uu.seUppsala University Publications
Change search
Link to record
Permanent link

Direct link
BETA
Puglia, Carla
Alternative names
Publications (10 of 37) Show all publications
Ciavardini, A., Coreno, M., Callegari, C., Spezzani, C., De Ninno, G., Ressel, B., . . . Piccirillo, S. (2019). Ultra-Fast-VUV Photoemission Study of UV Excited 2-Nitrophenol. Journal of Physical Chemistry A, 123(7), 1295-1302
Open this publication in new window or tab >>Ultra-Fast-VUV Photoemission Study of UV Excited 2-Nitrophenol
Show others...
2019 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 123, no 7, p. 1295-1302Article in journal (Refereed) Published
Abstract [en]

The initial deactivation pathways of gaseous 2-nitrophenol excited at 268 nm were investigated by time-resolved photoelectron spectroscopy (TRPES) with femtosecond-VUV light, produced by a monochromatized high harmonic generation source. TRPES allowed us to obtain new, valuable experimental information about the ultrafast excited-state dynamics of 2-nitrophenol in the gas phase. In accord with recent ab initio on-the-fly nonadiabatic molecular dynamic simulations, our results validate the occurrence of an ultrafast intersystem crossing leading to an intermediate state that decays on a subpicosecond time scale with a branched mechanisms. Two decay pathways are experimentally observed. One probably involves proton transfer, leading to the most stable triplet aci-form of 2-nitrophenol; the second pathway may involve OH rotation. We propose that following intersystem crossing, an ultrafast fragmentation channel leading to OH or HONO loss could also be operative.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-379260 (URN)10.1021/acs.jpca.8b10136 (DOI)000459836600003 ()30668129 (PubMedID)
Available from: 2019-03-15 Created: 2019-03-15 Last updated: 2019-03-15Bibliographically approved
Toffoli, D., Guarnaccio, A., Grazioli, C., Zhang, T., Johansson, F., de Simone, M., . . . Fronzoni, G. (2018). Electronic Structure Characterization of a Thiophene Benzo-Annulated Series of Common Building Blocks for Donor and Acceptor Compounds Studied by Gas Phase Photoelectron and Photoabsorption Synchrotron Spectroscopies. Journal of Physical Chemistry A, 122(44), 8745-8761
Open this publication in new window or tab >>Electronic Structure Characterization of a Thiophene Benzo-Annulated Series of Common Building Blocks for Donor and Acceptor Compounds Studied by Gas Phase Photoelectron and Photoabsorption Synchrotron Spectroscopies
Show others...
2018 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 44, p. 8745-8761Article in journal (Refereed) Published
Abstract [en]

The near-edge x-ray-absorption fine-structure (NEXAFS) and Xray photoelectron spectroscopy (XPS) spectra of benzo[b]thiophene (BBT) and dibenzothiophene (DBT) in the gas phase have been measured at the carbon Kedge and sulfur L-II,L-III-edge regions. The assignment of the spectral features has been provided by theoretical calculations based on density functional theory (DFT) and its time-dependent generalization (TDDFT) in the linear response regime. Observed trends in computed C 1s and S 2p ionization potentials (IPs) have been rationalized in terms of both the inductive effects due to the presence of S and the increased pi-electrons delocalization arising from the benzoannulation process. The analysis of the NEXAFS carbon K-edge and sulfur L-II,L-III-edge regions regions provided information on both low-lying delocalized virtual pi orbitals, and higher-lying localized sigma*(C-S) states. The evolution of the NEXAFS carbon K-edge spectral features along the series thiophene (T) and derivatives, BBT and DBT, is informative of a stabilizing effect due to increased aromaticity. This effect is however more pronounced in going from T to BBT compared to the introduction of a second annulated phenyl ring in DBT. The nature of the most intense sulfur L-II,L-III-edge NEXAFS spectral features is instead conserved along the series reflecting thus the localized nature of the virtual states involved in the S 2p core-excitation process.

Place, publisher, year, edition, pages
American Chemical Society, 2018
National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-368287 (URN)10.1021/acs.jpca.8b08333 (DOI)000449889100006 ()30351097 (PubMedID)
Funder
Carl Tryggers foundation
Available from: 2018-12-03 Created: 2018-12-03 Last updated: 2019-01-22Bibliographically approved
Zhang, T., Brumboiu, I. E., Grazioli, C., Guarnaccio, A., Coreno, M., de Simone, M., . . . Puglia, C. (2018). Lone-Pair Delocalization Effects within Electron Donor Molecules: The Case of Triphenylamine and Its Thiophene-Analog. The Journal of Physical Chemistry C, 122(31), 17706-17717
Open this publication in new window or tab >>Lone-Pair Delocalization Effects within Electron Donor Molecules: The Case of Triphenylamine and Its Thiophene-Analog
Show others...
2018 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 31, p. 17706-17717Article in journal (Refereed) Published
Abstract [en]

