Browsing by Subject "ELECTRONIC-STRUCTURE"

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  • Kokkonen, E.; Kaipio, M.; Nieminen, H. -E; Rehman, F.; Miikkulainen, V.; Putkonen, M.; Ritala, M.; Huotari, S.; Schnadt, J.; Urpelainen, S. (2022)
    An ambient pressure cell is described for conducting synchrotron-based x-ray photoelectron spectroscopy (XPS) measurements during atomic layer deposition (ALD) processes. The instrument is capable of true in situ and operando experiments in which it is possible to directly obtain elemental and chemical information from the sample surface using XPS as the deposition process is ongoing. The setup is based on the ambient pressure XPS technique, in which sample environments with high pressure (several mbar) can be created without compromising the ultrahigh vacuum requirements needed for the operation of the spectrometer and the synchrotron beamline. The setup is intended for chemical characterization of the surface intermediates during the initial stages of the deposition processes. The SPECIES beamline and the ALD cell provide a unique experimental platform for obtaining new information on the surface chemistry during ALD half-cycles at high temporal resolution. Such information is valuable for understanding the ALD reaction mechanisms and crucial in further developing and improving ALD processes. We demonstrate the capabilities of the setup by studying the deposition of TiO2 on a SiO2 surface by using titanium(IV) tetraisopropoxide and water as precursors. Multiple core levels and the valence band of the substrate surface were followed during the film deposition using ambient pressure XPS.
  • Baryshnikov, Glib; Valiev, Rashid R.; Nasibullin, Rinat T.; Sundholm, Dage; Kurten, Theo; Ågren, Hans (2020)
    The recently synthesized cyclo[18]carbon molecule has been characterized in a number of studies by calculating electronic, spectroscopic, and mechanical properties. However, cyclo[18] carbon is only one member of the class of cyclo[n]carbons-standalone carbon allotrope representatives. Many of the larger members of this class of molecules have not been thoroughly investigated. In this work, we calculate the magnetically induced current density of cyclo[n]carbons in order to elucidate how electron delocalization and aromatic properties change with the size of the molecular ring (n), where n is an even number between 6 and 100. We find that the Hiickel rules for aromaticity (4k + 2) and antiaromaticity (4k) become degenerate for large C-n rings (n > 50), which can be understood as a transition from a delocalized electronic structure to a nonaromatic structure with localized current density fluxes in the triple bonds. Actually, the calculations suggest that cyclo[n]carbons with n > 50 are nonaromatic cyclic polyalkynes. The influence of the amount of nonlocal exchange and the asymptotic behavior of the exchange-correlation potential of the employed density functionals on the strength of the magnetically induced ring current and the aromatic character of the large cyclo[n]carbons is also discussed.
  • Baryshnikov, Gleb V.; Valiev, Rashid R.; Karaush, Nataliya N.; Sundholm, Dage; Minaev, Boris F. (2016)
    Magnetically induced current densities and current pathways have been calculated for a series of fully annelated dicationic and dianionic tetraphenylenes, which are also named [8]circulenes. The gauge including magnetically induced current (GIMIC) method has been employed for calculating the current density susceptibilities. The aromatic character and current pathways are deduced from the calculated current density susceptibilities showing that the neutral [8]circulenes have two concentric pathways with aromatic and antiaromatic character, respectively. The inner octatetraene core (the hub) is found to sustain a paratropic (antiaromatic) ring current, whereas the ring current along the outer part of the macrocycle (the rim) is diatropic (aromatic). The neutral [8]circulenes can be considered nonaromatic, because the sum of the ring-current strengths of the hub and the rim almost vanishes. The aromatic character of the doubly charged [8]circulenes is completely different: the dianionic [8]circulenes and the OC-, CH-, CH2-, SiH-, GeH-, SiH2-, and GeH2-containing dicationic species sustain net diatropic ring currents i.e., they are aromatic, whereas the O-, S-, Se-, NH-, PH- and AsH-containing dicationic [8]circulenes are strongly antiaromatic. The present study also shows that GIMIC calculations on the [8]circulenes provide more accurate information about the aromatic character than that obtained using local indices such as nuclear-independent chemical shifts (NICSs) and H-1 NMR chemical shifts.
