S 2p and P 2p Core Level Spectroscopy of PPT Ambipolar Material and Its Building Block Moieties

The near-edge X-ray absorption fine structure (NEXAFS and X-ray photoelectron (XP) spectra of gas-phase 2,8-bis-(diphenylphosphoryl)dibenzo[b,d]thiophene (PPT) and triphenylphosphine oxide (TPPO) have been measured at the S and P L-II,L-III-edge regions. The time-dependent density functional theory (TDDFT) based on the relativistic two-component zeroth-order regular approximation approach has been used to provide an assignment of the experimental spectra, giving the contribution of the spin-orbit splitting and of the molecular-field splitting to the sulfur and phosphor binding energies. Computed XP and NEXAFS spectra agree well with the experimental measurements. In going from dibenzothiophene and TPPO to PPT, the nature of the most intense S 2p and P 2p NEXAFS features are preserved; this trend suggests that the electronic and geometric behaviors of the S and P atoms in the two building block moieties are conserved in the more complex system of PPT. This work enables us to shed some light onto the structure of the P-O bond, a still highly debated topic in the chemical literature. Since the S 2p and P 2p NEXAFS intensities provide specific information on the higher-lying localized sigma*(C-S) and sigma*(P-O) virtual MOs, we have concluded that P 3d AOs are not involved in the formation of the P-O bond. Moreover, the results support the mechanism of negative hyperconjugation, by showing that transitions toward sigma*(P-O) states occur at lower energies with respect to those toward it pi*(P-O) states

Carbon and Nitrogen K-Edge NEXAFS Spectra of Indole, 2,3-Dihydro-7-azaindole, and 3-Formylindole

The near-edge X-ray absorption fine structure (NEXAFS) spectra of indole, 2,3-dihydro-7-azaindole, and 3-formylindole in the gas phase have been measured at the carbon and nitrogen K-edges. The spectral features have been interpreted based on density functional theory (DFT) calculations within the transition potential (TP) scheme, which is accurate enough for a general description of the measured C 1s NEXAFS spectra as well as for the assignment of the most relevant features. For the nitrogen K-edge, the agreement between experimental data and theoretical spectra calculated with TP-DFT was not quite satisfactory. This discrepancy was mainly attributed to the many-body effects associated with the excitation of the core electron, which are better described using the time-dependent density functional theory (TDDFT) with the range-separated hybrid functional CAM-B3LYP. An assignment of the measured N 1s NEXAFS spectral features has been proposed together with a complete description of the observed resonances. Intense transitions from core levels to unoccupied antibonding π* states as well as several transitions with mixed-valence/Rydberg or pure Rydberg character have been observed in the C and N K-edge spectra of all investigated indoles

\u201cSimulation of core-electron spectroscopies of gas-phase molecules and adsorbates by DFT and TDDFT methods\u201d

The phD thesis entitled \u201cSimulation of core-electron spectroscopies of gas-phase molecules and adsorbates by DFT and TDDFT methods\u201d deals with the simulation and interpretation of data obtained from X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure Spectroscopy (NEXAFS) of molecules in the gas phase and adsorbed on metal surfaces. In particular, studies in the gas-phase have focused on the elucidation of the electronic structure of molecular building blocks that can be exploited for the design of novel high-performance electronic and optoelectronic devices, while investigations on surface chemistry put a special emphasis on the characterization of the electronic structure of boron-containing adsorbates that can be used for surface functionalization. The main collaborations implicated in these studies have involved experimentalists afferent to the Gas Phase Photoemission and ALOISA beam lines of the Elettra Synchrotron in Trieste, the Department of Physics and Astronomy, Molecular and Condensed Matter Physics of Uppsala University (Sweden), and the Molecular Solids Group of the Philipps University of Marburg (Germany). To establish and quantify the relationship between the measured spectral features and the electronic structure information, theoretical calculations by means of density functional theory (DFT) and its time-dependent generalization (TDDFT) in the linear response regime have been performed, thus supporting XPS and NEXAFS experimental measurements. In many instances, the agreement between theory and experiment has proven to be remarkable, allowing a reliable assignment of the main spectral features, and their association with the different atomic contributions. Furthermore, the employed computational methods have provided valuable and original outcomes, with new insights on the nature of the virtual states implicated in the X-ray absorption process

