Generalized trajectory surface-hopping method for internal conversion and intersystem crossing

Trajectory-based fewest-switches surface-hopping (FSSH) dynamics simulations have become a popular and reliable theoretical tool to simulate nonadiabatic photophysical and photochemical processes. Most available FSSH methods model internal conversion. We present a generalized trajectory surface-hopping (GTSH) method for simulating both internal conversion and intersystem crossing processes on an equal footing. We consider hops between adiabatic eigenstates of the non-relativistic electronic Hamiltonian (pure spin states), which is appropriate for sufficiently small spin-orbit coupling. This choice allows us to make maximum use of existing electronic structure programs and to minimize the changes to available implementations of the traditional FSSH method. The GTSH method is formulated within the quantum mechanics (QM)/molecular mechanics framework, but can of course also be applied at the pure QM level. The algorithm implemented in the GTSH code is specified step by step. As an initial GTSH application, we report simulations of the nonadiabatic processes in the lowest four electronic states (S0, S1, T1, and T2) of acrolein both in vacuo and in acetonitrile solution, in which the acrolein molecule is treated at the ab initio complete-active-space self-consistent-field level. These dynamics simulations provide detailed mechanistic insight by identifying and characterizing two nonadiabatic routes to the lowest triplet state, namely, direct S1 → T1 hopping as major pathway and sequential S1 → T2 → T1 hopping as minor pathway, with the T2 state acting as a relay state. They illustrate the potential of the GTSH approach to explore photoinduced processes in complex systems, in which intersystem crossing plays an important role

Possible discovery of the r-process characteristics in the abundances of metal-rich barium stars

We study the abundance distributions of a sample of metal-rich barium stars provided by Pereira et al. (2011) to investigate the s- and r-process nucleosynthesis in the metal-rich environment. We compared the theoretical results predicted by a parametric model with the observed abundances of the metal-rich barium stars. We found that six barium stars have a significant r-process characteristic, and we divided the barium stars into two groups: the r-rich barium stars ($C_r>5.0$, [La/Nd]\,$<0$) and normal barium stars. The behavior of the r-rich barium stars seems more like that of the metal-poor r-rich and CEMP-r/s stars. We suggest that the most possible formation mechanism for these stars is the s-process pollution, although their abundance patterns can be fitted very well when the pre-enrichment hypothesis is included. The fact that we can not explain them well using the s-process nucleosynthesis alone may be due to our incomplete knowledge on the production of Nd, Eu, and other relevant elements by the s-process in metal-rich and super metal-rich environments (see details in Pereira et al. 2011).Comment: 5 pages, 5 figures, accepted for publication in A&

An automated method for comparing motion artifacts in cine four-dimensional computed tomography images.

The aim of this study is to develop an automated method to objectively compare motion artifacts in two four-dimensional computed tomography (4D CT) image sets, and identify the one that would appear to human observers with fewer or smaller artifacts. Our proposed method is based on the difference of the normalized correlation coefficients between edge slices at couch transitions, which we hypothesize may be a suitable metric to identify motion artifacts. We evaluated our method using ten pairs of 4D CT image sets that showed subtle differences in artifacts between images in a pair, which were identifiable by human observers. One set of 4D CT images was sorted using breathing traces in which our clinically implemented 4D CT sorting software miscalculated the respiratory phase, which expectedly led to artifacts in the images. The other set of images consisted of the same images; however, these were sorted using the same breathing traces but with corrected phases. Next we calculated the normalized correlation coefficients between edge slices at all couch transitions for all respiratory phases in both image sets to evaluate for motion artifacts. For nine image set pairs, our method identified the 4D CT sets sorted using the breathing traces with the corrected respiratory phase to result in images with fewer or smaller artifacts, whereas for one image pair, no difference was noted. Two observers independently assessed the accuracy of our method. Both observers identified 9 image sets that were sorted using the breathing traces with corrected respiratory phase as having fewer or smaller artifacts. In summary, using the 4D CT data of ten pairs of 4D CT image sets, we have demonstrated proof of principle that our method is able to replicate the results of two human observers in identifying the image set with fewer or smaller artifacts

Rotation in galaxy clusters from MUSIC simulations with the kinetic Sunyaev-Zel'dovich effect

We propose in this work its application for the detection of possible coherent rotational motions in the hot intra-cluster medium. We select a sample of massive, relaxed and rotating galaxy clusters from Marenostrum-mUltidark SImulations of galaxy Clusters (MUSIC), and we produce mock maps of the temperature distortion produced by the kinetic Sunyaev-Zel'dovich effect by exploring six different lines of sight, in the best observational condition. These maps are compared with the expected signal computed from a suitable theoretical model in two cases: (i) focusing only on the contribution from the rotation, and (ii) accounting also for the cluster bulk motion. We find that the parameters of the model assumed for the radial profile of the rotational velocity, averaged over the considered lines of sight, are in agreement within two standard deviations at most with independent estimates from the simulation data, without being significantly affected by the presence of the cluster bulk term. The amplitude of the rotational signal is, on average, of the order of 23 per cent of the total signal accounting also for the cluster bulk motion, and its values are consistent with the literature. The projected bulk velocity of the cluster is also recovered at the different lines of sight, with values in agreement with the simulation dataASB acknowledges funding from Sapienza Università di Roma - Progetti per Avvio alla Ricerca Anno 2017, prot. AR11715C82402BC

