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Problem Set Solutions Chapter 7, Quantum Chemistry, 5 Ed., Levine

The document contains solutions to problems from a quantum chemistry textbook. It analyzes which operators are Hermitian and which satisfy requirements to represent physical quantities. It also finds the parity of hydrogen atom wavefunctions and calculates probabilities for measuring angular momentum components. The key results are: - Operators like d/dx and i*d/dx are Hermitian while d/dx and sqrt are not. - The 2s wavefunction is even parity while the 2px wavefunction is odd parity. - For a particle in a box, a measurement would most likely yield the first excited state energy based on the given initial wavefunction.

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204 views10 pages

Problem Set Solutions Chapter 7, Quantum Chemistry, 5 Ed., Levine

The document contains solutions to problems from a quantum chemistry textbook. It analyzes which operators are Hermitian and which satisfy requirements to represent physical quantities. It also finds the parity of hydrogen atom wavefunctions and calculates probabilities for measuring angular momentum components. The key results are: - Operators like d/dx and i*d/dx are Hermitian while d/dx and sqrt are not. - The 2s wavefunction is even parity while the 2px wavefunction is odd parity. - For a particle in a box, a measurement would most likely yield the first excited state energy based on the given initial wavefunction.

Uploaded by

Sabellano Loven Ralph
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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PROBLEM SET SOLUTIONS Chapter 7, Quantum Chemistry, 5th Ed.

, Levine

7.6 Which of the following operators are Hermitian? For a Hermitian operator, <A> = <A>*, or <fAg> = <gAf>*. Assume f & g are well-behaved at limits of integration. Integration by parts: u v' = uv - v u' (a) <fd/dxg> = f* (dg/dx) d = f*g - g (df/dx)* d = - <gd/dxf>* NO (b) <fi d/dxg> = f* (i dg/dx) d = i f*g + g (i df/dx)*d = <gi d/dxf>* YES

(c) <f4 d2/dx2g> = f* (4 d2g/dx2) d ; [u = f, v' = d2g/dx2, v = dg/dx, u' = df/dx] = 4 f*dg/dx - 4 (dg/dx) (df/dx)*d ; [u = df*/dx, v' = dg/dx, v = g, u' = d2f*/dx2] = -4 (df*/dx)g + 4 g d2f*/dx2 d = <g4 d2/dx2f> YES

(d) <fi d2/dx2g> = f* (i d2g/dx2) d ; [u = f, v' = d2g/dx2, v = dg/dx, u' = df/dx] = i f*dg/dx - i (dg/dx) (df/dx)*d ; [u = df*/dx, v' = dg/dx, v = g, u' = d2f*/dx2] = -i (df*/dx)g + i g d2f*/dx2 d = - g (i d2f/dx2)* d

= - <gi d2/dx2f>* NO

7.9 Which of the following operators meet all the requirements for a quantum mechancal operator that is to represent a physical quantity? Operator must be linear & Hermitian (a) SQRT = ( (b) d/dx (c) d2/dx2 (d) i d/dx )1/2 NOT LINEAR LINEAR, NOT HERMITIAN LINEAR & HERMITIAN LINEAR & HERMITIAN

7.17 For the hydrogenlike atom, V = -Z (e')2 (x2 + y2 + z2)-1/2 And the potential energy is an even function of the coordinates. (a) What is the parity of 2s?

2s = 1/[4(2)1/2] (Z/a)3/2 (2 - Zr/a) e-Zr/(2a) (x) = -x, (y) = -y, (z) = -z, (r) = r, () = - , () = + 2s= 1/[4(2)1/2] (Z/a)3/2 {(2 - Zr/a) e-Zr/(2a)} = 1/[4(2)1/2] (Z/a)3/2(2 - Zr/a) e-Zr/(2a) = 2s (b) EVEN What is the parity of 2px?

2px = 1/[4(2)1/2] (Z/a)5/2 r e-Zr/(2a) sin cos 2px = 1/[4(2)1/2] (Z/a)5/2 { r e-Zr/(2a) sin cos } = 1/[4(2)1/2] (Z/a)5/2 r e-Zr/(2a) sin ( - ) cos ( + ) sin ( - ) = sin cos - cos sin = 0 - (-1) sin = sin cos ( + ) = cos cos - sin sin = - cos - 0 = - cos 2px = 1/[4(2)1/2] (Z/a)5/2 r e-Zr/(2a) sin (- cos ) = - 2px ODD (c)2s + 2px = 1/[4(2)1/2] (Z/a)3/2 e-Zr/(2a) x{2 - Zr/a + rZ/a sin cos } H (2s + 2px ) = H 2s + H 2px = E22s + E22px = E2 (2s + 2px ) Yes, eigenfunction

(2s + 2px ) = 2s + 2px= 2s - 2px

neither even nor odd, no parity We showed previously that when V is even, the wavefunctions of a system with non-degenergate energy levels must be of definite parity. Here, the n=2 level is degenerate, hence no definite parity.