  • Delhommaye, S.; Radtke, G.; Brouder, Ch; Collins, S. P.; Huotari, Simo; Sahle, Ch; Lazzeri, M.; Paulatto, L.; Cabaret, D. (2021)
    This study aims at assessing the thermal nuclei motion effects on the multipole transition channels involved in two core-level spectroscopies, x-ray absorption spectroscopy (XAS) and x-ray Raman scattering (XRS). Temperature effects on the 1s -> s monopole, 1s -> p dipole, and 1s -> d quadrupole transitions are investigated using two reference systems for which we present original experimental data: alpha-Al2O3 at the Al K edge probed by XRS at room temperature and rutile TiO2 at the Ti K pre-edge probed by XAS at temperatures ranging from 6 to 700 K. Through the latter, this work enlightens the part of the pre-edge peak enhancement due to temperature in the K pre-edge region of 3d transition metal, which is known to be routinely used to determine the concentration, valence or symmetry of the probed element in a given sample. Nuclear thermal fluctuations are taken into account using a method based on density functional theory that consists in averaging spectra over atomic configurations, generated within the harmonic approximation and obeying quantum statistics at finite temperature. Since only a finite number of such configurations are used, the numerically averaged spectra generally lose the symmetry of the equilibrium crystal positions. In this paper, we demonstrate that the physical average has to be symmetric and propose a method to restore the physical angular dependence of the spectra. The approach is successfully applied to investigate the angular dependent XAS spectra in rutile as a function of temperature. The two systems under study allow to draw general conclusions regarding the effect of nuclear quantum fluctuations on the different transition channels available to both core-level spectroscopies.
  • Iivonen, Tomi; Heikkilä, Mikko J.; Popov, Georgi; Nieminen, Heta-Elisa; Kaipio, Mikko; Kemell, Marianna; Mattinen, Miika; Meinander, Kristoffer; Mizohata, Kenichiro; Räisänen, Jyrki; Ritala, Mikko; Leskelä, Markku (2019)
    Herein, we report an atomic layer deposition (ALD) process for Cu2O thin films using copper(II) acetate [Cu(OAc)(2)] and water vapor as precursors. This precursor combination enables the deposition of phase-pure, polycrystalline, and impurity-free Cu2O thin films at temperatures of 180-220 degrees C. The deposition of Cu(I) oxide films from a Cu(II) precursor without the use of a reducing agent is explained by the thermally induced reduction of Cu(OAc)(2) to the volatile copper(I) acetate, CuOAc. In addition to the optimization of ALD process parameters and characterization of film properties, we studied the Cu2O films in the fabrication of photoconductor devices. Our proof-of-concept devices show that approx- imately 20 nm thick Cu2O films can be used for photodetection in the visible wavelength range and that the thin film photoconductors exhibit improved device characteristics in comparison to bulk Cu2O crystals.
  • De Temmerman, Gregory; Heinola, Kalle; Borodin, Dmitriy; Brezinsek, Sebastijan; Doerner, Russell P.; Rubel, Marek; Fortuna-Zalesna, Elzbieta; Linsmeier, Christian; Nishijima, Daisuke; Nordlund, Kai; Probst, Michael; Romazanov, Juri; Safi, Elnaz; Schwarz-Selinger, Thomas; Widdowson, Anna; Braams, Bastiaan J.; Chung, Hyun-Kyung; Hill, Christian (2021)
    ITER will use beryllium as a plasma-facing material in the main chamber, covering a total surface area of about 620 m(2). Given the importance of beryllium erosion and co-deposition for tritium retention in ITER, significant efforts have been made to understand the behaviour of beryllium under fusion-relevant conditions with high particle and heat loads. This paper provides a comprehensive report on the state of knowledge of beryllium behaviour under fusion-relevant conditions: the erosion mechanisms and their consequences, beryllium migration in JET, fuel retention and dust generation. The paper reviews basic laboratory studies, advanced computer simulations and experience from laboratory plasma experiments in linear simulators of plasma-wall interactions and in controlled fusion devices using beryllium plasma-facing components. A critical assessment of analytical methods and simulation codes used in beryllium studies is given. The overall objective is to review the existing set of data with a broad literature survey and to identify gaps and research needs to broaden the database for ITER.