Triphenylamine (TPA) and its thiophene-analog, N,N-diphenyl-2-thiophenamine (DPTA), are both well-known as electron-donating molecules implemented in optoelectronic devices such as organic solar cells and LEDs. Comprehensive valence and core level photoelectron spectroscopy, as well as near edge X-ray absorption spectroscopy (NEXAFS), measurements have been performed on gas phase TPA and DPTA. The experimental results have been compared to density functional theory calculations, providing a detailed description of the molecular electronic structure. Specifically, the C 1s photoelectron lines of both TPA and DPTA were resolved in the different C atom contributions and their binding energies explained as the result of two counter-acting effects: (1) the electronegativity of the nitrogen atom (and sulfur atom in DPTA) and (2) the the N (and S in DPTA) lone-pair electrons. In addition, the C K-edge NEXAFS spectrum of DPTA reveals that the lowest unoccupied molecular orbital (LUMO) energy position is affected differently if the core hole site is on the phenyl compared to the thiophene ring. The electron-donating properties of these two molecules are largely explained by the significant contribution of the N lone-pair electrons (p(z)) to the highest occupied molecular orbital. The contribution to the LUMO and to the empty density of states of the sulfur of the thiophene ring in DPTA explains the better performance of donor-pi-acceptor molecules containing this moiety and implemented in photoenergy conversion devices.

National Category
Physical Sciences Theoretical Chemistry Condensed Matter Physics
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-355118 (URN)10.1021/acs.jpcc.8b06475 (DOI)000441484600014 ()
Funder
Swedish Research Council, VR 2014-3776Carl Tryggers foundation
Note

Title in thesis list of papers: Lone Pair Delocalization Effect within Electron Donor Molecules:The Case of Triphenylamine (TPA) and Its Thiophene-Analog(DPTA)

Available from: 2018-06-29 Created: 2018-06-29 Last updated: 2018-10-15Bibliographically approved
Lanzilotto, V., Silva, J. L., Zhang, T., Stredansky, M., Grazioli, C., Simonov, K., . . . Puglia, C. (2018). Spectroscopic Fingerprints of Intermolecular H-Bonding Interactions in Carbon Nitride Model Compounds. Chemistry - A European Journal, 24(53), 14198-14206
Open this publication in new window or tab >>Spectroscopic Fingerprints of Intermolecular H-Bonding Interactions in Carbon Nitride Model Compounds
Show others...
2018 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 24, no 53, p. 14198-14206Article in journal (Refereed) Published
Abstract [en]

The effect of intermolecular H-bonding interactions on the local electronic structure of N-containing functional groups (amino group and pyridine-like N) that are characteristic of polymeric carbon nitride materials p-CN(H), a new class of metal-free organophotocatalysts, was investigated. Specifically, the melamine molecule, a building block of p-CN(H), was characterized by X-ray photoelectron (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The molecule was studied as a noninteracting system in the gas phase and in the solid state within a H-bonded network. With the support of DFT simulations of the spectra, it was found that the H-bonds mainly affect the N1s level of the amino group, leaving the N1s level of the pyridine-like N mostly unperturbed. This is responsible for a reduction of the chemical shift between the two XPS N1s levels relative to free melamine. Consequently, N K-edge NEXAFS resonances involving the amino N1s level also shift to lower photon energies. Moreover, the solid-state absorption spectra showed significant modification/quenching of resonances related to transitions from the amino N1s level to sigma* orbitals involving the NH2 termini.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2018
Keywords
density functional calculations, hydrogen bonds, carbon nitrides, photoelectron spectroscopy, X-ray absorption spectroscopy
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:uu:diva-366732 (URN)10.1002/chem.201802435 (DOI)000445177600028 ()30009392 (PubMedID)
Funder
Carl Tryggers foundation
Available from: 2018-12-11 Created: 2018-12-11 Last updated: 2018-12-11Bibliographically approved
Zhang, T., Brumboiu, I. E., Lanzilotto, V., Luder, J., Grazioli, C., Giangrisostomi, E., . . . Puglia, C. (2017). Conclusively Addressing the CoPc Electronic Structure: A Joint Gas-Phase and Solid-State Photoemission and Absorption Spectroscopy Study. The Journal of Physical Chemistry C, 121(47), 26372-26378
Open this publication in new window or tab >>Conclusively Addressing the CoPc Electronic Structure: A Joint Gas-Phase and Solid-State Photoemission and Absorption Spectroscopy Study
Show others...
2017 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 47, p. 26372-26378Article in journal (Refereed) Published
Abstract [en]

