Recent work suggests that the long-lived coherences observed in both natural and artificial light-harvesting systems (such as the Fenna-Matthews-Olson complex) could be attributed to the mixing of the pigments' electronic and vibrational degrees of freedom. To investigate the underlying mechanism of these long coherence lifetimes, a sophisticated description of interactions between the molecular aggregates and the nonequilibrium fluctuations in the surrounding environment is necessary. This is done by implementing the hierarchical equations of motion approach on model homodimers, a method used in the intermediate coupling regime for many molecular aggregates wherein the nonequilibrium environment phonons play nontrivial roles in exciton dynamics. Here we report a character change in the vibronic states-reflective of property mixing between the electronic and vibrational states-induced by an interplay between system coupling parameters within the exciton-vibrational near-resonance regime. This mixing dictates vital aspects of coherence lifetime; by tracking the degree of mixing, we are able to elucidate the relationship between coherence lifetime and both the electronic energy fluctuation and the vibrational relaxation dephasing pathways.

Methylamine is an abundant amine compound detected in the atmosphere which can affect the nature of atmospheric aerosol surfaces, changing their chemical and optical properties. Molecular dynamics simulation results show that methylamine accommodation on water is close to unity with the hydrophilic head group solvated in the interfacial environment and the methyl group pointing into the air phase. A detailed analysis of the hydrogen bond network indicates stronger hydrogen bonds between water and the primary amine group at the interface, suggesting that atmospheric trace gases will likely react with the methyl group instead of the solvated amine site. These findings suggest new chemical pathways for methylamine acting on atmospheric aerosols in which the methyl group is the site of orientation specific chemistry involving its conversion into a carbonyl site providing hydrophilic groups for uptake of additional water. This conversion may explain the tendency of aged organic aerosols to form cloud condensation nuclei. At the same time, formation of NH 2 radical and formaldehyde is suggested to be a new source for NH 2 radicals at aerosol surfaces, other than by reaction of absorbed NH 3 . The results have general implications for the chemistry of other amphiphilic organics, amines in particular, at the surface of atmospherically relevant aerosols. Published by AIP Publishing. [http://dx

G protein-coupled receptors (GPCRs) constitute a large family of receptor proteins that sense molecular signals on the exterior of a cell and activate signal transduction pathways within the cell. Modeling how an agonist activates such a receptor is fundamental for an understanding of a wide variety of physiological processes and it is of tremendous value for pharmacology and drug design. Inelastic electron tunneling spectroscopy (IETS) has been proposed as a model for the mechanism by which olfactory GPCRs are activated by a bound agonist. We apply this hyothesis to GPCRs within the mammalian nervous system using quantum chemical modeling. We found that non-endogenous agonists of the serotonin receptor share a particular IET spectral aspect both amongst each other and with the serotonin molecule: a peak whose intensity scales with the known agonist potencies. We propose an experiential validation of this model by utilizing lysergic acid dimethylamide (DAM-57), an ergot derivative, and its deuterated isotopologues; we also provide theoretical predictions for comparison to experiment. If validated our theory may provide new avenues for guided drug design and elevate methods of in silico potency/activity prediction.

The uncertainty relation is a fundamental limit in quantum mechanics and is of great importance to quantum information processing as it relates to quantum precision measurement. Due to interactions with the surrounding environment, a quantum system will unavoidably suffer from decoherence. Here, we investigate the dynamic behaviors of the entropic uncertainty relation of an atom-cavity interacting system under a bosonic reservoir during the crossover between Markovian and non-Markovian regimes. Specifically, we explore the dynamic behavior of the entropic uncertainty relation for a pair of incompatible observables under the reservoir-induced atomic decay effect both with and without quantum memory. We find that the uncertainty dramatically depends on both the atom-cavity and the cavity-reservoir interactions, as well as the correlation time, τ, of the structured reservoir. Furthermore, we verify that the uncertainty is anti-correlated with the purity of the state of the observed qubit-system. We also propose a remarkably simple and efficient way to reduce the uncertainty by utilizing quantum weak measurement reversal. Therefore our work offers a new insight into the uncertainty dynamics for multi-component measurements within an open system, and is thus important for quantum precision measurements.

