DOCSLIB.ORG

Structure of Endohedral Fullerene Eu@C74 W

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Structure of Endohedral Fullerene Eu@C74 W View Online / Journal Homepage / Table of Contents for this issue PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics Structure of endohedral fullerene Eu@C74w Dmitrij Rappoport* and Filipp Furche Received 2nd February 2009, Accepted 12th May 2009 First published as an Advance Article on the web 10th June 2009 DOI: 10.1039/b902098e Structure determination of endohedral fullerenes in the absence of X-ray data is difficult and often controversial. Here we show that the structure of endohedral fullerene Eu@C74 may be determined by density functional theory aided interpretation of its electronic, infrared and Raman spectra. The use of recently developed analytical polarizability gradient methods to simulate resonance-enhanced Raman spectra is crucial for this approach and allows for a nearly complete assignment of the experimental spectra. Eu@C74 is assigned a pear-shaped C2v symmetric structure and shows strong ionic interaction between the encapsulated metal and the fullerene p system. 1. Introduction spectrum of Eu@C74 to predictions from time-dependent density functional theory (TDDFT) to identify the frontier Endohedral metallofullerenes constitute a large class of molecular orbitals, specifically the electronic configuration of fullerene inner complexes with metal atoms or small metal europium. The structure of the carbon cage is inferred from an clusters.1,2 Group 2 and 3 metals and lanthanides form a assignment of infrared and Raman spectra of Eu@C74. number of endohedral fullerene complexes notable for their An important tool in the structure elucidation of endohedral electronic absorption in the near infrared and for their large fullerenes is 13C nuclear magnetic resonance (NMR) spectro- 1–3 third-order nonlinear susceptibilities. Lanthanide endohedral scopy. 13C NMR was used in conjunction with density fullerenes have recently attracted attention as high-relaxivity functional calculations to determine the structures of the 4,5 contrast agents for magnetic resonance imaging and as spin closed-shell endohedral fullerenes Ca@C 14 and Yb@C .15 6 74 74 qubits for quantum computing. 13 However, no C NMR data have been reported for Eu@C74 A major challenge in endohedral fullerene chemistry is the which makes the present theory-aided interpretation of complicated preparation and purification procedure yielding electronic and vibrational spectra particularly useful. The 1,7 only milligrams or less of substance. Structure determination present approach is applicable to other paramagnetic endohedral by X-ray crystallography is further complicated by the low fullerenes. crystallization tendency of fullerenes and crystal disorder.8 Downloaded by University of California - Irvine on 23 February 2012 Published on 10 June 2009 http://pubs.rsc.org | doi:10.1039/B902098E These difficulties may be alleviated by co-crystallization with 9 10 metalloporphyrins, e.g., for Tb3N@C80 or Ba@C74 or using 11 2. Computational details covalent adducts such as La@C74C6H3Cl3. Nevertheless, experimental structural data are still unavailable for many The theoretical tools for prediction of the vibrational proper- fullerene metal complexes including all europium endohedral ties of Eu@C74 are based on analytical derivative methods in fullerenes. Eu@C74 was the first isolated endohedral europium the framework of density functional theory (DFT). Molecular fullerene and was characterized spectroscopically and electro- force constants of large molecules are efficiently computed 12 chemically ten years ago. However, the structure of Eu@C74 from analytical second energy derivatives with respect to has not been established to date. nuclear displacements.16,17 However, due to the large number In a pioneering study, Vietze, Seifert and Fowler (VSF) of vibrations and the low symmetry of Eu@C74, vibrational applied semi-empirical density functional tight-binding theory frequencies alone contain too little information for a complete 13 (DFTB) methods to Eu@C74. Their work focused on vibrational band assignment. Infrared intensities and Raman tentative structures and relative energies of low-lying isomers. scattering cross sections provide additional characterization VSF did not provide predictions of experimentally accessible and are essential for correlating computed vibrational