Photodynamics of Schiff Base Salicylideneaniline: Trajectory Surface-Hopping Simulations

We report a computational study on the photochemistry of the prototypical aromatic Schiff base salicylideneaniline in the gas phase using static electronic structure calculations (TDDFT, OM2/MRCI) and surface-hopping dynamics simulations (OM2/MRCI). Upon photoexcitation of the most stable cis-enol tautomer into the bright S1 state, we find an ultrafast excited-state proton transfer that is complete within tens of femtoseconds, without any C═N double bond isomerization. The internal conversion of the resulting S1 cis-keto species is initiated by an out-of-plane motion around the C–C single bond, which guides the molecule toward a conical intersection that provides an efficient deactivation channel to the ground state. We propose that the ease of this C–C single bond rotation regulates fluorescence quenching and photocoloration in condensed-phase environments. In line with previous work, we find the S1 cis-keto conformer to be responsible for fluorescence, especially in rigid surroundings. The S0 cis-keto species is a transient photoproduct, while the stable S0 trans-keto photoproduct is responsible for photochromism. The trajectory calculations yield roughly equal amounts of the S0 cis-enol and trans-keto photoproducts. Methodologically, full-dimensional nonadiabatic dynamics simulations are found necessary to capture the preferences among competitive channels and to gain detailed mechanistic insight into Schiff base photochemistry

How Photoisomerization Drives Peptide Folding and Unfolding: Insights from QM/MM and MM Dynamics Simulations

Photoswitchable azobenzene cross-linkers can control the folding and unfolding of peptides by photoisomerization and can thus regulate peptide affinities and enzyme activities. Using quantum mechanics/molecular mechanics (QM/MM) methods and classical MM force fields, we report the first molecular dynamics simulations of the photoinduced folding and unfolding processes in the azobenzene cross-linked FK-11 peptide. We find that the interactions between the peptide and the azobenzene cross-linker are crucial for controlling the evolution of the secondary structure of the peptide and responsible for accelerating the folding and unfolding events. They also modify the photoisomerization mechanism of the azobenzene cross-linker compared with the situation in vacuo or in solution

Mechanism for the Nonadiabatic Photooxidation of Benzene to Phenol: Orientation-Dependent Proton-Coupled Electron Transfer

An efficient catalytic one-step conversion of benzene to phenol was achieved recently by selective photooxidation under mild conditions with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as the photocatalyst. Herein, high-level electronic structure calculations in the gas phase and in acetonitrile solution are reported to explore the underlying mechanism. The initially populated 1ππ* state of DDQ can relax efficiently through a nearby dark 1nπ* doorway state to the 3ππ* state of DDQ, which is found to be the precursor state involved in the initial intermolecular electron transfer from benzene to DDQ. The subsequent triplet-state reaction between DDQ radical anions, benzene radical cations, and water is computed to be facile. The formed DDQH and benzene-OH radicals can undergo T1→S0 intersystem crossing and concomitant proton-coupled electron transfer (PCET) to generate the products DDQH2 and phenol. Two of the four considered nonadiabatic pathways involve an orientation-dependent triplet PCET process, followed by intersystem crossing to the ground state (S0). The other two first undergo a nonadiabatic T1→S0 transition to produce a zwitterionic S0 complex, followed by a barrierless proton transfer. The present theoretical study identifies novel types of nonadiabatic PCET processes and provides detailed mechanistic insight into DDQ-catalyzed photooxidation

X-Ray Spectral Variability of Extreme BL Lac AGN H1426+428

Between 7 March 2002 and 15 June 2002, intensive X-ray observations were carried out on the extreme BL Lac object H1426+428 with instruments on board the Rossi X-ray Timing Explorer (RXTE). These instruments provide measurements of H1426+428 in the crucial energy range that characterizes the first peak of its spectral energy distribution. This peak, which is almost certainly due to synchrotron emission, has previously been inferred to be in excess of 100 keV. By taking frequent observations over a four-month campaign, which included $\sim$450 ksec of RXTE time, studies of flux and spectral variability on multiple timescales were performed, along with studies of spectral hysteresis. The 3-24 keV X-ray flux and spectra exhibited significant variability, implying variability in the location of the first peak of the spectral energy distribution. Hysteresis patterns were observed, and their characteristics have been discussed within the context of emission models.Comment: accepted for publication in Astrophysical Journa