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  • 1
    Electronic Resource
    Electronic Resource
    Energy-exchange processes by tunneling electrons (1994)
    Springer
    Applied physics 59 (1994), S. 155-161 
    Details
    ISSN: 1432-0630
    Keywords: 61.16 ; 65.00 ; 73.40
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Resistive heating, emission heating or cooling (e.g., the Nottingham effect), and thermal fluctuation radiation are examples of energy exchange processes which are fundamental in electron field emission and in tunneling junctions of scanning tunneling microscopy. These exchange processes are analyzed for both electronic tunneling processes. We first discuss the energy delivered by a monoatomic tip in the field emission process. Strong phonon excitation is expected for field emission currents exceeding 1 nA. Secondly we present a theoretical calculation of the thermal deposition associated with the Nottingham effect in a tunneling junction. The calculation is based on the free electron model for the electrode materials and the tunneling process across a planar vacuum gap. Our results show that the thermal power is deposited not only at the electron receiving electrode but also at the emitting electrode. This originates from a finite probability for electrons below the Fermi level to tunnel through the tunneling barrier replaced by electrons starting from the Fermi level. The comparison between the calculations and the recent STM measurements is given. Finally we discuss the other energy exchange processes in the tunneling junction, and conclude that the thermal coupling between the tip and the sample of STM is extremely small under UHV conditions. This is important for high temperature STM.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00332209
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  • 2
    Electronic Resource
    Electronic Resource
    1,2-Diphospha-3,4-diboretane und 1,3-Diphospha-2,4,5-triborolan: Synthese und Struktur sowie Berechnungen zur Molekülstruktur Über den Einfluß von Substituenten auf die Struktur von 1,2-Diphospha-3,4-diboretan (1995)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1111-1122 
    Details
    ISSN: 0044-2313
    Keywords: 1,2-Diphospha-3,4-diboretanes ; 1,3-diphospha-2,4,5-triborolane derivative ; preparation ; molecular structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,2-Diphospha-3,4-diboretanes and 1,3-Diphospha-2,4,5-triborolane: Synthesis and Structure as well as Calculations on the Molecular Structure On the Effect of Substituents on the Structure of 1,2-Diphospha-3,4-diboretane[2 + 2]-Cyclocondensation reactions led to the synthesis of the 1,2-diphospha-3,4-diboretanes [(t-BuP)2B2(NMe2)2], 1 a, and [(t-BuP)2B(NMe2)B(NiPr2)], 1 b. Their molecular structures have been determined by X-ray methods, and these are compared with the structure of [(t-Bu)P—BN(iPr2)]2, 2 a. Compounds 1 show a folded B2P2 four membered ring having tert.-butyl groups in anti-positions. Ab initio calculations on 1,2-diphospha-3,4-diboretanes demonstrate that two conformers with anti-orientation of the substituents at the phosphorus atoms can be expected. These differ by the relative orientation of the almost planar P2BR groups to the BP2 plane. The influence of substituents (H and NH2 at the B atoms, and H and Me at the P atoms) on the ring conformation has been studied. Finally, the first derivative of a 1,3-diphospha-2,4,5-triborolane, 3 a, is reported.
    Notes: Durch [2 + 2]-Cyclokondensationen wurden die 1,2-Diphospha-3,4-diboretane [(t-BuP)2B2(NMe2)2], 1 a, und [(t-BuP)2B(NMe2)B(NiPr2)], 1 b, dargestellt, ihre Molekülstrukturen mit Röntgenbeugungsmethoden bestimmt und mit der Struktur von [(t-Bu)P—B(NiPr2)]2, 2 a, verglichen. In den Verbindungen 1 liegen gefaltete B2P2-Vierringe vor mit anti-ständigen tert.-Butylgruppen, während das Ringsystem in 2 a planar gebaut ist, die tert.-Butylgruppen aber ebenfalls anti-Stellung einnehmen. Ab initio-Rechnungen an 1,2-Diphospha-3,4-diboretanen belegen, daß zwei unterschiedliche Konformere mit anti-Orientierung der Substituenten an den P-Atomen stabil sind, die sich durch die relative Orientierung der annähernd trigonal-planaren P2BR-Baugruppen zur BP2-Ebene voneinander unterscheiden. Der Einfluß von Substituenten (H und NH2 am B-Atom, H und CH3 am P-Atom) wird ermittelt. Beschrieben wird ferner das erste Derivat eines 1,3-Diphospha-2,4,5-triborolans, 3 a.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19956210702
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  • 3
    Electronic Resource
    Electronic Resource
    1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolan und 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborin: Synthese und Struktur sowie Berechnungen zur MolekülstrukturProfessor Hans-Georg von Schnering zum 65. Geburtstage gewidmet (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 1462-1470 
    Details
    ISSN: 0044-2313
    Keywords: 1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane ; 1,2-bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine ; preparation ; NMR ; molecular structures ; ab initio calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane and 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine: Synthesis and Structure as well as Calculations on the Molecular StructureThe diphosphides K2[(C6H5)P—(C6H5)P—P(C6H5)], 4 or K2[(tBuP)—(tBuP)2—P(tBu)], 5, react with (ClBNMe2)2 to form the binary 5-membered ring system 1,2-bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolane (C6H5P)3(BNMe2)2, 2a, and the 6-membered ring system 1,2-bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborine, (tBuP)4(BNMe2)2, 3a, respectively. 2a and 3a could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analyses. The two ring systems are folded; 2a exists in the „envelope“- 3a in the „boat“-conformation. Ab initio computations for 3,4,5-triphospha-1,2-diborolane M5 show that the global minimum is characterized by one B—P double bond. The parent compound geometry M6 is characterized by transannular bonding in the PH—BH—BH—PH moiety which differs in character from those in the four- and five-membered rings (BH)2(PH)2 and (BH)2(PH)3 M5 d, respectively. Explicit calculation of the influence of amino substituents on boron improved agreement of the bond length between computed and X-ray data.
    Notes: Die Diphosphide K2[(C6H5)P—(C6H5)P—P (C6H5)], 4, bzw. K2[(tBuP)—(tBuP)2—P(tBu)], 5, reagieren mit (ClBNMe2)2 zu dem binären Fünfringsystem 1,2-Bis(dimethylamino)-3,4,5-triphenyl-3,4,5-triphospha-1,2-diborolan (C6H5P)3(BNMe2)2, 2a, bzw. dem Sechsringsystem 1,2-Bis(dimethylamino)-3,4,5,6-tetra-tbutyl-3,4,5,6-tetraphospha-1,2-diborin, (tBuP)4(BNMe2)2, 3a. 2a und 3a konnten in reiner Form isoliert, NMR-spektroskopisch und durch Röntgenstrukturanalysen charakterisiert werden. Beide Ringsysteme sind gefaltet; 2a zeigt eine „envelope“- 3a eine „Wannen“-Konformation.Ab initio Berechnungen an 3,4,5-Triphospha-1,2-diborolan M5 zeigen, daß im globalen Minimum eine B—P-Doppelbindung mit annähernd planarem σ3-Phosphor vorliegt. Die Geometrie der Stammverbindung des Sechsringes M6 weist „durch-den-Ring“-Bindung in der PH—BH—BH—PH-Baugruppe auf, welche sich von jenen im Vier- und Fünfring M5 d unterscheidet. Durch die explizite Berechnung des Einflusses von Aminosubstituenten an Bor auf die Geometrien des Fünf- und Sechsringes verbessert sich die Übereinstimmung der Bindungslängen mit den Daten der Röntgenstrukturanalyse.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220906
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