  • Sokka, Iris Katariina; Ekholm, Filip S.; Johansson, Mikael P. (2019)
    Monomethyl auristatin E and monomethyl auristatin F are widely used cytotoxic agents in antibody-drug conjugates (ADCs), a group of promising cancer drugs. The ADCs specifically target cancer cells, releasing the auristatins inside, which results in the prevention of mitosis. The auristatins suffer from a potentially serious flaw, however. In solution, the molecules exist in an equal mixture of two conformers, cis and trans. Only the trans-isomer is biologically active and the isomerization process, i.e., the conversion of cis to trans is slow. This significantly diminishes the efficiency of the drugs and their corresponding ADCs, and perhaps more importantly, raises concerns over drug safety. The potency of the auristatins would be enhanced by decreasing the amount of the biologically inactive isomer, either by stabilizing the transisomer or destabilizing the cis-isomer. Here, we follow the computer-aided design strategy of shifting the conformational equilibrium and employ high-level quantum chemical modeling to identify promising candidates for improved auristatins. Coupled cluster calculations predict that a simple halogenation in the norephedrine/phenylalanine residues shifts the isomer equilibrium almost completely toward the active trans-conformation, due to enhanced intramolecular interactions specific to the active isomer.
  • Rabaa, Hassan; Omary, Mohammad A.; Taubert, Stefan; Sundholm, Dage (2018)
    The molecular structure of stacked cyclic trinuclear gold(I) complexes [Au-3(RN=CR'(3)](n), with n = 1-4, where R = H, methyl (Me), cyclopentyl ((c)Pe), and phenyl (Ph) and R' = OH and methoxy (OMe) were studied computationally at the second-order Moller-Plesset (MP2) and density functional theory (DFT) levels of theory. At the DFT level, the aurophilic and dispersion interactions were accounted for by using the TPSS functional in combination with the semiempirical D3 correction. The structure optimizations yielded the lowest energy for a slided stacked structure of the [Au-3(HN=COH)(3)](2) dimer, where monomers are slightly shifted relative to one another. At the MP2 level, the slided structure is 32 kJ/mol more stable than the staggered dimer structure, which in turn is energetically 11 kJ/mol below the eclipsed structure. The calculations show that aromatic ligands lead to a planar and prismatic structure of [Au-3(PhN=COMe)(3)](4), whereas for [Au-3('PeN=COMe)(3)](4), a chair conformation is obtained due to steric effects. Excitation energies were calculated for [Au-3(RN=CR')(3)] and [Au-3(RN=CR'(3)](2) with R = H, Me, and 'Pe and R' = OH and OMe at the time-dependent DFT level using the optimized molecular structures of the singlet ground state. To simulate the luminescence spectra, the lowest triplet excitation energy was also calculated for the molecular structure of the lowest triplet state. The calculated excitation energies of [Au-3(HN=COH)(3)] and [Au-3(HN=COH)(3)](2) are compared with values obtained at the approximate singles and doubles coupled cluster (CC2) and the second-order algebraic diagrammatic construction (ADC(2)) levels of theory. The calculated absorption and emission energies reproduce the experimental trends, with extremely large Stokes shifts. A solvoluminescence mechanism is also proposed.
  • Nieminen, Heta; Miikkulainen, Ville; Settipani, Daniel; Simonelli, Laura; Hönicke, Philipp; Zech, Claudia; Kayser, Yves; Beckhoff, Burkhard; Honkanen, Ari-Pekka; Heikkilä, Mikko; Mizohata, Kenichiro; Meinander, Nils Kristoffer; Ylivaara, Oili M. E.; Huotari, Simo; Ritala, Mikko (2019)
    LiMn2O4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn2O4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li+ ions into an ALD-grown beta-MnO2 thin film was studied. Samples were prepared by pulsing (LiOBu)-Bu-t and H2O for different cycle numbers onto about 100 nm thick MnO2 films at 225 degrees C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for
  • Paredes-Mellone, O. A.; Stutz, G. E.; Ceppi, S. A.; Arneodo Larochette, P.; Huotari, S.; Gilmore, K. (2019)
    The Li 1s core excitation spectra in LiH was studied by means of x-ray Raman scattering (XRS) spectroscopy in a wide range of momentum transfers q. The analysis of the near-edge region of the measured spectra in combination with q-dependent ab initio calculations of XRS spectra based on the Bethe-Salpeter equation (BSE) reveals that the prominent peak at the excitation onset arises from two main contributions, namely a pre-edge peak associated to a p-type core exciton and strong transitions to empty states near the bottom of the conduction band, which is in contrast to previous experimental studies that attributed that feature to a single excitonic peak. The p-like angular symmetry of the core exciton is supported by BSE calculations of the relative contributions to the XRS spectra from monopole and dipole transitions and by the observed decrease of its normalised intensity for increasing momentum transfers. Higher energy spectral features in the measured XRS spectra are well reproduced by BSE, as well as by real-space multiple-scattering calculations.