The Heisenberg uncertainty principle describes a basic restriction on an observer's ability of precisely predicting the measurement of a pair of noncommuting observables, and virtually is at the core of quantum mechanics. Herein, the aim is to study the entropic uncertainty relation (EUR) under the background of a Schwarzschild black hole and its control. Explicitly, dynamical features of the measuring uncertainty via entropy are developed in a practical model where a stationary particle interacts with its surrounding environment while another particle-serving as a quantum memory reservoir-undergoes free fall in the vicinity of the event horizon of the Schwarzschild space-time. It shows higher Hawking temperatures would give rise to an inflation of the entropic uncertainty on the measured particle. This is suggestive of the fact the measurement uncertainty is strongly correlated with degree of mixing present in the evolving particles. Additionally, based on information flow theory, a physical interpretation for the observed dynamical behaviors related with the entropic uncertainty in such a genuine scenario is provided. Finally, an efficient strategy is proposed to reduce the uncertainty by non-tracing-preserved operations. Therefore, our explorations may improve the understanding of the dynamic entropic uncertainty in a curved space-time, and illustrate predictions of quantum measurements in relativistic quantum information sciences.

This study examines the impact of two of the most advanced dust emission schemes on the predictions of the weather research and forecasting model with chemistry (WRF-Chem) over the Middle East during a summer time period. Results show significant differences between the two simulations in the spatial distribution of dust emissions as well as in their size-resolved mass discretization. The AFWA scheme simulation predicts 30 % higher dust emission fluxes than the S11 module over the Arabian Peninsula (6.7 lg m -2 s -1 compared to 4.5 lg m -2 s -1 , respectively). In the S11 simulation 70 % of the emitted dust is in the 10-20 lm size range while the AFWA simulation assigns 50 % of dust emitted particles in the 6-12 lm size section. Both simulations reproduce the majority of the ambient PM 10 data (more than 70 %) within a factor of two. However, the S11 simulation predicts, on average, 50 % lower PM 10 concentrations compared to AFWA over the high resolution (2 9 2 km 2 ) domain of Qatar. Previous applications of WRF-Chem may have substantially overestimated the simulated dust in this region.

The vibrational theory of olfaction is an attempt to describe a possible mechanism for olfaction which is explanatory and provides researchers with a set of principles which permit predictions allowing for structure-odor relations. Similar theories have occurred several times throughout olfactory science; this theory has again recently come to prominence by Luca Turin, who suggested that inelastic electron tunneling is the method by which vibrations are detected by the olfactory receptors within the hose. This work is intended to convey to the reader an up-to-date account of the vibrational theory of olfaction, both the historical iterations as well as the present iteration. This text is designed to give a chronological account of both theoretical and experimental studies on the topic, while providing context, comments, and background where they were found to be needed.

The state-dependent spectroscopy of α-methylbenzyl radical (α-MeBz) has been studied under jet-cooled conditions. Two-color resonant two-photon ionization (2C-R2PI), laser-induced fluorescence, and dispersed fluorescence spectra were obtained for the D0-D1 electronic transition of this prototypical resonance-stabilized radical in which the methyl group is immediately adjacent to the primary radical site. Extensive Franck-Condon activity in hindered rotor levels was observed in the excitation spectrum, reflecting a reorientation of the methyl group upon electronic excitation. Dispersed fluorescence spectra from the set of internal rotor levels are combined with the excitation spectrum to obtain a global fit of the barrier heights and angular change of the methyl group in both D0 and D1 states. The best-fit methyl rotor potential in the ground electronic state (D0) is a flat-topped 3-fold potential (V3" = 151 cm(-1), V6" = 34 cm(-1)) while the D1 state has a lower barrier (V3' = 72 cm(-1), V6' = 15 cm(-1)) with Δφ = ± π/3, π, consistent with a reorientation of the methyl group upon electronic excitation. The ground state results are compared with calculations carried out at the DFT B3LYP level of theory using the 6-311+G(d,p) basis set, and a variety of excited state calculations are carried out to compare against experiment. The preferred geometry of the methyl rotor in the ground state is anti, which switches to syn in the D1 state and in the cation. The calculations uncover a subtle combination of effects that contribute to the shift in orientation and change in barrier in the excited state relative to ground state. Steric interaction favors the anti conformation, while hyperconjugation is greater in the syn orientation. The presence of a second excited state close by D1 is postulated to influence the methyl rotor properties. A resonant ion-dip infrared (RIDIR) spectrum in the alkyl and aromatic CH stretch regions was also recorded, probing in a complementary way the state-dependent conformation of α-MeBz. Using a scheme in which infrared depletion occurs between excitation and ionization steps of the 2C-R2PI process, analogous infrared spectra in D1 were also obtained, probing the response of the CH stretch fundamentals to electronic excitation. A reduced-dimension Wilson G-matrix model was implemented to simulate and interpret the observed infrared results. Finally, photoionization efficiency scans were carried out to determine the adiabatic ionization threshold of α-MeBz (IP = 6.835 ± 0.002 eV) and provide thresholds for ionization out of specific internal rotor levels, which report on the methyl rotor barrier in the cation state.