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Homework 3 Solution

Chapter 3

3.10 Line spectra of hydrogenic atoms

Spectra of hydrogen-like atoms are classified in terms of electron transitions to a common lower energy level. a. All transitions from energy levels n = 2, 3, ... to n = 1 (the K shell) are labeled K lines and constitute the Lyman series. The spectral line corresponding to the smallest energy difference (n = 2 to n = 1) is labeled the K line, next is labeled K , and so on. The transition from n = to n = 1 has the largest energy difference and defines the greatest photon energy (shortest wavelength) in the K series; hence it is called the absorption edge Ke. What is the range of wavelengths for the K lines? What is Ke? Where are these lines with respect to the visible spectrum? b. All transitions from energy levels n = 3, 4, ... to n = 2 (L shell) are labeled L lines and constitute the Balmer series. What is the range of wavelengths for the L lines (i.e., L and Le)? Are these in the visible range? c. All transitions from energy levels n = 4, 5, to n = 3 (M shell) are labeled M lines and constitute the Paschen series. What is the range of wavelengths for the M lines? Are these in the visible range? d. How would you expect the spectral lines to depend on the atomic number Z?

Solution

Consider the expression for the energy change for a transition from n = n2 to n = n1, 1 1 2 E = Z EI 2 2 n2 n1 (1)

where EI = 13.6 eV is the ionization energy from the ground state (n = 1) and Z is the atomic number; for hydrogen Z = 1. The absorption wavelength is given by = hc / E. a and For the Lyman series (K-shell), n1 = 1. For K, n2 = 2, which gives E = 10.2 eV from Eqn. (1)

( K ) =

34 8 1 hc (6.626 10 J s)(3.0 10 m s ) = 91.2 nm ( Ke ) = = E (13.6 eV)(1.602 10 19 J/eV )

The wavelengths range from 91.2 nm to 122 nm; much shorter than the visible spectrum. b For the Balmer series (L-shell), n1 = 2. For La, n2 = 3, which gives E = 1.889 eV and

34 3.0 108 m s 1 ) hc (6.626 10 J s ) ( = 657 nm ( L ) = = E (1.889 eV )(1.602 10 19 J/eV )

3.1

Homework 3 Solution

34 3.0 108 m s 1 ) hc (6.626 10 J s ) ( = 365 nm ( Le ) = = 19 E (3.4 eV)( 1.602 10 J/eV)

The wavelengths range from 365 nm to 657 nm. Part of this is in the visible spectrum (blue and green). c For the Paschen series (M-shell), n1 = 3. For Ma, n2 = 4, which gives E = 0.6611 eV and

34 (3.0 108 m s 1 ) = 1877 nm hc (6.626 10 J s ) = 19 E (0.6611 eV)( 1.602 10 J/eV )

( M ) =

34 3.0 108 m s 1 ) hc (6.626 10 J s ) ( = 821 nm ( Me ) = = 19 E (1.511 eV)( 1.602 10 J/eV)

The wavelengths range from 821 nm to 1877 nm which is in the infrared region. d The transition energy depends on Z2, and therefore the emitted photon wavelength of the spectral lines depends inversely on Z2

For each of the following atoms and ions, sketch the electronic structure, using a box for an orbital wavefunction and an arrow (up or down) for an electron: a. Manganese, [Ar]3d54s2 b. Cobalt, [Ar]3d74s2 c. Iron ion, Fe+2, given that Fe is [Ar]3d64s2 d. Neodymium ion, Nd+3, given that Nd is [Xe]4f46s2.

Solution

4s 3d

Mn Cobalt

[ Ar] 3 d5 4 s2 4s [ Ar] 3 d7 4 s2 4s 3d 3d

Fe + 2 Nd+3

[ Ar] 3 d4 4 s2 6s [ Xe] 4 f 1 6 s2 4f

3.2

Homework 3 Solution

Chapter 4

4.1 Phase of an atomic orbital

a. What is the functional form of a 1s wavefunction, (r)? Sketch schematically the atomic wavefunction 1s(r) as a function of distance from the nucleus. b. What is the total wavefunction 1s(r,t)? c. What is meant by two wavefunctions 1s(A) and 1s(B) that are out of phase? d. Sketch schematically the two wavefunctions 1s(A) and 1s(B) at one instant.

Solution

1s(r) decays exponentially as exp(r/ao), where ao is the Bohr radius (Table 3.2 in the a textbook).