modes properties of Eu@C74, and thus a conclusive assignment of the to observed bands in vibrational spectra of Eu@C74. structure was not possible. Here we show how modern density The present structural assignment of Eu@C74 became possible functional methods can help to extract structural information by the recently developed efficient method for computing from electronic, infrared and Raman spectra of Eu@C74. This Raman scattering cross sections in the framework of leads to the first definitive structure assignment of this TDDFT.18 Within polarizability theory, Raman scattering endohedral fullerene. We compare the electronic excitation cross sections are determined from first-order derivatives of the frequency-dependent polarizability with respect to normal-mode displacements.19,20 Efficient computation of Department of Chemistry, University of California, Irvine, polarizability derivatives has long been the time-limiting CA 92697-2025, USA. E-mail: [email protected] w Electronic supplementary information (ESI) available: Atomic step in Raman calculations. Methods based on numerical coordinates. See DOI: 10.1039/b902098e differentiation of frequency-dependent polarizabilities were This journal is c the Owner Societies 2009 Phys.Chem.Chem.Phys., 2009, 11, 6353–6358 | 6353 View Online 21 applied to the molecules as large as buckminsterfullerene C60, 3. Results and discussion exploiting its high point group symmetry. The major drawback of numerical derivative methods is that they require a large 3.1 Minimum energy structure number of polarizability evaluations that increases with the The empty C74 cage is known to have a D3h symmetric 38 number of nuclear degrees of freedom. In contrast, the recently structure. In Eu@C74 the carbon cage is distorted from proposed analytical derivative method based on a Lagrangian D3h symmetry along one of the three equivalent dihedral formulation of frequency-dependent polarizabilities18 yields all axes. The resulting three degenerate energy minima have Cartesian polarizability derivatives at approximately 2–3 times symmetry-equivalent C2v symmetric structures one of which the cost of a single polarizability calculation, independent of the is depicted in Fig. 1. The europium atom is symmetrically number of nuclear degrees of freedom. In contrast to the coordinated to a [6,6]-bond of a pyracyclene unit with widely used analytical Hartree–Fock-based implementation of europium–carbon distances of 254 pm. Four carbon atoms Frisch and co-workers,22 the Lagrangian method18 includes adjacent to the coordinated [6,6]-bond are at a distance of the frequency-dependence of polarizability derivatives in a 267 pm from europium, which is even shorter than the natural way. This is particularly important for molecules europium–carbon distances of 277–282 pm found in 40–42 with low excitation energies such as fullerenes because the europium cyclopentadienyl complex Eu(C5Me5)2. resonance enhancement is significant at experimental excitation The carbon cage is visibly distorted near the encapsulated frequencies.23,24 metal: the cage surface is bulged out at the coordination site The structures of the energy minima and transition states of while the coordinated C–C bond is elongated by 6 pm Eu@C74 were optimized in C2v point group symmetry using compared to the empty C74 cage. 25,26 the BP86 exchange–correlation functional and the resolution The formation of the Eu@C74 endohedral complex from of the identity approximation (RI-J).27 Basis sets were of neutral species is associated with a large binding energy of À1 split-valence quality with polarization (SVP) for carbon28 359 kJ mol . The counterpoise correction for the basis set and of triple-zeta valence quality with two sets of polarization superposition error (BSSE) reduces the binding energy to À1 functions (TZVPP) for europium29 together with corresponding 324 kJ mol . The three energy minima of Eu@C74 are auxiliary basis sets.27,29 Effective core potentials (ECP) were symmetry-equivalent, in agreement with only one Eu@C74 12 used for europium.30 Reoptimization of the energy minimum fraction found in the HPLC separation procedure. The structure using triple-zeta valence quality basis set on all atoms degenerate interconversion of neighboring energy minima resulted in changes in bonding distances of 1 pm or less. Thus, proceeds via a C2v-symmetric transition state with a sizeable À1 À1 SVP basis sets were used for carbon atoms, and