Computational NEXAFS Characterization of Molecular Model Systems for 2D Boroxine Frameworks

The electronic properties of 2D boroxine networks are computationally investigated by simulating the NEXAFS spectra of a series of molecular models, with or without morphologic defects, with respect to the ideal honeycomb structure. The models represent portions of an irregular 2D boroxine framework obtained experimentally, as supported by the Au(111) surface. The B K-edge NEXAFS spectra are calculated within the transition potential (TP) approximation (DFT-TP). The role of the Au(111) supporting surface on the spectral features has also been investigated by comparing the calculated spectra of a defect-rich model in its free-standing and supported form. The calculated NEXAFS spectra differ from the experimental ones, as the position of the main resonance does not match in the two cases. This finding could suggest the presence of a strong interaction of the 2D boroxine network with the Au substrate, which is not captured in the model calculations. However, good agreement between measured and calculated B K-edge NEXAFS spectra is obtained for a model system, namely, trihydroxy boroxine, in which the B atoms are less screened by the valence electrons compared to the B–B linked boroxine network models considered here. These results suggest catalytic activity in the gold substrate in promoting a weakening or even the breaking of the B–B bond, which is not revealed by calculations

Correlation effects in B1s core-excited states of boronic-acid derivatives: An experimental and computational study

We performed a theoretical investigation on the influence of electronic correlation effects on the B1s NEXAFS spectrum of boronic acid derivatives, namely, boric acid [B(OH)3], phenyl boronic acid (PBA), and 1,4-phenyl diboronic acid (PDBA), employing different computational schemes of increasing complexity, ranging from the purely one-electron scheme based on the transition potential method of density functional theory (DFT-TP), time-dependent DFT (TDDFT), and multiconfigurational self-consistent field (MCSCF). We also report experimental measurements of the B1s NEXAFS spectra of the aforementioned molecules together with the high-resolution C1s NEXAFS spectrum of PBA. We demonstrate that due to the shallow B1s core energy levels compared to C, O, and N, the inclusion of static correlation effects, which can be incorporated by using multireference approaches to excited states, assumes a decisive role in reconciling experiment and theory on B1s core-electron excitation energies and oscillator strengths to valence states. This claim is corroborated by the good agreement that we find between the DFT-TP calculated C1s NEXAFS spectrum and that experimentally measured for PBA and by the failure of both DFT-TP and TDDFT approaches with a selection of xc functionals kernels to properly describe the B1s NEXAFS spectrum of PBA and PDBA, at variance with the good agreement with the experiment that is found by employing the MCSCF wave function approach

PPT Isolated Molecule and Its Building Block Moieties Studied by C1s and O 1s Gas Phase X\u2011ray Photoelectron and Photoabsorption Spectroscopies

ABSTRACT: The present study is focused on the comprehensive gas phase electronic structure characterization of 2,8-bis-(diphenylphosphoryl)-dibenzo[b,d]thiophene (PPT), a promising ambipolar phosphorescent host material recently introduced in organic light-emitting diodes (OLEDs). This molecular system can be considered ideally formed by two diphenylphosphine oxide (dPPO) moieties functionalizing the small dibenzothiophene (DBT) core. PPT is characterized by high triplet energy and is known as good vacuum sublimable electron transporting material for blue OLEDs. The triphenyl phosphine oxide (TPPO) molecule has been chosen as the model compound of the dPPO groups in PPT. A combined experimental and theoretical study by density functional theory of the gas phase electronic structure of TPPO and PPT has been performed through X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy measured at the carbon and oxygen 1s regions. The study represents a detailed characterization of the impact of the single building blocks on the electronic structure of the whole PPT molecule. Moreover, it confirms that the phosphine oxide groups act as breaking points of the \u3c0-conjugation between the DBT core of PPT and the outer groups, leaving the electronic structures of the compound practically matching those of the central DBT moiety