Singlet fission spin dynamics from molecular structure: a modular computational pipeline

Singlet fission, which has applications in areas ranging form solar energy to quantum information, relies critically on transitions within a multi-spin manifold. These transitions are driven by fluctuations in the spin-spin exchange interaction, which have been linked to changes in nuclear geometry or exciton migration. Whilst simple calculations have supported this mechanism, to date little effort has been made to model realistic fluctuations which are informed by the actual structure and properties of physical materials. In this paper, we develop a modular computational pipeline for calculating singlet fission spin dynamics by way of electronic structural calculations, molecular dynamics, and numerical models of spin dynamics. The outputs of this pipeline aid in the interpretation of measured spin dynamics and allow us to place constraints on geometric fluctuations which are consistent with these observations.Comment: 23 pages (including SI), 7 Figure

Hydrogen-atom Attack on Phenol and Toluene is \u3cem\u3eortho\u3c/em\u3e-directed

The reaction of H + phenol and H/D + toluene has been studied in a supersonic expansion after electric discharge. The (1 + 1′) resonance-enhanced multiphoton ionization (REMPI) spectra of the reaction products, at m/z = parent + 1, or parent + 2 amu, were measured by scanning the first (resonance) laser. The resulting spectra are highly structured. Ionization energies were measured by scanning the second (ionization) laser, while the first laser was tuned to a specific transition. Theoretical calculations, benchmarked to the well-studied H + benzene → cyclohexadienyl radical reaction, were performed. The spectrum arising from the reaction of H + phenol is attributed solely to the ortho-hydroxy-cyclohexadienyl radical, which was found in two conformers (syn and anti). Similarly, the reaction of H/D + toluene formed solely the ortho isomer. The preference for the ortho isomer at 100–200 K in the molecular beam is attributed to kinetic, not thermodynamic effects, caused by an entrance channel barrier that is ∼5 kJ mol−1 lower for ortho than for other isomers. Based on these results, we predict that the reaction of H + phenol and H + toluene should still favour the ortho isomer under elevated temperature conditions in the early stages of combustion (200–400 °C)

Tricuspid Valve Replacement in a Patient with a Leadless Cardiac Pacemaker: Current Guidelines and Recommendations for Perioperative Management

Leadless cardiac pacemakers were developed to reduce complications associated with conventional transvenous pacemakers. While this technology is still relatively new, devices are increasingly being implanted. The perioperative management of patients with these devices has been underreported; we thus seek to add to the limited body of knowledge of perioperative management of patients with leadless cardiac pacemakers. An elderly female patient with a Micra VR transcatheter pacing system leadless cardiac pacemaker placed for tachycardia-bradycardia syndrome with intermittent complete heart block was scheduled for elective tricuspid valve replacement for severe tricuspid regurgitation. Pacemaker interrogation was performed several hours prior to the scheduled surgery based on the electrophysiologist's availability; the device was kept in its programmed VVIR mode, and the base rate was increased from 60 to 80 beats per minute in anticipation of the upcoming surgery. Upon preoperative evaluation, the anesthesiologist asked that the electrophysiology team be placed on standby intraoperatively due to the concern that either oversensing in the setting of pacemaker dependence and/or undesirable tachycardia from rate-responsive pacing could occur. The surgeon used monopolar electrocautery for the duration of the cardiac surgery. Despite the patient having evidence of pacemaker dependence in the intensive care unit preoperatively, no electromagnetic interference leading to oversensing nor rate modulation was detected during intraoperative electrocardiographic and intraarterial invasive monitoring. Evidence-based guidelines regarding perioperative management specifically of leadless cardiac pacemakers do not exist. As these devices become more prevalent, further evaluation will be paramount to determine whether existing guidelines for perioperative management of conventional transvenous pacemakers apply

Energy transfer in pendant perylene diimide copolymers

We report the synthesis, characterisation and polymerisation of two novel asymmetric perylene diimide acrylate monomers. The novel monomers form a sensitiser–acceptor pair capable of undergoing Förster resonance energy transfer, and were incorporated as copolymers with tert-butyl acrylate. The tert-butyl acrylate units act as spacers along the polymer chain allowing high concentrations of dye while mitigating aggregate quenching, leading to persistent fluorescence in the solid state at high concentrations of up to 0.3 M. Analysis of fluorescence kinetics showed efficient energy transfer between the optically dense sensitiser and the lower concentration acceptor luminophores within the polymer. This reduced reabsorption within the material demonstrates that the copolymer-scaffold energy transfer system has potential for use in luminescent solar concentrators

The optical spectrum of a large isolated polycyclic aromatic hydrocarbon: hexa-peri-hexabenzocoronene, C42H18

The first optical spectrum of an isolated polycyclic aromatic hydrocarbon large enough to survive the photophysical conditions of the interstellar medium is reported. Vibronic bands of the first electronic transition of the all benzenoid polycyclic aromatic hydrocarbon hexa-peri-hexabenzocoronene were observed in the 4080-4530 Angstrom range by resonant 2-color 2-photon ionization spectroscopy. The strongest feature at 4264 Angstrom is estimated to have an oscillator strength of f=1.4x10^-3, placing an upper limit on the interstellar abundance of this polycyclic aromatic hydrocarbon at 4x10^12 cm^-2, accounting for a maximum of ~0.02% of interstellar carbon. This study opens up the possibility to rigorously test neutral polycyclic aromatic hydrocarbons as carriers of the diffuse interstellar bands in the near future.Comment: 9 pages, 1 figure. Fixed a typo on the frequency of the 'b' ban

Decoupled sedimentary records of combustion : causes and implications

Author Posting. © American Geophysical Union, [year]. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 43 (2016): 5098–5108, doi:10.1002/2016GL069253.Pyrogenic carbon (PyC) is a collective term for carbon-rich residues comprised of a continuum of products arising from biomass burning and fossil-fuel combustion. PyC is ubiquitous in the environment where it can be transported by wind and water before being deposited in aquatic sediments. We compare results from four different methods used to trace PyC that were applied to a high-temporal resolution sedimentary record in order to constrain changes in PyC concentrations and fluxes over the past ~250 years. We find markedly discordant records for different PyC tracers, particularly during the preindustrial age, implying different origins and modes of supply of sedimentary PyC. In addition to providing new insights into the composition of sedimentary combustion products, this study reveals that elucidation of past combustion processes and development of accurate budgets of PyC production and deposition on local to regional scales requires careful consideration of both source characteristics and transport processes.UZH; NSF Grant Numbers: OCE-9708478, CHE-00891722016-11-3