TZVPP basis activation barrier of 46 kJ mol (42 kJ mol including the sets were used for europium for all structure optimizations and BSSE correction). As a consequence, the diffusional motion of the europium atom throughout the carbon cage is strongly force constant calculations in this study. Electronic excitation 13 energies and oscillator strengths were obtained from TDDFT hindered. C-NMR experiments on Ca@C74 showed that the 31,32 33 site-hopping motion of the calcium atom is observable at the calculations using the RI-J approximation. The exchange– 14 Downloaded by University of California - Irvine on 23 February 2012 time scale of the NMR experiment. An activation barrier of Published on 10 June 2009 http://pubs.rsc.org | doi:10.1039/B902098E correlation functional and basis sets were the same
Load more

Recommended publications
  • Photoionization of the Cerium Isonuclear Sequence and Cerium Endohedral Fullerene
    University of Nevada, Reno Photoionization of the Cerium Isonuclear Sequence and Cerium Endohedral Fullerene A dissertation submitted in partial ful¯llment of the requirements for the degree of Doctor of Philosophy in Physics by Mustapha Habibi Prof. Ronald A. Phaneuf/Dissertation Advisor May, 2009 THE GRADUATE SCHOOL We recommend that the dissertation prepared under our supervision by MUSTAPHA HABIBI entitled Photoionization Of The Cerium Isonuclear Sequence And Cerium Endohedral Fullerene be accepted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Ronald A. Phaneuf, Ph. D., Advisor Jeffrey S. Thompson, Ph. D., Committee Member Peter Winkler, Ph. D., Committee Member Paul Neill, Ph. D., Committee Member Mohammed S. Fadali, Ph. D., Graduate School Representative Marsha H. Read, Ph. D., Associate Dean, Graduate School May, 2009 To the souls of my mother and my father, to my beloved wife and daughters, to all my family, friends and colleagues for their love and unconditional support. i Abstract This dissertation presents an experimental photoionization study of the cerium isonuclear sequence ions in the energy range of the 4d inner-shell giant resonance. In addition, single and double photoionization and photofragmentation cross sections of the cerium endohe- + dral ion Ce@C82 were also measured and studied in the 4d excitation-ionization energy range of cerium. Relative and absolute cross-section measurements were performed at un- dulator beamline 10.0.1 of the Advanced Light Source (ALS) for nine parent cerium ions: Ce+ { Ce9+. Double-to-single ionization cross-section ratios were measured for photoion- + + ization of the endohedral Ce@C82 and empty fullerene C82 molecular ions.
    [Show full text]
  • Synthesis and Characterization of Non-IPR Monometallic Actinide
    Article Cite This: J. Am. Chem. Soc. XXXX, XXX, XXX−XXX pubs.acs.org/JACS Synthesis and Characterization of Non-Isolated-Pentagon-Rule C ‑ Actinide Endohedral Metallofullerenes U@ 1(17418) C76, C ‑ C ‑ U@ 1(28324) C80, and Th@ 1(28324) C80: Low-Symmetry Cage Selection Directed by a Tetravalent Ion † § ⊥ ‡ ⊥ † ⊥ † ∥ † Wenting Cai, , , Laura Abella, , Jiaxin Zhuang, , Xingxing Zhang, Lai Feng, Yaofeng Wang, ‡ § # § Roser Morales-Martínez, Ronda Esper, Mauro Boero, Alejandro Metta-Magaña, ‡ ‡ § † Antonio Rodríguez-Fortea, Josep M. Poblet,*, Luis Echegoyen,*, and Ning Chen*, † Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, PR China ‡ Departament de Química Física i Inorganica,̀ Universitat Rovira i Virgili, c/Marcel·lí Domingo 1, 43007 Tarragona, Spain § Department of Chemistry, University of Texas at El Paso, 500 W University Avenue, El Paso, Texas 79968, United States # University of Strasbourg, CNRS, Institut de Physique et Chimie des Materiaux́ de Strasbourg UMR 7504, 23 rue du Loess, F-67034 Strasbourg, France ∥ Soochow Institute for Energy and Materials InnovationS (SIEMIS), College of Physics, Optoelectronics and Energy & Collaborative, Soochow University, Suzhou, Jiangsu 215006, PR China *S Supporting Information ABSTRACT: For the first time, actinide endohedral metal- lofullerenes (EMFs) with non-isolated-pentagon-rule (non-IPR) carbon cages, U@C80,Th@C80,andU@C76, have been successfully synthesized and fully characterized by mass spectrometry, single crystal X-ray diffractometry, UV−vis−NIR and Raman spectroscopy, and cyclic voltammetry. Crystallo- graphic analysis revealed that the U@C80 and Th@C80 share the same non-IPR cage of C1(28324)-C80, and U@C76 was assigned to non-IPR U@C1(17418)-C76.
