Problems and Solutions in Quantum Chemistry and Physics

INDEX

CHAPTER 1

ATOMIC PHYSICS AND THE OLD QUANTUM THEORY

In this first chapter we emphasize the early experiments and theory which motivated the development of quantum mechanics. By the year 1900 Classical or Newtonian mechanics was available in the powerful formulations of Lagrange and Hamilton, and the classical electromagnetic theory was embodied in the differential equations of Maxwell. Defects were, however, made evident by the failure of the classical theories to explain the frequency dependence of the intensity of radiation emitted by a blackbody. A turning point for the theory came with Planck’s explanation of blackbody radiation (1900) and Einstein’s description of the photoelectric effect (1905). Both of these quantum theories postulated a discreteness of energy. For a blackbody the radiating oscillators were allowed to have only certain discrete energies, and in the photoelectric effect the radiation was assumed to consist of energy quanta or photons. A major success of the quantum idea was Bohr’s theory of one-electron atoms (1911).

From 1900 to 1925 quantum phenomena were treated by imposing quantum restrictions on the classical solutions for mechanical systems. The most general formulation of the old quantum theory is the Wilson-Sommerfeld quantization rule (1915), but it is clear that before 1925 there was no satisfactory, general theory. A major step in the direction of quantum mechanics was de Broglie’s association of wave properties with matter (1923).

The problems in this chapter concentrate on classical mechanics and the application of simple quantization rules. The properties of waves will be treated in detail in Chapter 2. In all numerical problems SI units are used. For a discussion of units see Appendix 1.

Suggested general reading: VW; JA; HI; PW, Chapters 1 and 2.

PROBLEMS

1.1 Consider a projectile that has been fired from the earth. Take the vertical direction as y and the horizontal direction as x.

(a) Write out the Lagrangian function L for the system and use it with Lagrange’s equation to derive the two differential equations which describe the motion of the projectile, (neglect air friction)

(b) Write out the Hamiltonian function H for the system and use it to obtain the canonical equations of motion. (q1 = x, q2 = y)

Solution: Ref. G0,23

(a) The Lagrangian function for the projectile is:

where g is the acceleration of gravity. Lagrange’s equation is

For the x equation we find

so that

For the y equation we find

The resulting differential equation is

(b) The Hamiltonian function is

Hamilton’s canonical equations give

and

In this simple problem the direct application of Newton’s law f = ma is clearly the preferred procedure.

1.2 Show that the total kinetic energy of two particles of masses m1 and m2 can be written as

where

and

= the velocity of m1 relative to m2

Solution : Ref. GO,58

The velocity of the center of mass is then given by:

we find

Thus

The total kinetic energy is, therefore, the sum of the energy of motion of the center of mass and the energy of motion about the center of mass.

is

is the moment of inertia and ω is the angular velocity of the system. (Hint: Separate the kinetic energy of the motion of the center of mass from the total kinetic energy to obtain the rotational kinetic energy.)

Solution: Ref. GO,59

From Problem 1.2 we have

The first term is the translational kinetic energy of the center of mass while the second term must be the rotational kinetic energy.

in spherical polar coordinates we find

Rx = Rsinθcosφ, Ry = Rsinθsinφ, Rz = Rcosθ

Taking time derivatives with R constant we find

So that

Then

where ω is the angular velocity. The rotational energy may also be written as

E = J²/2I

where the angular momentum J is defined as Iω.

1.4 In a simple harmonic oscillator two point masses m1 and m2 are connected by a spring so that Hooke’s Law is obeyed.

where

k = the force constant

R = the instantaneous separation of the masses

Re = the equilibrium separation

(a) Show that the total vibrational energy can be written as

where μ is the reduced mass.