  • Taubert, Stefan; Sundholm, Dage; Pichierri, Fabio (2010)
  • Taubert, Stefan; Sundholm, Dage; Pichierri, Fabio (2010)
  • Taubert, Stefan; Sundholm, Dage; Pichierri, Fabio (2010)
  • Sundholm, Dage; Wirz, Lukas N.; Schwerdtfeger, Peter (2015)
    A new family of cavernous all-carbon structures is proposed. These molecular cage structures are constructed by edge subdivisions and leapfrog transformations from cubic polyhedra or their duals. The obtained structures were then optimized at the density functional level. These hollow carbon structures represent a new class of carbon allotropes which could lead to many interesting applications.
  • Sundholm, Dage; Rauhalahti, Markus; Özcan, Nergiz; Mera-Adasme, Raul; Kussmann, Jorg; Luenser, Arne; Ochsenfeld, Christian (2017)
    Nuclear magnetic shieldings have been calculated at the density functional theory (DFT) level for stacks of benzene, hexadehydro[12]annulene, dodecadehydro[18]annulene, and hexabenzocoronene. The magnetic shieldings due to the ring currents in the adjacent molecules have been estimated by calculating nucleus independent molecular shieldings for the monomer in the atomic positions of neighbor molecules. The calculations show that the independent shielding model works reasonably well for the H-1 NMR shieldings of benzene and hexadehydro[12]annulene, whereas for the larger molecules and for the C-13 NMR shieldings the interaction between the molecules leads to shielding effects that are at least of the same size as the ring current contributions from the adjacent molecules. A better agreement is obtained when the nearest neighbors are also considered at full quantum mechanical (QM) level. The calculations suggest that the nearest solvent molecules must be included in the quantum mechanical system, at least when estimating solvent shifts at the molecular mechanics (MM) level. Current density calculations show that the stacking does not significantly affect the ring current strengths of the individual molecules, whereas the shape of the ring current for a single molecule differs from that of the stacked molecules.
  • Greiner, Jonas; Valiev, Rashid R.; Sundholm, Dage (2020)
    Rate constants for radiative and non-radiative transitions of the [Au(HN & xe001;COH)](3) complex and its dimer were calculated within the Herzberg-Teller approximation based on quantum mechanical principles. A high triplet quantum yield was estimated for the monomer. Internal conversion (IC) was found to be the major competing process to the intersystem crossing (ISC) from the lowest excited singlet state (S-1) to the lowest triplet state (T-1). ISC and IC from the spin-mixed T & x303;(1) state also dominate the triplet relaxation process resulting in a negligible phosphorescence quantum yield for the monomer. The IC and ISC rate constants of the dimer are considerably smaller due to much lower Franck-Condon factors. For the dimer a triplet quantum yield of 0.71 was estimated using the extended multi-configuration quasi-degenerate second-order perturbation theory (XMCQDPT2) method to calculate the transition energies. Fluorescence is the major competing process to the ISC relaxation of the S-1 state of the dimer. The ISC and IC processes are insignificant for the relaxation of the T-1 state, resulting in unity phosphorescence quantum yield. The high triplet and phosphorescence quantum yields of the [Au(HN & xe001;COH)](3) dimer make it and its higher oligomers potential candidates as dopants for phosphorescent organic light emitting diodes and as down-converters in solid-state lighting systems.
  • Fathi-Rasekh, Mahtab; Rohde, Gregory T.; Hart, Mason D.; Nakakita, Toshinori; Zatsikha, Yuriy V.; Valiev, Rashid R.; Barybin, Mikhail V.; Nemykin, Victor N. (2019)
    Two isomeric ruthenium(II)/5,10,15,20-tetraphe-nylporphyrin complexes featuring axially coordinated redox-active, low-optical gap 2- or 6-isocyanoazulene ligands have been isolated and characterized by NMR, UV-vis, and magnetic circular dichroism (MCD) spectroscopic methods, high-resolution mass spectrometry, and single-crystal X-ray crystallography. The UV-vis and MCD spectra support the presence of the low-energy, azulene-centered transitions in the Q band region of the porphyrin chromophore. The first coordination sphere in new L2RuTPP complexes reflects compressed tetragonal geometry. The redox properties of the new compounds were assessed by electrochemical and spectroelectrochemical means and correlated with the electronic structures predicted by density functional theory and CASSCF calculations. Both experimental and theoretical data are consistent with the first two reduction processes involving the axial azulenic ligands, whereas the oxidation profile (in the direction of increasing potential) is exerted by the ruthenium ion, the porphyrin core, and the axial azulenic moieties.
