Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Simultaneous tunability of the electronic and phononic gaps in SnS2 under normal compressive strain

Controlled variation of the electronic properties of. two-dimensional (2D) materials by applying strain has emerged as a promising way to design materials for customized applications. Using density functional theory (DFT) calculations, we show that while the electronic structure and indirect band gap of SnS2 do not change significantly with the number of layers, they can be reversibly tuned by applying biaxial tensile (BT), biaxial compressive (BC), and normal compressive (NC) strains. Mono to multilayered SnS2 exhibit a reversible semiconductor to metal (S-M) transition with applied strain. For bilayer (2L) SnS2, the S-Mtransition occurs at the strain values of 17%,-26%, and -24% under BT, BC, and NC strains, respectively. Due to weaker interlayer coupling, the critical strain value required to achieve the S-Mtransition in SnS2 under NC strain is much higher than for MoS2. From a stability viewpoint, SnS2 becomes unstable at very low strain values on applying BC (-6.5%) and BT strains (4.9%), while it is stable even up to the transition point (-24%) in the case of NC strain. In addition to the reversible tuning of the electronic properties of SnS2, we also show tunability in the phononic band gap of SnS2, which increases with applied NC strain. This gap increases three times faster than for MoS2. This simultaneous tunability of SnS2 at the electronic and phononic levels with strain, makes it a potential candidate in field effect transistors (FETs) and sensors as well as frequency filter applications.

Influence of ion energy and substrate temperature on the optical and electronic properties of tetrahedral amorphous carbon (ta-C) films

The properties of amorphous carbon (a-C) deposited using a filtered cathodic vacuum arc as a function of the ion energy and substrate temperature are reported. The sp3 fraction was found to strongly depend on the ion energy, giving a highly sp3 bonded a-C denoted as tetrahedral amorphous carbon (ta-C) at ion energies around 100 eV. The optical band gap was found to follow similar trends to other diamondlike carbon films, varying almost linearly with sp2 fraction. The dependence of the electronic properties are discussed in terms of models of the electronic structure of a-C. The structure of ta-C was also strongly dependent on the deposition temperature, changing sharply to sp2 above a transition temperature, T1, of ≈200°C. Furthermore, T1 was found to decrease with increasing ion energy. Most film properties, such as compressive stress and plasmon energy, were correlated to the sp3 fraction. However, the optical and electrical properties were found to undergo a more gradual transition with the deposition temperature which we attribute to the medium range order of sp2 sites. We attribute the variation in film properties with the deposition temperature to diffusion of interstitials to the surface above T1 due to thermal activation, leading to the relaxation of density in context of a growth model. © 1997 American Institute of Physics.

Electronic structure and surface properties of SrBi2Ta2O9 and related oxides

The electronic structure of SrBi2Ta2O9 and related oxides such as SrBi2Nb2O9, Bi2WO6 and Bi3Ti4O12 have been calculated by the tight-binding method. In each case, the band gap is about 4.1 eV and the band edge states occur on the Bi-O layers and consist of mixed O p/Bi s states at the top of the valence band and Bi p states at the bottom of the conduction band. The main difference between the compounds is that Nb 5d and Ti 4d states in the Nb and Ti compounds lie lower than the Ta 6d states in the conduction band. The surface pinning levels are found to pin Schottky barriers 0.8 eV below the conduction band edge.

Electronic structure of the layered ferroelectric perovskite SrBi2Ta2O9

The band structure of the Bi layered perovskite SrBi2Ta2O9 (SBT) has been calculated by the tight binding method. We find both the valence and conduction band edges to consist of states primarily derived from the Bi-O layer rather than the perovskite Sr-Ta-O block. The valence band maximum arises from O p and some Bi s states, while the conduction band minimum consists of Bi p states, with a band gap of 5.1 eV. It is argued that the Bi-O layers largely control the electronic response of SBT while the ferroelectric response originates from the perovskite Sr-Ta-O block. Bi and Ta centered traps are calculated to be shallow, which may account in part for the excellent fatigue properties of SBT.

Electronic structure of the ferroelectric layered perovskite SrBi2Ta2O9

The band structure of the layered perovskite SrBi2Ta2O9 (SBT) was calculated by tight binding and the valence band density of states was measured by x-ray photoemission spectroscopy. We find both the valence and conduction band edges to consist of states primarily derived from the Bi-O layer rather than the perovskite Sr-Ta-O blocks. The valence band maximum arises from O p and some Bi s states, while the conduction band minimum consists of Bi p states, with a wide band gap of 5.1 eV. It is argued that the Bi-O layers largely control the electronic response whereas the ferroelectric response originates mainly from the perovskite Sr-Ta-O block. Bi and Ta centered traps are calculated to be shallow, which may account in part for its excellent fatigue properties. © 1996 American Institute of Physics.