The occupied and empty densities of states of cobalt phthalocyanine (CoPc) were investigated by photoelectron and X-ray absorption spectroscopies in the gas phase and in thin films deposited on a Au(111) surface. The comparison between the gas-phase results and density functional theory single-molecule simulations confirmed that the CoPc ground state is correctly described by the (2)A(1g) electronic configuration. Moreover, photon-energy-dependent valence photoemission spectra of both the gas phase and thin film confirmed the atomic character of the highest occupied molecular orbital as being derived from the organic ligand, with dominant contributions from the carbon atoms. Multiplet ligand-field theory was employed to simulate the Co L-edge X-ray absorption spectroscopy results.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-345249 (URN)10.1021/acs.jpcc.7b08524 (DOI)000417228500026 ()
Funder
Swedish Research CouncilCarl Tryggers foundation
Available from: 2018-03-09 Created: 2018-03-09 Last updated: 2018-03-09Bibliographically approved
Zhang, T., Brumboiu, I. E., Lanzilotto, V., Luder, J., Grazioli, C., Giangrisostomi, E., . . . Puglia, C. (2017). Conclusively Addressing the CoPc Electronic Structure: A Joint Gas-Phase and Solid-State Photoemission and Absorption Spectroscopy Study. The Journal of Physical Chemistry C, 121(47), 26372-26378
Open this publication in new window or tab >>Conclusively Addressing the CoPc Electronic Structure: A Joint Gas-Phase and Solid-State Photoemission and Absorption Spectroscopy Study
Show others...
2017 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 47, p. 26372-26378Article in journal (Refereed) Published
Abstract [en]

The occupied and empty densities of states of cobalt phthalocyanine (CoPc) were investigated by photoelectron and X-ray absorption spectroscopies in the gas phase and in thin films deposited on a Au(111) surface. The comparison between the gas-phase results and density functional theory single-molecule simulations confirmed that the CoPc ground state is correctly described by the (2)A(1g) electronic configuration. Moreover, photon-energy-dependent valence photoemission spectra of both the gas phase and thin film confirmed the atomic character of the highest occupied molecular orbital as being derived from the organic ligand, with dominant contributions from the carbon atoms. Multiplet ligand-field theory was employed to simulate the Co L-edge X-ray absorption spectroscopy results.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2017
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-344315 (URN)10.1021/acs.jpcc.7b08524 (DOI)000417228500026 ()
Funder
Swedish Research CouncilCarl Tryggers foundation
Available from: 2018-03-08 Created: 2018-03-08 Last updated: 2018-06-29Bibliographically approved
Totani, R., Grazioli, C., Zhang, T., Bidermane, I., Lüder, J., de Simone, M., . . . Puglia, C. (2017). Electronic structure investigation of biphenylene films. Journal of Chemical Physics, 146(5), Article ID 054705.
Open this publication in new window or tab >>Electronic structure investigation of biphenylene films
Show others...
2017 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 146, no 5, article id 054705Article in journal (Refereed) Published
Abstract [en]

Photoelectron Spectroscopy (PS) and Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy have been used to investigate the occupied and empty density of states of biphenylene films of different thicknesses, deposited onto a Cu(111) crystal. The obtained results have been compared to previous gas phase spectra and single molecule Density Functional Theory (DFT) calculations to get insights into the possible modification of the molecular electronic structure in the film induced by the adsorption on a surface. Furthermore, NEXAFS measurements allowed characterizing the variation of the molecular arrangement with the film thickness and helped to clarify the substrate-molecule interaction. Published by AIP Publishing.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2017
National Category
Chemical Sciences Physical Sciences
Identifiers
urn:nbn:se:uu:diva-320469 (URN)10.1063/1.4975104 (DOI)000394576600053 ()28178795 (PubMedID)
Available from: 2017-04-26 Created: 2017-04-26 Last updated: 2017-04-26Bibliographically approved
Lüder, J., Puglia, C., Ottosson, H., Eriksson, O., Sanyal, B. & Brena, B. (2016). Many-body effects and excitonic features in 2D biphenylene carbon. Journal of Chemical Physics, 144(2), Article ID 024702.
Open this publication in new window or tab >>Many-body effects and excitonic features in 2D biphenylene carbon
Show others...
2016 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 144, no 2, article id 024702Article in journal (Refereed) Published
Abstract [en]

The remarkable excitonic effects in low dimensional materials in connection to large binding energies of excitons are of great importance for research and technological applications such as in solar energy and quantum information processing as well as for fundamental investigations. In this study, the unique electronic and excitonic properties of the two dimensional carbon network biphenylene carbon were investigated with GW approach and the Bethe-Salpeter equation accounting for electron correlation effects and electron-hole interactions, respectively. Biphenylene carbon exhibits characteristic features including bright and dark excitons populating the optical gap of 0.52 eV and exciton binding energies of 530 meV as well as a technologically relevant intrinsic band gap of 1.05 eV. Biphenylene carbon's excitonic features, possibly tuned, suggest possible applications in the field of solar energy and quantum information technology in the future.