    [Show full text]
  • Crystalline C60 Fulleride with Metal Inside
    Crystalline C60 fulleride with metal inside Ayano Nakagawa1, Makiko Nishino1, Hiroyuki Niwa1, Katsuma Ishino1, Zhiyong Wang1, Haruka Omachi1, Ko Furukawa2, Takahisa Yamaguchi3, Tatsuhisa Kato3, Shunji Bandow4, Jeremy Rio5, Chris Ewels5, Shinobu Aoyagi6 & Hisanori Shinohara1* 1Department of Chemistry and Institute for Advanced Research, Nagoya University, Nagoya 464-8602, Japan. 2Center for Coordination of Research Facilities, Institute for Research Promotion, Niigata University, Niigata 950-2181, Japan. 3Graduate School of Human and Environmental Sciences, Kyoto University, Sakyo-ku, Kyoto 606- 8501, Japan. 4Faculty of Science and Technology, Department of Applied Chemistry, Meijo University, Nagoya 468-8502, Japan. 5Institut des Materiaux Jean Rouxel (IMN), Université de Nantes, CNRS UMR6502, BP3229, 44322 Nantes, France 6Department of Information and Basic Science, Nagoya City University, Nagoya 467-8501, Japan. Endohedral metallofullerenes have been extensively studied, since the first experimental observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, all of these studies have been carried out on metallofullerenes larger than C60 such as (metal)@C82, and there + - are no reported purified C60-based metallofullerenes except for [Li@C60] (SbCl6) salt. Pure (metal)@C60 has not been obtained because of their extremely high chemical reactivity. We report here the first isolation, structural determination and electromagnetic properties of crystalline C60- based metallofullerenes, Gd@C60(CF3)5 and La@C60(CF3)5. Synchrotron X-ray single-crystal diffraction reveals that La and Gd atoms are indeed encapsulated in the Ih-C60 fullerene. The HOMO-LUMO gaps of Gd@C60 and La@C60 are significantly widened by an order of magnitude with addition of CF3- groups. Magnetic measurements show the presense of a weak antiferromagnetic coupling in Gd@C60(CF3)3 crystals at low temperatures.
    [Show full text]
  • Endohedral Fullerenes: the Importance of Electronic, Size and Shape Complementarity Between the Carbon Cages and the Corresponding Encapsulated Clusters† Maira R
    Research Article Received: 6 September 2013, Revised: 24 September 2013, Accepted: 6 October 2013, Published online in Wiley Online Library: 9 January 2014 (wileyonlinelibrary.com) DOI: 10.1002/poc.3245 Endohedral fullerenes: the importance of electronic, size and shape complementarity between the carbon cages and the corresponding encapsulated clusters† Maira R. Ceróna, Fang-Fang Lia and Luis A. Echegoyena* Cage-cluster complementarity is of crucial importance in determining the sizes and structures, as well as the properties of endohedral fullerenes. The encapsulated atoms or clusters, which are typically in a positively charged state, are irreversibly, mechanically, and electrostatically trapped inside the typically negatively charged cages. These rather exotic compounds exhibit exquisitely complementary properties between their components. Here, we present a short overview to show that size and shape are crucial in determining the specific structures that are formed, and the presence of electrostatic interactions result in structural motifs that are never observed for pristine fullerene cages. Copyright © 2014 John Wiley & Sons, Ltd. Keywords: electronic properties; endohedral fullerenes; fullerene and cluster cage sizes; fullerene and cluster shapes INTRODUCTION understand the most important factors involved in determining the specific structures that are observed and their relative importance. The discovery and increased interest and to some degree, fascina- tion of trapping and studying atoms and clusters inside the carbon cages
    [Show full text]
  • Actinide-Based Endohedral Metallofullerenes
    Actinide-Based Endohedral Metallofullerenes Bailey Bouley Literature Seminar November 14th, 2019 In 1985, Smalley, Curl, and Kroto synthesized a new allotrope of carbon, C60, by laser vaporization methods under a helium atmosphere.1 The discovery of the structure that formed, deemed buckminsterfullerene by the authors, along with the discovery of fullerenes of other sizes with Cn configurations, won them the Nobel Prize in Chemistry in 1996. Two weeks after their discovery, the same authors published the first example of a metal ion encapsulated within the cavity of a fullerene, La-Cn (n = 44 – 76), where the lower carbon count Cn configurations appeared to exhibit an increase in stability with the metal ion inclusion.2 This discovery sparked interest in chemical research focused on using these so-named endohedral metallofullerenes (EMFs) as a new approach to the construction of superconductors (for alkali metal EMFs),3 and as isolated environments to study fundamental principles of poorly understood f-block elements. The first actinide-containing EMF was discovered in 1992, when the authors hypothesized an appropriately sized tetravalent ion would be able to stabilize C28, a fullerene that had been previously detected by TOF-MS, but not isolated due to poor stability.4 The low stability of this cluster was attributed to the presence of highly reactive sites centralized on fused pentagon rings, systems that violated the isolated pentagon rule (IPR), which states that fullerenes containing fused 5 pentagon rings are destabilized due to high geometric strain. It was believed, and subsequently supported by DFT calculations, that non-IPR cages can be stabilized through an ionic model in which electrons are transferred from the metal atom to the cage itself, localizing negative charge on the reactive carbon center, resulting in stabilization of these sites.6,7 Figure 1.
