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    Didik Krisdiyanto
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    Lab Handout Experiment 05

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    Didik Krisdiyanto
    ghv

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    © All Rights Reserved
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    Revised une 2008 CHEMISTRY 461 Experiment 5 - SPECTRA OF POLYENES AND NANOPARTICLES (by Bryant Fujimoto, Philip Reid, and David Ginger) L HAZARDS Ethanol is flammable and should be kept away from flames. Zine Acetate, Zine Oxide and Tetramethy! Ammonium Hydroxide are toxic, and should be disposed of as described below. Il. WASTE DISPOSAL, ‘The product of the reactions is ZnO in ethanol. It should be placed in the marked bottle in the hood. If you are not working in a hood, take a 250 ml erlenmeyer flask and label it nanoparticle waste. Collect the waste solution in the flask until you have a chance to empty the flask into the waste bottle in the hood. IIL THEORY Particle In a Box Model ‘Semiconductor nanoparticles are nanometer-sized crystals of semiconductors such as CdSe or ZnO. The electronic absorption spectra of these particles is strongly dependent on size for nanoparticles with diameters ranging from 1-20. Because the size dependence of the absorption spectra arises from quantum-mechanical “particle-in-a-box” confinement effects, semiconductor nanoparticles are often called “quantum dots” and their size-dependent absorption spectra provide a simple and convenient way to monitor particle size during growth. In this laboratory you will investigate the effects of quantum confinement on the optical properties of both one- dimension systems (Linear alkenes) and three-dimension systems (semiconductor nanoparticles). The dependence of an absorption spectrum on particle size can be understood using the particle- in-a-box model introduced in undergraduate quantum mechanics. For a particle in a one dimensional box of length L, the potential V(x) is given by: wo x<0 V(x)=10 OsxsL oO x>b Ohm Figure 1. The potential for a one dimensional particle in a box. ‘The time-independent Schrédinger equation for a particle in this potential is: ~— St aky Osxsk Where fis Planck’s constant divided by 2x, m is the mass of the particle, y is the wavefunction describing the particle, and E is the total energy of the particle, Imposing boundary conditions and normalizing, the solutions to the above equation are the familiar particle-in-a-box ‘wavefunctions and associated energy levels: 2. (nax vac [2 sn( 2) 242 " 8mi? A few of these wavefunctions are shown in Figure 2. The number 7 is called the quantum number and is constrained to integer values beginning at one (i.e., n 3, ...). Different wavefunctions or energy levels are specified using their corresponding quantum number (Wis¥'21--- Ey» Eyy--.)- Notice that the number of nodes in the wavefunctions (points where the wavefunction equals zero) increases as the energy increases, E hea) n=3 oh? a Bma* n=2 .. by = L 0 z— h Figure 2, Particle in a box energies, wavefunctions and probabilities. Application of the Particle in a Box Model to Linear Alkenes Chemical bonding can be described using molecular orbitals (MO) constructed from linear combinations of atomic orbitals. As an example, consider ethene (CH»=CHa). In ethene, the carbons are sp” hybridized such that the 2s, 2p,, and 2p, atomic are combined to produce sp” orbitals localized on each carbon. Carbon-hydrogen bonds is formed by the overlap of one of the (sp) orbitals with the H(Is) orbital. The o-bond between the two carbons is formed by overlap of the C(sp’) orbitals from each carbon, Two 2p, orbitals remain on each carbon atom, labeled 2pa and 2pz, and these orbitals overlap to form a x bond. There are two ways to combine the p orbitals as illustrated in Figure 3: (2p + 2pz2) and (2p. ~ 2pm). When the orbitals are combined as (2p21 + 2p.2) a m bonding orbital is formed, and when combined as (2p.1 ~ 2pa) a7 anti- bonding orbital is formed. The anti-bonding orbital has a reduced electron density between the carbon atoms in comparison to the bonding orbital; therefore, the energy of the anti-bonding orbital is greater as shown in Figure 3 Energy at AntiBonding MO . 8 ~|" Figure 3. x bonding in ethene. Figure 4 presents a qualitative energy diagram for ethene. Since o bonds are stronger than = bonds, the c bonds are located at lower energy relative to the w bonds. Also, since the C-H bond is stronger than the C-C bond (413 kJ/mole vs 347 kJ/mole) the C-H bond are placed at lowest energy. dl — to, ieee he ace Figure 4. Qualitative energy level diagram for Ethene. Left diagram is the ground state and the right diagram is the first excited state, ‘The 12 valence electrons in ethene are added to these energy levels according to the Aufbau principle and Hund's rules. Since the x electrons are “delocalized” between the carbon atoms, wwe can describe the energetics of the m orbitals using the particle-in-a-box model. ‘The lowest- energy transition corresponds to the advancement of an electron from the highest occupied x orbital to the lowest unoccupied 7 orbital. The energy difference between these levels can be defined in terms of the quantum numbers j and n as: ‘The lowest-energy transition corresponds to j = n+1; therefore, that the energy difference is: AE, insta _ Qn iP a ~ 8mi? Emam Ey Question 1: Derive the above expression, For ethene, the highest occupied x orbital corresponds to n= I so that: 3 Ag, = 2" 8m? 2 This difference in energy is related to the wavelength of light corresponding to this transition (162 nm as indicated in Figure 4), corresponding to a “box” length of: pot mc 1-4 =3.8x10" m=3.8A ime This length is quite different from the C=C bond length of 1.34 A (184% error!). Recall, the particle-in-a-box model assumes an infinitely steep potential; however, the x orbitals extend past the centers of the carbon nuclei such that this model potential is approximate. How does this model work for linear alkenes of variable size or box length? To address this question, we will apply the one-dimensional particle-in-a-box model to the following diphenyl substituted alkenes: O~~9 O10 1,4 diphenyl-1,3-butadiene 1,6 dipheny!-1,3,5 hexatriene Om) 1,8 diphenyl-1,3,5,7 octatetraene The electrons in the x orbitals of the alkene chains are localized to a “box” defined by the distance between the phenyl rings. To calculate a theoretical box length we will use 1.39 A as the average length of a carbon-carbon bond in these molecules. For 1,4 diphenyl-1,3-butadiene, there are 5 bonds between the two phenyl rings such that the length of the box is 5 x 1.39 A = 6.95 A. The number of electrons in the box is the number of electrons in the 1-bonding orbitals. For 1,4 diphenyl-1,3-butadiene, there are 2 double bonds corresponding to 4 electrons in the box. In the ground state electron configuration, there are two electrons in the n= 1 level and two in the n=2 level. Therefore, the lowest-energy electronic transition corresponds to an advancement of an electron from the n = 2 (the highest occupied molecular orbital) to the n = 3 (the lowest unoccupied molecular orbital) level. According to the particle in a box model, the difference is energy between these levels is given by: Sr ye Bm A Sha AEy = 8me By measuring the location of the lowest-energy the absorption band of 1,4 diphenyl-1,3- budatiene, one can determine 2, and use this information to determine L. This process is repeated for the other two diphenyl alkenes. Pat je in an Infinite Spherical Well Following our approximation of the linear alkenes as one-dimensional boxes, one is tempted to treat the electronic properties of spherical nanoparticles using a “particle-in-a-sphere” model. Indeed, this is a very useful starting point. In spherical polar coordinates, the time-independent Schrédinger equation is: (eo 28 S| 425 |r, ee r Sve Om For a particle confined to a sphere of radius a by an infinite potential, V(7)=0 for r

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