Dissertation > Excellent graduate degree dissertation topics show

The DFT Study on Structures and Second-order Nonlinear Optical Properties of Closo-Metallacarborane Half-sandwich Complexes

Author: ZouHaiYan
Tutor: ChouYongQing
School: Northeast Normal University
Course: Physical and chemical
Keywords: Ferradicarbollide Rhenacarborane Sandwich complexes DFT Second-orderNLO Property
CLC: O641.4
Type: Master's thesis
Year: 2013
Downloads: 15
Quote: 0
Read: Download Dissertation

Abstract


Metallacarboranes are a class of inorganic polyhedral clusters containing carbon, boron,hydrogen, and metal atoms in various combinations. One typical of them is the sandwichcomplexes that whose structures are similar with ferrocenes. Metallacarboranes are becominga subject of growing interest for chemical workers owing to their unique combination offeatures and properties including the rigidity of the cages, hydrophobicity, and the chemicaland thermal stability due to delocalized charge. Process in this field has been discussed in anumber of experimental and theoretical reviews. In recent years, metallacarboranes are foundto be good candidates as the nonlinear optics （NLO） materials for their well performed NLOproperties, as well as the relative optical transparency. This work employed the quantumchemistry calculation method with the FF method to calculate the NLO properties offerradicarbollide and rhenacarborane half-sandwich complexes. The results show that:（1） The nonlinear optical （NLO） properties of a series of sandwich complexes which arecoordinated by7,10,12vertexes ferradicarbaboranes and1,2,4,5-Me4C6H2（dur1）,1,2,3,4-Me4C5H（dur2） were investigated by density functional theory （DFT） CAM-B3LYPmethod. The results indicate that the vertexes of ferradicarbaboranes and the substituteposition of nitryl both affect the molecular geometry and then affect the NLO properties of themolecules. The dipole moment and the polarizability are both enhanced with the increase ofthe vertexes of ferradicarbaboranes. The HOMO-LUMO energy gaps of molecules with10vertexes ferradicarbaboranes are relatively smaller, so the first hyperpolarizabilities（tot）values of them are larger than the molecules with12and7vertexes ferradicarbaboranes.When replacing of the atom H of Fe（Ⅱ） para-position by nitro, the totvalues of moleculesare larger than the non-substitution molecules；However, the atom H of Fe（Ⅱ） ortho-positionis substituted by nitro, the totvalues of molecules are smaller than the non-substitutionmolecules. In the studied molecules, the carboranes can act as either electronic donor oracceptor.（2） Three sets of n-legged piano stool shaped （-Re（CO）3or-Re（CO）3I）12-vertexrhenacarborane half-sandwich complexes （n=3or4） have been investigated by densityfunctional theory （DFT）. Natural bond orbital （NBO） analysis shows that introducing iodine（I） atom changes the bond formations between rhenium （Re） ion and carborane cage or3/4-legged piano stools. The redox-switchable second-order nonlinear optics （NLO）properties of sets1and3are different, notably, the total first hyperpolarizability （βtot） ofcomplex231eis about20times larger than that of its parent complex3. Furthermore,time-dependent density functional theory （TDDFT） calculations were employed to accountfor the redox-switchable NLO properties, the plots of frontier molecular orbitals （FMOs） andelectron density difference maps （EDDM） visually indicate that the intramolecularinteractions among I atom, Re ion and carborane cage contribute to the redox property of set3.

Related Dissertations

  1. Density Functional Theory Study of Dimethyl Ether Adsorption on the Low-Index Pt Surface,O485
  2. The Algorithm of DFT with a Subset of Output Points Based on TS101 and Its Software Implementation,TN911.72
  3. Theoretical Studies on Cyclization Mechanism and Regioselectivities of Selected Organic Reactions,O643.12
  4. Hydrogen complex photochemical Theoretical Study,O641.1
  5. Pyridine Metal Complexes electronic spectra and redox properties of theoretical research,O627
  6. The Oxygen Reduction Activity of the Pt-Based Catalyst: First Principles Study,TM911.4
  7. First-Principles Studies on CeO2 -Based Catalysts,O469
  8. A Density Functional Theory Study for Wn C0,± （n=1-6） Clusters,O641.1
  9. The DFT Study on Second-order Nonlinear Optical Property of the Terpyridyl Complexes,O626.1
  10. Study on Catalytic Properties of Metal Cluster/Low-Dimensional Carbon,TB383.1
  11. Spin- flip transition metals react with acetonitrile relativistic density functional theory study,O621.13
  12. The Exploitation and Investigation of Efficient Catalysts for the Preparation of Ethylene Glycol Via Ethylene Oxide Hydration,TQ223.162
  13. By determining the initial ionization mass spectrometry to predict the characteristics of sites indole alkaloids law cracking,O657.63
  14. Detection of BPA by Surface-Enhanced Raman Scattering,TQ243.1
  15. Mechanism Studies on Cycloisomerisation of 1,6-dienes Catalyzed by Ruthenium,TQ203.1
  16. Study, Design and Implementation of Channelization Technology Based on Filterbanks for Shortwave Signals,TN713
  17. The Study on Graphene’s Structure with DFT and ABEEMσπ,O613.71
  18. Adsorption of H2 on MgO Clusters Studied by Ab Initio Methods,O647.3
  19. Research on Synchronized Phasor Measurement Algorithms in Power System,TM73
  20. The DFT Study on Second-order Nonlinear Optical Property of the Open-shell Schiff Base Ligands and Complexes,O641.4
  21. Occlusive substituted carborane derivatives NLO properties of DFT Study,O627.8

CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Structural Chemistry > Complex chemistry ( coordination chemistry )
© 2012 www.DissertationTopic.Net  Mobile