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We present a spectral analysis of NuSTAR and NICER observations of the luminous, persistently accreting neutron star (NS) low-mass X-ray binary Cygnus X-2. The data were divided into different branches that the source traces out on the Z-track of the X-ray color–color diagram; namely, the horizontal branch, the normal branch, and the vertex between the two. The X-ray continuum spectrum was modeled in two different ways that produced comparable quality fits. The spectra showed clear evidence of a reflection component in the form of a broadened Fe K line, as well as a lower-energy emission feature near 1 keV likely due to an ionized plasma located far from the innermost accretion disk. We account for the reflection spectrum with two independent models (RELXILLNS and RDBLUR* RFXCONV). The inferred inclination is in agreement with earlier estimates from optical observations of ellipsoidal lightcurve modeling (RELXILLNS: i = 67° ± 4°; RDBLUR* RFXCONV: i = 60° ± 10°). The inner disk radius remains close to the NS (Rin 1.15 RISCO) regardless of the source position along the Z-track or how the 1 keV feature is modeled. Given the optically determined NS mass of 1.71 ± 0.21 Me, this corresponds to a conservative upper limit of Rin 19.5 km for M = 1.92 Me or Rin 15.3 km for M = 1.5 Me. We compare these radius constraints to those obtained from NS gravitational wave merger events and recent NICER pulsar lightcurve modeling measurements.

The electronic spectroscopy and photophysics of 1,2-benzazulene (BzAz) have been examined in solution and in thin solid films, with the objective of comparing its intramolecular and intermolecular excited state decay processes with those of azulene. Unlike azulene, the S2 – S0 absorption and fluorescence spectra exhibit a clear mirror image relationship dominated by a single strong Franck-Condon active progression. Picosecond transient absorption spectra and non-linear S2 fluorescence upconversion experiments reveal lifetimes that follow a well-established energy gap law correlation, indicative of a dominant S2 – S1 decay route. Mechanistic interpretations, including the possibility of S2 singlet fission in aggregates, are discussed.

Calix[4]azulene is a non-alternant aromatic calixarene composed of four azulene chromophores linked by methylene groups. Its photochemical stability, photophysical properties and an analysis of its electronic spectra are reported using monomeric azulene as a known reference standard. The molecule is stable when excited in its visible and near uv absorptions and, unlike azulene, produces no measurable “anti-Kasha” fluorescence when excited to its second excited singlet state, S2. This lack of fluorescence places the lifetime of the initially excited, photochemically stable S2 species at less than 1 picosecond. A significant, bathochromic shift of the S2 absorption band system in the calixarene, and the appearance of an additional weak, broad absorption immediately to the red signals significant intramolecular chromophore interaction. Femtosecond transient absorption spectroscopy using excitation in this red-shifted tail of the S2 band system reveals a very weak transient signal most of which decays within one ps, but with suggestions of a slightly longer-lived underlying component. No longer-lived T1 triplet transient is observed. A complete analysis of the data using monomeric azulene as a reference suggests, following elimination of several alternate mechanisms, that the initially excited S2 species may be relaxing via a novel singlet-singlet fission process.

A zinc porphyrin-pendant norbornene polymer with a rigid backbone characterized by a 2:1 E/Z isomeric structure ratio has been synthesized, and its spectroscopic and photophysical properties are examined. Zinc tetraphenylporphyrin, the porphyrin-substituted norbornene monomer, and a previously reported zinc porphyrin-pendant polymer with a flexible polymethylene backbone have been used as comparators. Unlike its flexible counterpart, the rigid norbornene polymer exhibits clear exciton splitting of its Soret band, much more rapid relaxation rates of its excited singlet states, and a very small yield of an unusually short-lived triplet state. Unlike the flexible pendant polymer, which exhibits excimeric S2 fluorescence as a result of chromophore rotation, anti-Kasha emission from the norbornene polymer originates primarily from the unperturbed porphyrin E region. The low triplet yield in the polymer is attributed to greatly increased rates of competing internal conversion within the singlet manifold. Nevertheless, upconverted delayed fluorescence that is quenched by oxygen is observed upon intense steady-state Q-band excitation of degassed polymer solutions, signaling direct triplet involvement. Consistent with the polymer’s rigid structure, this biexcitonic process is assigned to ultrafast singlet exciton migration and triplet–triplet annihilation following absorption of a second photon by the small steady-state concentration of polymer triplets.