    [Show full text]
  • Nanotechnology - Fundamentals and Applications 1
    D. Cremer, CHEM 6342, Nanotechnology - Fundamentals and Applications 1 CHEM 6342 Nanotechnology – Fundamentals and Applications Class location: TBD Lectures, time and location: TBD Lab times and location: TBD Instructor: Dieter Cremer, 325 FOSC, ext 8-1300, [email protected] http://smu.edu/catco/ Office Hours: By appointment Units: 3 Grading: ABC Letter Grade Class number TBD 1. Rationale: Nanotechnology (NT) is a rather young discipline, which came up in the nineties. Nevertheless, NT has gained so much importance within the last years that universities at all rankings have introduced or are going to introduce NT teaching programs. Predictions say that NT will change our lives and society more than computer technology and electricity have done together. The course will provide an overview over NT. It will show that the nano regime is so different from other regimes because both classical and quantum effects can be active thus leading to unique properties of nano devices. NT is a highly interdisciplinary science, which will be reflected in the course by making reference to chemistry, physics, biology, pharmacy, and engineering. Applications of NT, as they are already in use today or as they are planned for the future, will be discussed. 2. Course Recommendations: The course is designed to reach all graduate students who had have an education in chemistry, physics, engineering or biology. It does not require special knowledge in mathematics or theoretical physics. The course contents will be presented in self-sustained modules, which make it possible to follow the course without special knowledge. The course will prepare for the interdisciplinary work in NT.
    [Show full text]
  • Understanding Charge Transport in Endohedral Fullerene Single- Crystal Field-Effect Transistors
    Understanding Charge Transport in Endohedral Fullerene Single- Crystal Field-Effect Transistors Xiaoming Zhao,1† Tianjun Liu,2† Wenda Shi,1 Xueyan Hou,1 Zilu Liu,3 T. John S. Dennis1* 1 School of Physics and Astronomy, Queen Mary University of London, Mile End Road, London E1 4NS, United Kingdom 2 School of Engineering and Materials Science, Queen Mary University of London, Mile End Road, London E1 4NS, United Kingdom. 3 School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS, United Kingdom † X. Zhao and T. Liu have the equivalent contribution Abstract: The encapsulation of nitrogen within C60 forms non-metallic endohedral fullerene N@C60. Previous calculations show that the encapsulated nitrogen may favor more efficient charge injection and transport under external electric fields when compared to C60, suggesting that N@C60 may be a promising candidate for application in organic electronic devices. However, owing to difficulties in both synthesis and purification, the potential application of N@C60 under external electric field has not been previously studied experimentally and its intrinsic charge transport mechanism remains unknown, which hinders more widely applications of endohedral fullerene in organic electronic devices. Here, we demonstrate the field-effect study and photo-detective applications of solution-grown N@C60 single crystals. Organic field- effect transistors (OFETs) based on them exhibit electron mobilities up to 2.23 cm2 V- 1 1 s-1. Furthermore, the electrical properties show a favorable band-like charge transport mechanism from 180K to 300K, and photodetectors based on them yield a highly sensitive photo-conductive property under the near-infrared (NIR) illumination with a responsivity of 177.3 A W-1.
