Beebefitzgerald1531

The Ã2A1-X̃2E electronic transition of the jet-cooled trichlorosiloxy (SiCl3O) free radical has been observed for the first time in the 650-590 nm region by laser induced fluorescence (LIF) detection. The radical was produced by a pulsed electric discharge through a mixture of silicon tetrachloride and oxygen in high pressure argon at the exit of a pulsed molecular beam valve. The LIF spectrum shows low frequency intervals, which we assign as activity in the normally forbidden degenerate v5' and v6' modes, indicative of a significant Jahn-Teller effect in the ground state. Single vibronic level emission spectra show level dependent spin-orbit splittings in the ground state and Jahn-Teller predictable variations depending on which upper state level is pumped. The measured lower state energy levels have been fitted to a Jahn-Teller model that simultaneously includes spin-orbit coupling and linear and quadratic multimode coupling. In SiCl3O, the Jahn-Teller interaction predominates over spin-orbit effects.Velocity-map ion imaging has been used to study the vibrational predissociation dynamics of the HCl dimer following infrared (IR) excitation in the HCl stretch overtone region near 1.77 Å. HCl monomer predissociation products were detected state-selectively using 2 + 1 resonance-enhanced multiphoton ionization spectroscopy. The IR action spectrum shows the free HCl stretch (2ν1), the bound HCl stretch (2ν2), and a combination band involving the intermolecular van der Waals stretching mode (2ν2 + ν4). Fragment speed distributions extracted from ion images obtained for a range of HCl(v = 0, 1; J) levels following vibrational excitation on the 2ν1 and 2ν2 bands yield the correlated product pair distributions. All product pairs comprise HCl(v = 1) + HCl(v = 0) and show a strong propensity to minimize the recoil kinetic energy. Highly non-statistical and mode-dependent HCl product rotational distributions are observed, in contrast to that observed following stretch fundamental excitation. Predissociation lifetimes are also mode-dependent excitation of the free HCl leads to τVP = 13 ± 1 ns, while the bound stretch has a shorter lifetime τVP ≤ 6 ns. The dimer dissociation energy determined from energy conservation (D0 = 397 ± 7 cm-1) is slightly smaller than the previously reported values. The results are discussed in the context of previous observations for (HF)2 and (HCl)2 after excitation of HX stretch fundamentals and models for vibrational predissociation.Photocatalysis is a promising sustainable method to generate solar fuels for the future, as well as having other applications such as water/air purification. However, the performance of photocatalysts is often limited by poor charge carrier dynamics. To improve charge carrier dynamics, it is necessary to characterize and understand charge carrier behavior in photocatalytic systems. This critical review will present Transient Absorption Spectroscopy (TAS) as a useful technique for understanding the behavior of photoexcited charges in semiconductor photocatalysts. The role of TAS amongst other techniques for characterizing charge carrier behavior will be outlined. Basic principles behind TAS will be introduced, and interpretation of TAS spectra and kinetics will be discussed in the context of exemplar literature. It will be demonstrated that TAS is a powerful technique to obtain fundamental understanding of the behavior of photoexcited charges.CP2K is an open source electronic structure and molecular dynamics software package to perform atomistic simulations of solid-state, liquid, molecular, and biological systems. It is especially aimed at massively parallel and linear-scaling electronic structure methods and state-of-the-art ab initio molecular dynamics simulations. Excellent performance for electronic structure calculations is achieved using novel algorithms implemented for modern high-performance computing systems. This review revisits the main capabilities of CP2K to perform efficient and accurate electronic structure simulations. The emphasis is put on density functional theory and multiple post-Hartree-Fock methods using the Gaussian and plane wave approach and its augmented all-electron extension.Many-electron wavepacket dynamics based on time-dependent configuration interaction (TDCI) is a numerically rigorous approach to quantitatively model electron transfer across molecular junctions. see more TDCI simulations of cyanobenzene thiolates-para- and meta-linked to an acceptor gold atom-show donor states conjugating with the benzene π-network to allow better through-molecule electron migration in the para isomer compared to the meta counterpart. For dynamics involving non-conjugating states, we find electron injection to stem exclusively from distance-dependent non-resonant quantum mechanical tunneling, in which case the meta isomer exhibits better dynamics. The computed trend in donor-to-acceptor net-electron transfer through differently linked azulene bridges agrees with the trend seen in low-bias conductivity measurements. Disruption of π-conjugation has been shown to be the cause of diminished electron injection through 1,3-azulene, a pathological case for a graph-based diagnosis of the destructive quantum interference. Furthermore, we demonstrate the quantum interference of many-electron wavefunctions to drive para-vs-meta selectivity in the coherent evolution of superposed π(CN)- and σ(NC-C)-type wavepackets. Analyses reveal that in the para-linked benzene, σ and π MOs localized at the donor terminal are in-phase, leading to the constructive interference of electron density distribution, while the phase-flip of one of the MOs in the meta isomer results in the destructive interference. These findings suggest that a priori detection of orbital phase-flip and quantum coherence conditions can aid in molecular device design strategies.Light absorption or fluorescence excitation spectroscopy of alkali atoms attached to 4He droplets is investigated as a possible way for detecting the presence of vortices. To this end, we have calculated the equilibrium configuration and energetics of alkali atoms attached to a 4He1000 droplet hosting a vortex line using 4He density functional theory. We use them to study how the dipole absorption spectrum of the alkali atom is modified when the impurity is attached to a vortex line. Spectra are found to be blue-shifted (higher frequencies) and broadened compared to vortex-free droplets because the dimple in which the alkali atom sits at the intersection of the vortex line and the droplet surface is deeper. This effect is smaller for lighter alkali atoms and all the more so when using a quantum description since, in this case, they sit further away from the droplet surface on average due to their zero-point motion. Spectral modifications due to the presence of a vortex line are minor for np ← ns excitation and therefore insufficient for vortex detection.