  • Shtepliuk, I.; Pliatsikas, N.; Jian, J.; Ben Sedrine, N.; Iakimov, T.; Sarakinos, K.; Ivanov, I. G.; Sun, Jianwu; Yakimova, R. (2021)
    The paucity of research on hydrogen evolution reaction (HER) under neutral conditions, which is a more sustainable way to produce H-2 compared to acidic and alkaline HER, encourages the development of efficient catalytic materials and devices and deeper investigation of the mechanisms behind neutral HER. We present an electrode concept for facilitating HER under neutral conditions. The concept entails the use of annealing-reshaped silver (Ag) nanoparticle array on monolayer epitaxial graphene (MEG) on 4H-SiC. Measurements of HER performance show more positive onset potential of the cathodic HER for Ag-decorated MEG compared to that for pristine MEG, indicating improved water dissociation at Ag/MEG electrodes. Complementary morphological characterization, absorption measurements, and Raman mapping analysis enable us to ascribe the enhanced catalytic performance of electrodes decorated with 2 nm thick annealed Ag on the synergetic effect originating from simultaneous water reduction on circular Ag nanoparticles of 31 nm in diameter and on compressively strained Ag-free graphene regions. The overall results pave the way toward development of stable van der Waals heterostructure electrodes with a tunable metal-carbon interaction for fast HER under neutral conditions. (C) 2021 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (
  • Schwerdtfeger, Peter; Smits, Odile R.; Pyykkö, Pekka (2020)
    As the International Year of the Periodic Table came to an end in 2019, the authors reflect on the chemistry and physics that drive the periodic table of the elements. This includes aspects of periodic trends, relativistic electronic-structure theory, nuclear-structure theory and the astrophysical origin of the elements. Mendeleev's introduction of the periodic table of elements is one of the most important milestones in the history of chemistry, as it brought order into the known chemical and physical behaviour of the elements. The periodic table can be seen as parallel to the Standard Model in particle physics, in which the elementary particles known today can be ordered according to their intrinsic properties. The underlying fundamental theory to describe the interactions between particles comes from quantum theory or, more specifically, from quantum field theory and its inherent symmetries. In the periodic table, the elements are placed into a certain period and group based on electronic configurations that originate from the Pauli and Aufbau principles for the electrons surrounding a positively charged nucleus. This order enables us to approximately predict the chemical and physical properties of elements. Apparent anomalies can arise from relativistic effects, partial-screening phenomena (of type lanthanide contraction) and the compact size of the first shell of everyl-value. Further, ambiguities in electron configurations and the breakdown of assigning a dominant configuration, owing to configuration mixing and dense spectra for the heaviest elements in the periodic table. For the short-lived transactinides, the nuclear stability becomes an important factor in chemical studies. Nuclear stability, decay rates, spectra and reaction cross sections are also important for predicting the astrophysical origin of the elements, including the production of the heavy elements beyond iron in supernova explosions or neutron-star mergers. In this Perspective, we critically analyse the periodic table of elements and the current status of theoretical predictions and origins for the heaviest elements, which combine both quantum chemistry and physics.
  • Rauhalahti, M.; Munoz-Castro, A.; Sundholm, D. (2016)
    We have computationally investigated the possible formation of large hollow gold nanostructures based on a Au-32 core covered with a thiolate layer using relativistic density functional theory calculations. We have found that [Au-32@Au-12(SR)(18)](6-) is a plausible candidate that retains the structural, electronic and spherical aromatic properties of the Au-32 cage of its parent bare Au-32 golden fullerene. The study shows that the low-energy part of the optical spectrum can serve as a guide to identify such hollow gold structures among other small-sized gold nanoclusters with similar nuclearities. The low-lying excited states are dominated by 1f -> 1g transitions, which significantly distinguish hollow clusters from other nanoclusters, like the prominent [Au-25(SR)(18)](-) cluster, whose low-lying excitations are dominated by 1p /1d transitions. The gold nanoclusters studied here can serve as model compounds for assessing the metallic core size effects on the absorption energies and the influence of the surface structure of the gold core on the cluster properties. The present study suggests that it is also plausible that even larger hollow structures derived from Au-42, Au-72, and Au-92 golden fullerenes can exist.