    [Show full text]
  • Spin Quantum Computing with Endohedral Fullerenes
    Spin Quantum Computing with Endohedral Fullerenes W. Harneit Spin Quantum Computing with Endohedral Fullerenes W. Harneit, Fachbereich Physik, Universität Osnabrück 1. Introduction 1,2 More than twenty years after its inception, the idea of using quantum information to outperform classical 3 computers remains an inspiring and challenging goal for the experimentalist. Even in 2016, it is still unclear which of the numerous hardware concepts offers the most viable route to a large or even medium-scale implementation, i.e., a quantum processor using significantly more than a handful of quantum bits. We take the opportunity to review here the present state of the art in using endohedral 60 60 fullerenes for building a quantum computer. We will concentrate on N@C and P@C with their well-known favorable spin properties since they have been most studied in 4 the quantum computing context. The related systems of metallo5 -fullerenes and other molecular atom cages like silsesquioxanes are largely disregarded here, although recent studies indicate that 6–9 they may also have some favorable properties for quantum information science. After a brief introduction to solid-state spin quantum computing (§1), we start with fundamental considerations about the system architecture for a scalable fullerene-based quantum register element (§2), outline the main developments in endohedral fullerene materials science relevant for realizing such a register (§3), review experimental implementations of quantum operations in endohedral fullerene ensembles (§4), illustrate the ongoing quest to realize an efficient single-spin read-out for these materials (§5), and conclude with a very brief outlook on further experimental challenges and opportunities (1.1.
    [Show full text]
  • Fullerenes Revisited
    GENERAL ¨ ARTICLE Fullerenes Revisited Materials Chemistry and Applications of C60 Molecules Pradeep P Shanbogh and Nalini G Sundaram The serendipitous discovery of C60 fullerene, which resulted in the prestigious Nobel Prize in Chemistry in 1996, spurred the finding of other fullerenes possessing carbon atoms rang- ing from 16 to hundreds. In this article, we offer a bird’s eye view of the synthesis, properties and recent applications of this class of carbon allotropes with special emphasis on C (left) Pradeep P Shanbogh 60 is a PhD student in PPISR, molecules. The versatility of the molecule and its applications Bangalore. His research interlinking the various interdisciplinary areas of science are work is on synthesis, solid described. state chemistry and structural aspects of History of the Fullerene photocatalytic and photoluminescent Fullerenes are the carbon allotropes composed entirely of carbon nanomaterials, and on organic and inorganic and exist in the form of a hollow sphere (buckyballs), ellipsoid or reactions involving various tube(buckytubes or carbonnanotubes). The existenceof fullerenes novel materials. was first predicted by Eiji Osawa of Toyohashi University of (right) Nalini G Sundaram Technology in 1970 and was discovered experimentally for the is a faculty at PPISR, first time in September 1985. It was detected in the time-of-flight Bangalore. She teaches mass spectrometer from the product of laser vaporization of crystallography and materials science. Her graphite. Fullerene C60, the most abundant molecule, was first research interests are in the synthesized in 1990 by Kramster et al,byanelectricarcresistive synthesis of novel functional heating of graphite rods [1]. nanomaterials, structural elucidation of novel Interestingly, the first fullerene discovered, known as the photocatalytic and Buckminster fullerene, is also called the Bucky ball [2].
    [Show full text]
  • Lawrence Berkeley National Laboratory Recent Work
    Lawrence Berkeley National Laboratory Recent Work Title Photoionization and photofragmentation of singly charged positive and negative Sc3 N@ C80 endohedral fullerene ions Permalink https://escholarship.org/uc/item/0b15m4tn Journal Physical Review A, 99(6) ISSN 2469-9926 Authors Müller, A Martins, M Kilcoyne, ALD et al. Publication Date 2019-06-03 DOI 10.1103/PhysRevA.99.063401 Peer reviewed eScholarship.org Powered by the California Digital Library University of California 1 Photoionization and photofragmentation of singly charged positive and negative 2 Sc3N@C80 endohedral fullerene ions 1, ∗ 2 3 4 1 5 5 6 3 A. M¨uller, M. Martins, A. L. D. Kilcoyne, R. A. Phaneuf, J. Hellhund, A. Borovik Jr., K. Holste, S. Bari, 5 6 5 2 7 6 5 4 T. Buhr, S. Klumpp, A. Perry-Sassmannshausen, S. Reinwardt, S. Ricz, K. Schubert, and S. Schippers 1 5 Institut f¨urAtom- und Molek¨ulphysik,Justus-Liebig-Universit¨atGießen, 6 Leihgesterner Weg 217, 35392 Giessen, Germany 2 7 Institut f¨urExperimentalphysik, Universit¨atHamburg, 8 Luruper Chaussee 149, 22761 Hamburg, Germany 3 9 Advanced Light Source, Lawrence Berkeley National Laboratory, 10 1 Cyclotron Road, M.S. 7R0222, Berkeley, CA 94720-8229, USA 4 11 Department of Physics, University of Nevada, Reno, NV 89557-0058, USA 5 12 I. Physikalisches Institut, Justus-Liebig-Universit¨atGießen, 13 Heinrich-Buff-Ring 16, 35392 Giessen, Germany 6 14 Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany 7 15 Institute for Nuclear Research, Hungarian Academy of Sciences, P.O. Box 51, 4001 Debrecen, Hungary 16 (Dated: April 6, 2019) + − Photoprocesses of the endohedral fullerene ions Sc3N@C80 and Sc3N@C80 in the gas phase have been investigated in the photon energy ranges 30 - 50 eV and 280 - 420 eV.
