similar irradiation conditions. The surrounding solvent cage restricts the full separation of the monomer components, meaning that the dimer is reformed and returns to the ground state structure via a similar buckled structure but over a much longer, ∼100 ps, timescale. [ABSTRACT FROM AUTHOR]

We apply an intense infrared laser pulse in order to perturb the electronic and vibrational states in the three-dimensional charge density wave material 1T-VSe2. Ultrafast snapshots of the light-induced hot carrier dynamics and nonequilibrium quasiparticle spectral function are collected using time- and angle-resolved photoemission spectroscopy. The hot carrier temperature and time-dependent electronic self-energy are extracted from the time-dependent spectral function, revealing that incoherent electron-phonon interactions heat the lattice above the charge density wave critical temperature on a timescale of (200±40) fs. Density functional perturbation theory calculations establish that the presence of hot carriers alters the overall phonon dispersion and quenches efficient low-energy acoustic phonon scattering channels, which results in a new quasiequilibrium state that is experimentally observed.

Understanding processes induced by XUV excitation of Polycyclic Aromatic Hydrocarbons (PAHs) is at the heart of molecular astrophysics, which aims at understanding molecular evolution in interstellar media. We used ultrashort XUV pulses to produce highly excited PAHs cations. The photo-induced dynamics is probed using a pump-probe XUV-IR spectroscopy. By studying PAH from small (naphthalene) to large (hexabenzocoronene) PAHs, we show that the dynamic is governed by the large density of states, in which many-body quantum effects are dominant.

We present an interferometric HHG-2ω0 scheme and compare it to the usual XUV-IR RABBIT method that is widely used in attosecond science. Both methods are able to reconstruct the properties of an attosecond pulse train and can be used to measure attosecond ionization time delays in atoms and molecules. While they have several similarities, they also have conceptual differences. Here, we present some particularities of the HHG-2ω0 method and its advantages and drawbacks, which would help to define situations where it can provide information inaccessible by other technics. [ABSTRACT FROM AUTHOR]

The ejection process of triatomic molecular hydrogen ions produced by the interaction of benzene with ultrafast laser pulses of moderate strong intensity (∼1014 W/cm2) is studied by means of TOF mass spectrometry. The H3+ formation can only take place through the rupture of two C–H bonds and the migration of hydrogen atoms within the molecular structure. The H3+ fragments are released with high kinetic energy (typically 2–8 eV) and at laser intensities ≥1014 W/cm2, well above that required for the double ionization of benzene, suggesting that its formation is taking place within multiply charged parent ions. The relative ejection efficiency of H3+ molecular hydrogen ions with respect to the atomic ones is found to be strongly decreasing as a function of the laser intensity and pulse duration (67–25 fs). It is concluded that the H3+ formation is only feasible within parent molecular precursors of relatively low charged states and before significant elongation of their structure takes place, while the higher multiply charged molecular ions preferentially dissociate into H+ ions. The ejection of H2+ ions is also discussed in comparison to the production of H3+ and H+ ions. Finally, by recording the mass spectra of two deuterium label isotopes of benzene (1,2-C6H4D2, 1,4-C6H4D2) it is verified that the ejection efficiency of some molecular fragments, such as D2H+, DH+, is dependent on the specific position of hydrogen atoms in the molecular skeleton prior dissociation. [ABSTRACT FROM AUTHOR]

We report on the electronic structure and optical properties of conducting ternary transition metal nitrides consisting of metals of different groups of the periodic table of elements. For the study of the bonding, electronic structure, and optical properties of conducting TixTa1-xN film growth, optical spectroscopy and ab initio calculations were used. Despite the different valence electron configuration of the constituent elements, Ta(d3s2) and Ti(d2s2), we show that TiN and TaN are completely soluble due to the hybridization of the d and sp electrons of the metals and N, respectively, that stabilizes the ternary TixTa1-xN systems to the rocksalt structure. The optical properties of TixTa1-xN have been studied using spectroscopic methods and detailed electronic structure calculations, revealing that the plasma energy of the fully dense TixTa1-xN is varying between 7.8 and 9.45 eV. Additional optical absorption bands are manifested due to the N p¿Ti/Ta d interband transition the t2g¿eg transition due to splitting of the metals¿ d band, with the major exception of the Ti0.50Ta0.50N, where the eg unoccupied states are not manifested due to the local structure of the ternary system; this finding is observed for the first time and proves previous assignments of optical transitions in TaN. [ABSTRACT FROM AUTHOR]

The spectroscopic methods were used to study the electronic structure and optical properties of conducting ternary transition metal nitrides consisting of metals of different groups of the periodic table of elements. The results provide insight into the plasma energy of the fully dense [Ti.sub.x][Ta.sub.1-x]N varying between 7.8 and 9.45 eV and the optical absorption bands manifested due to the N p -> Ti/Ta d interband transition.