7.26

For a hydrogen atom in a p state, the possible outcomes of a measurement of Lz are -h, 0, and h. For each of the following wavefunctions give the probabilities of each of these three results.

Lz 2pm = m h 2pm; for a p state, m = -1, 0, 1 Write as a linear combination of eigenfunctions of Lz. The probability of getting a particular value when the property is measured is the square of the corresponding coefficient. Probability of measuring property i = ci2 1 = ci2 (a) 2pz = 2p0 = c1 2p-1 + c2 2p0 + c3 2p1 c1= c3= 0. c2= 1 Probability of measuring h is square of coefficient of 2p1 : 0 Probability of measuring -h is square of coefficient of 2p-1 : 0 Probability of measuring 0 is square of coefficient of 2p0 : 1. Note: c12 = c22 + c32 = 1 = 0 + 1 + 0 (b) 2py = -i/2 2p1 + i/2 2p-1

Probability of measuring h is square of coefficient of 2p1 : -i/22 = (-i/2) (-i/2)* = 1/2 Probability of measuring -h is square of coefficient of 2p-1 : i/22 = (i/2) (i/2)* = 1/2 Probability of measuring 0 is square of coefficient of 2p0 : 0 Note: c12 = c22 + c32 = 1 = 1/2 + 1/2 + 0 (c) 2p1 = c1 2p-1 + c2 2p0 + c3 2p1

c1 = 0 = c2, c3 = 1 & c12 = c22 + c32 = 1 Probability of measuring h is square of coefficient of 2p1 : 1

Probability of measuring -h is square of coefficient of 2p-1 : 0 Probability of measuring 0 is square of coefficient of 2p0 : 0.

7.27

(3rd Ed.; like example, p. 185, 5th Ed.) Consider a particle in a nonstationary state in a onedimensional box of length L with infinite walls. Suppose at time t0 its state function is the parabolic function (t0) = N x (L - x) 0<x<L

where N is the normalization constant. If at time t0 we were to make a measurement of the particle's energy, what would be the possible outcomes of the measurement & what would be the probability for each such outcome?

For a 1D particle in a box, H = -h2/(2m) d2/dx2; V = 0 (0 < x < L), V = (x < 0, x > L) The complete set of eigenfunctions of the H operator for a 1D particle in a box are the n n = (2/L)1/2 sin (nx/L) n = 0 0<x<L x < 0, x > L

Since (t0) is an arbitrary function, we can expand it in terms of the eigenfunctions of H: (t0) = c n n, where c n = <(t0) n>. The probability of obtaining the eigenfunction En when making a measurement is c n2. Find c
n

c n = <(t0) n> = 0L (t0) n dx = 0L N x (L - x) (2/L)1/2 sin (nx/L) dx = N (2/L)1/2 {L 0L x sin (nx/L) dx - 0L x2 sin (nx/L) dx} = N (2/L)1/2 [L/(n)]3 {- (n)2 cos (n) + [(n)2 -2] cos (n) + 2} = N (2/L)1/2 [L/(n)]3 2 (1 - cos (n))

If n = 1, 3, 5, cos (n) = -1. If n = 2, 4, 6, cos (n) = 1. c n = N 23/2 L5/2/ (n)3 (1 - (-1)) = N 25/2 L5/2/ (n)3, n = 1, 3, 5, c n = N 23/2 L5/2/ (n)3 (1 - 1) = 0, n = 2, 4, 6, Probability of measuring E n is c n2. c n2 = 0, n = 2, 4, 6, (t0) = N x (L - x), 0 < x < L, is odd function n = (2/L)1/2 sin (nx/L), 0 < x < L, is even & so doesn't contribute to (t0)

c n2 = N2 25 L5/ (n)6, n = 1, 3, 5, To evaluate c n need normalization constant N: <(t0) (t0)> = 0L N2 x2 (L - x) 2 dx = 0L N2 x2 (L2 - L x + x2) dx = N2 (L2 0L x2 dx - 2L 0L x3 dx + 0L x4 dx) = N2 {L2 (x3/3)0L - 2L (x4/4)0L + (x5/5)0L} = N2 {L5/3 - 2 L5/4 + L5/5} = N2 L5{1/3 - 2/4 + 1/5} = N2 L5/30 = 1 , if N = SQRT (30/ L5) c n2 = (30/ L5) 25 L5/ (n)6, n = 1, 3, 5, = (30) (32)/(n)6 c 12 = (30) (32)/()6 = 0.99855 c 32 = (30) (32)/(2)6 = 0.001370 c 52 = (30) (32)/(4)6 = 0.000064 Most of the contribution comes from 1 because it losely resembles (t0)--See Fig. 7.3, p. 186, 5th Ed.

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