    [Show full text]
  • Formation of Dimers of Light Noble Atoms Under Encapsulation Within Fullerene’S Voids Tymofii Yu Nikolaienko1 and Eugene S Kryachko2*
    Nikolaienko and Kryachko Nanoscale Research Letters (2015) 10:185 DOI 10.1186/s11671-015-0871-x NANO REVIEW Open Access Formation of dimers of light noble atoms under encapsulation within fullerene’s voids Tymofii Yu Nikolaienko1 and Eugene S Kryachko2* Abstract Van der Waals (vdW) He2 diatomic trapped inside buckminsterfullerene’s void and preserving its diatomic bonding is itself a controversial phenomenon due to the smallness of the void diameter comparing to the He-He equilibrium distance. We propound a computational approach, including smaller fullerenes, C20 and C28, to demonstrate that encapsulation of He2 inside the studied fullerenes exhibits an interesting quantum behavior resulting in a binding at shorter, non-vdW internuclear distances, and we develop a computational model to interpret these He-He bonding patterns in terms of Bader’s atom-in-molecule theory. We also conjecture a computational existence of He2@C60 on a solid basis of its theoretical UV absorption spectrum and a comparison with that of C60. Keywords: Fullerene confinement; Noble atoms dimers; Bonding patterns; QTAIM Review bond length of approximately 28 Å and the binding − Background introduction energy of 0.0039 cm 1 (approximately 0.56 mK) [9]. At the recent lecture of Prof. Ihor R. Yukhnovskii ‘Phase Another surprise came in 2000 when the diffraction Transition of the First Order Below the Liquid-Gas Critical experiments [10] of molecular beam consisting of small Point,’ partly published elsewhere [1], one of the authors clusters of He finally resolved the longstanding paradox 4 of the titled work, E.S.K., has been actually impressed by a with the van der Waals He2 dimer.
    [Show full text]
  • Metallofullerene and Fullerene Formation from Condensing Carbon Gas Under Conditions of Stellar Outflows and Implication to Stardust
    Metallofullerene and fullerene formation from condensing carbon gas under conditions of stellar outflows and implication to stardust Paul W. Dunka,b,1, Jean-Joseph Adjizianc, Nathan K. Kaiserb, John P. Quinnb, Gregory T. Blakneyb, Christopher P. Ewelsc,1, Alan G. Marshalla,b,1, and Harold W. Krotoa,1 aDepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306; bIon Cyclotron Resonance Program, National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310; and cInstitut des Matériaux Jean Rouxel, Centre National de la Recherche Scientifique, Unité Mixte de Recherche 6502, Université de Nantes, BP 32229 Nantes, France Contributed by Harold W. Kroto, August 29, 2013 (sent for review June 13, 2013) Carbonaceous presolar grains of supernovae origin have long confirmed to exist in circumstellar and interstellar environments. been isolated and are determined to be the carrier of anomalous C60 and C70 were first unequivocally detected in a planetary 22Ne in ancient meteorites. That exotic 22Ne is, in fact, the decay nebula in 2010, which was thought to be hydrogen deficient (11). isotope of relatively short-lived 22Na formed by explosive nucleo- Thereafter, Buckminsterfullerene was detected in hydrogen- synthesis, and therefore, a selective and rapid Na physical trapping rich [including the least H-deficient R Coronae Borealis stars] mechanism must take place during carbon condensation in super- (12, 13) and oxygen-rich environments (14), as well as the ISM nova ejecta. Elucidation of the processes that trap Na and produce (15) and a protoplanetary nebula (16). Moreover, fullerenes large carbon molecules should yield insight into carbon stardust have been detected in a host of other circumstellar and in- enrichment and formation.
    [Show full text]