National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-278016 (URN)10.1063/1.4939273 (DOI)000368618400036 ()26772582 (PubMedID)
Funder
Knut and Alice Wallenberg Foundation
Available from: 2016-02-23 Created: 2016-02-23 Last updated: 2017-11-30Bibliographically approved
Bidermane, I., Lüder, J., Ahmadi, S., Grazioli, C., Bouvet, M., Brena, B., . . . Witkowski, N. (2016). When the Grafting of Double Decker Phthalocyanines on Si(100)-2 × 1 Partly Affects the Molecular Electronic Structure. The Journal of Physical Chemistry C, 120(26), 14270-14276
Open this publication in new window or tab >>When the Grafting of Double Decker Phthalocyanines on Si(100)-2 × 1 Partly Affects the Molecular Electronic Structure
Show others...
2016 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 26, p. 14270-14276Article in journal (Refereed) Published
Abstract [en]

A combined X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and density functional theory (DFT) study has been performed to characterize the adsorbate interaction of lutetium biphthalocyanine (LuPc2) molecules on the Si(100)-2 × 1 surface. Large molecule–substrate adsorption energies are computed and are found to compete with the molecule–molecule interactions of the double decker molecules. A particularly good matching between STM images and computed ones confirms the deformation of the molecule upon the absorption process. The comparison between DFT calculations and XP spectra reveals that the electronic distribution in the two plateaus of the biphthalocyanine are not affected in the same manner upon the adsorption onto the silicon surface. This finding can be of particular importance in the implementation of organic molecules in hybrid devices.

Keywords
lutetium bi-phthalocyanine, XPS, STM, XAS, DFT, Si(100)
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:uu:diva-281565 (URN)10.1021/acs.jpcc.6b05552 (DOI)000379457000044 ()
Funder
EU, FP7, Seventh Framework Programme, 321319Knut and Alice Wallenberg Foundation, KAW-2013.0020Swedish Research Council, 2014-3776
Available from: 2016-03-24 Created: 2016-03-24 Last updated: 2017-11-30Bibliographically approved
Bidermane, I., Brumboiu, I., Totani, R., Grazioli, C., Shariati Nilsson, M. N., Herper, H., . . . Puglia, C. (2015). Atomic Contributions to the Valence Band Photoelectron Spectra of Metal-free, Iron and Manganese Phthalocyanines. Journal of Electron Spectroscopy and Related Phenomena, 205, 92-97
Open this publication in new window or tab >>Atomic Contributions to the Valence Band Photoelectron Spectra of Metal-free, Iron and Manganese Phthalocyanines
Show others...
2015 (English)In: Journal of Electron Spectroscopy and Related Phenomena, ISSN 0368-2048, E-ISSN 1873-2526, Vol. 205, p. 92-97Article, review/survey (Other academic) Published
Abstract [en]

The present work reports a photoelectron spectroscopy study of the low-energy region of the valence band of metal-free phthalocyanine (H2Pc) compared with those of iron phthalocyanine (FePc) and manganese phthalocyanine (MnPc). We have analysed in detail the atomic orbital composition of the valence band both experimentally, by making use of the variation in photoionization cross-sections with photon energy, and theoretically, by means of density functional theory. The atomic character of the Highest Occupied Molecular Orbital (HOMO), reflected on the outermost valence band binding energy region, is different for MnPc as compared to the other two molecules. The peaks related to the C 2p contributions, result in the HOMO for H2Pc and FePc and in the HOMO-1 for MnPc as described by the theoretical predictions, in very good agreement with the experimental results. The DFT simulations, discerning the atomic contribution to the density of states, indicate how the central metal atom interacts with the C and N atoms of the molecule, giving rise to different partial and total density of states for these three Pc molecules.

Keywords
Valence band; X-ray photoelectron spectroscopy; DFT; Phthalocyanines
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:uu:diva-217083 (URN)10.1016/j.elspec.2015.09.004 (DOI)000367282400011 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg FoundationCarl Tryggers foundation
Available from: 2014-01-29 Created: 2014-01-29 Last updated: 2017-12-06Bibliographically approved
Organisations

Search in DiVA

Show all publications