(b) Solve Lagrange’s equation of motion for this system and show that the natural frequency of vibration is

Solution: Ref. BL.64

(a) The total energy of the system is

(1)

Since Hooke’s law is obeyed we have

(2)

where

Integration of (2) yields

(3)

where the constant of integration is chosen so that

V(Re) = 0

This fixes the zero of energy. If TCM is taken as the translational kinetic energy of the center of mass, we have

(4)

Since

we may further write

. Thus, using the same procedure as in Problem 1.3 we find

Since Erot results from R² (θ² + sin²φ²), we then have for the vibrational energy

(b) The Lagrangian function for this system is

and Lagrange’s equation of motion is

The general solution of the differential equation

is

or

The natural frequency of the oscillation is clearly given by

1.5 A sphere of radius a with a total charge of +e has a uniform distribution of positive charge throughout. When an electron is released inside this sphere, what frequency of oscillation is predicted by classical mechanics? Compute the numerical value of the frequency assuming that a = 1 Å. This problem is based on the model of the atom that was proposed by Thomson in 1903. (Hint: First show that the force on the electron is -kr where k is a constant and r is the distance of the electron from the center of the sphere.)

Solution: Ref. JA,70; S3,27

The potential energy of interaction of the point charges q1 and q2 is

where r is their separation. Here we are using the rationalized MKS system of units. A discussion of units is given in Appendix 1. Now consider the interaction of the charge q1 with the shell of thickness drs and charge density p shown in Fig. 1.5.

Fig. 1.5

The charge element dq2 in the ring rs to rs + drs and θ to θ + dθ is given by

dq2 = p(2πrssinθ)rsdθdrs

and the potential energy of interaction between q1 and dq2 is

The contribution from the entire shell of radius rs is obtained by integrating over θ:

But we know that:

D² = rs²+ r²–2rsrcosθ, DdD = rsrsinθdθ

So

Therefore each shell having rs < r contributes

(1)

to the total potential while each shell having rs > r contributes

(2)

If the charge q1 is situated a distance r from the center of a sphere of uniform charge density e, the total potential energy becomes

where a ls the radius of the sphere and rs < a. Integration leads to the result

And the force on q1 is

For the Thomson atom q1 = -e and p = +e/(4na³/3). The force equation becomes

and we are dealing with a simple harmonic oscillator. From Problem 1.4 we have

Thus the radiation from an electron in this model of the atom (Thomson’s atom) is expected to lie in the ultraviolet part of the spectrum. This model does not agree with the results of atomic spectroscopy where many different frequencies are found even for the hydrogen atom.

It is interesting to note that the analogous problem can be carried through for the gravitational attraction of masses m1 and m2. A solid sphere with a hole drilled through its center and a small test mass released in the hole could in principle be used to measure the gravitational constant G. Of course, the experiment would have to be carried out under free fall conditions.

1.6 A mass is suspended by a massless elastic rod having a rectangular cross-section as shown in Figure 1.6.

Fig. 1.6

A small displacement

r = xi + yj Y3

of the mass perpendicular to the axis of the rod leads to the restoring force

(a) Set up the Lagrangian function for this system in the x’y’ axis system.

(b) Derive the differential equations which describe the motion of the mass in the x’y’ axis system after a small displacement from equilibrium and solve for the natural frequencies of the motion.

Solution: Ref. HZ3,62

(a) From Problem 1.4 we see that the potential energy is given by

The displacements in the xy frame can be written in terms of the displacements in the x’y’ frame using the relations

x = x’cosθ + y’sinθ, y =–x’sinθ + y’cosθ

Therefore

The kinetic energy T has the form

and

(b) Lagrange’s equation has the form

where in this problem q1 = x’ and q2 = y’. Therefore, we obtain the equations

The natural frequencies can be obtained by assuming that the displacements carry out simple harmonic motions with the angular frequency ω so that

where φ is a constant phase factor. We then have

This set of equations has non-trivial solutions for x’ and y’ only when the determinant of coefficients vanishes. This becomes evident when a solution is attempted by Cramer’s rule. The only unknown is the ratio x’/y’ and there are two equations. Hence, the numerators vanish and one is left with the trivial solution x’ = y’ = 0 except when the denominator vanishes.