1s(r)

Figure 4Q1-1 Atomic wavefunction as a function of distance from the nucleus. b 1s(r,t) = 1s(r) exp(jEt/h) = 1s(r) exp(jt) where = E/h is an angular frequency (Section 3.2.2 of the textbook). The total wavefunction is harmonic in time. Recall that exp(j) = cos + jsin so that exp(jt) = cost + jsint. c Two sine waves of the same frequency will have a certain phase difference which represents the time delay between the time oscillations of the two waves. Two waves will be in phase if their maxima coincide and out of phase if the maximum of one coincides with the minimum of the other. Two 1s wavefunctions, 1s(A) and 1s(B) will have the same frequency. Like two sine waves of the same frequency, the waves can be in phase or out of phase. When they are out of phase, if 1s(A) = 1 then 1s(B) = 1 and vice versa. d

1 s(A) 1 s(B)

r A

Figure 4Q1-2 Two 1s wavefunctions which are out of phase (sketches at the same instant)

3.3

Homework 3 Solution

Consider a linear chain of five identical atoms representing a hypothetical molecule. Suppose that each atomic wavefunction is 1s wavefunction. This system of identical atoms has a center of symmetry C with respect to the center of molecule (third atom from the end) and all molecular wavefunctions must be either symmetric or antisymmetric about C. a. Using LCAO principle, sketch the possible molecular orbitals. b. Sketch the probability distribution

2

c. If more nodes in the wavefunction lead to greater energies, order the energies of the molecular orbitals.

Solution

POSSIBLE MOLECULAR ORBITALS IN INCREACING ENERGY ORDER PROBABILITY DISTRIBUTIONS

3.4

Homework 3 Solution

Germanium, silicon, and diamond have the same crystal structure, that of diamond. Bonding in each case involves sp3 hybridization. The bonding energy decreases as we go from C to Si to Ge, as noted in Table 4Q3-1. Table 4Q3-1 Property Diamond Silicon Melting temperature, 0C 3800 Covalent radius, nm 0.077 Bond energy, eV 3.60 First ionization energy, eV 11.26 Bandgap, eV ? Germanium 1417 0.117 1.84 8.15 1.12 Tin 937 0.122 1.7 7.88 0.67

a. What would you expect for the band gap of diamond? How does it compare with the experimental value of 5.5 eV? b. Tin has a tetragonal crystal structure, which makes it different than its group members, diamond, silicon, and germanium. 1. Is it a metal or a semiconductor? 2. What experiments do you think would expose its semiconductor properties?

Solution

Given the properties in Table 4Q3-1, we have the following plots:

3.5

Homework 3 Solution

Energy Gap, eV 8 7 6 5 Diamond 4 3

Diamond

(a) Energy gap versus melting temperature. From the plot, it seems that diamond has an Eg = 3.4 eV and Sn has Eg 0 or is a metal

(b) Energy gap versus bond energy. From the plot, it seems that diamond has an Eg = 6.8 eV and Sn has Eg 0.9 or is a metal

Energy Gap, eV 7

Diamond

(c) Energy gap versus covalent radius. From the plot, it seems that diamond has an Eg = 4.7 eV and Sn has Eg 1.5 eV or is a metal.

(d) Energy gap versus first ionization energy. From the plot, it seems that diamond has an Eg = 6.3 eV and Sn has Eg 0.3 eV or is a metal.

Figure 4Q3-1

Each is a plot of the band gap Eg (or energy gap) vs. some property. The straight line in each is drawn to pass through Si and Ge. Diamond and tin points are then located on this straight line at the intersections with the vertical lines representing the corresponding properties of diamond and tin.

3.6

Homework 3 Solution

a Diamond has an Eg greater than Si and Ge. Averaging the four Eg for diamond we find 5.3 eV which is close to the experimental value of 5.5 eV. b (1) All the four properties indicate that tin has Eg 0 or is a metal.

(2) Tins semiconductivity can be tested by examining its electrical conductivity and optical absorption (see Chapter 5 in the textbook). For example, for metals the conductivity should NOT be thermally activated over a wide temperature range, whereas for semiconductors there will be an Arrhenius temperature dependence over at least some temperature range. Further, semiconductors have an absorption edge that corresponds to h > Eg (Chapter 5 in the textbook).

Indium as an element is a metal. It has a valency of III. Sb as an element is a metal and has a valency of V. InSb is a semiconductor, with each atom bonding to four neighbors, just like in silicon. Explain how this is possible and why InSb is a semiconductor and not a metal alloy. (Consider the electronic structure and sp3 hybridization for each atom.)

Solution

The one s and three p orbitals hybridize to form 4 hyb orbitals. In Sb there are 5 valence electrons. One hyb has two paired electrons and 3 hyb have 1 electron each as shown in Figure 4Q4-1. In In there are 3 electrons so one hyb is empty. This empty hyb of In can overlap the full hyb of Sb. The overlapped orbital, the bonding orbital, then has two paired electrons. This is a bond between In and Sb even though the electrons come from Sb (this type of bonding is called dative bonding). It is a bond because the electrons in the overlapped orbital are shared by both Sb and In. The other 3 hyb of Sb can overlap 3 hyb of neighboring In to form "normal bonds". Repeating this in three dimensions generates the InSb crystal where each atom bonds to four neighboring atoms as shown. As all the bonding orbitals are full, the valence band formed from these orbitals is also full. The crystal structure is reminiscent of that of Si, as all the valence electrons are in bonds. Since it is similar to Si, InSb is a semiconductor.

Sb

Sb atom (Valency V)

In

In atom (Valency III)

hyb orbitals

Valence electron

hyb orbitals

Valence electron

In Sb In Sb Sb In Sb In In Sb In Sb Sb In Sb In

3.7

Homework 3 Solution

3.8

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