Setting the determinant of coefficients equal to zero we have

And expanding the determinant we find

or

and the two roots are

’ and ÿ’ are uncoupled and can be solved separately to obtain ωx and ωy.

1.7 In the classical planetary model of a hydrogen-like atom an electron with mass me and charge -e is assumed to move in a circular orbit around a nucleus which has a mass M and a charge +Ze. The only forces acting on the particles arise from the coulombic attraction of the charges and it is assumed that M» me.

(a) Obtain an equation for the total energy E of the atom in terms of the radius r of a stable orbit. Neglect the radiation of energy by the accelerating electron.

(b) Derive an equation for the radius r of a stable orbit in terms of me, e, and the orbital angular momentum £ of the electron. Show that the radius r for a stable orbit can be written as

Solution: Ref. KP,20; HZ1.15; PW,36; SI,395

(a) The coulombic attraction provides the centripetal force to maintain a circular orbit.

Therefore

(1)

The total energy is given by

(2)

and using Eq. (1) we have

(3)

where r is the radius of a stable orbit. z

(b) From Eqs. (1) and (2) we have

(4)

= mvr, v² can be eliminated from Eq. (4) tc give

The solutions given here are based on the assumption that no radiation is emitted even though the electron is accelerating toward the nucleus. It should be realized that an electron moving in a circular orbit with the fixed radius r and the angular frequency w has the acceleration ω²r toward the center. Since an accelerating charge does radiate, the classical planetary model of the atom fails.

1.8 Two particles having the same mass are connected by springs with equal force constants as shown in Figure 1.8. If we choose the displacements of the masses from their equilibrium positions to be x1 and x2 in the same direction, then we may write the potential energy as

Assuming that the particles move on a frictionless plane, show that the natural frequencies for motion of the particles are

Fig. 1.8

Solution: Ref. WDC, 28

The Lagrangian T-V is

The two equations of motion are then

(1)

(2)

Choosing

x1 = A1cos(wt + α) and x2 = A2cos(wt + α)

we find by substitution into (1) and (2)

(3)

This equation has nontrivial solutions only if the determinant of the 2x2 matrix vanishes.

Thus

The roots are

Since

ω1 = 2πν1

we have

Substitution of ν1 and ν2 back into (3) allows determination of the relative amplitudes:

for ν1: A1 = A2, thus both masses are moving to the right (see Fig. 1.8)

for ν2: A1 =–A2, the two balls are moving in opposite directions (see Fig. 1.8)

1.9 The term black-body radiation refers in practice to the radiation emitted from a small orifice of a heated hollow cavity. The experimental dependence of the energy density of such radiation on temperature and wavelength is shown in Fig. 1.9. The energy density ρ(ν) in the range ν to ν + dν was shown by Planck to be

where

<ε> is the average energy of the oscillators which are assumed to make up the walls of the cavity and which are in equilibrium with the radiation field inside the cavity,

N(v)dv is the number of modes of the radiation field in a cavity of volume V in the frequency range ν to ν + dν

This problem is concerned with the evaluation of <ε>.

Fig. 1.9

(a) According to classical statistical mechanics, the average energy <ε> for systems in thermal equilibrium is

where kB is Boltzmann’s constant. For a simple harmonic oscillator

Evaluate the integral to obtain an equation for <ε>.

(b) If the energy of an oscillator can only take on the values

ε1 = ihν

where i is an integer, then the integral in part (a) must be replaced by

). i=0

Solution: Ref. PI1,3; EI,57; S3,253; WS,450

(a) For a continuous distribution of energy

Thus each quadratic term in ε contributes an amount kBT/2 to <ε>. The generalization of this result is called the Principle of Equiparition of Energy.

(b) For a discrete distribution of energy

where

Since

and

we have

In the case that kBT » hν

so that

Thus as the spacing between the levels goes to zero (kBT » hν), the classical result of part (a) is reclaimed.

1.10 A string is attached between two supports that are separated by a distance L as shown in Fig. 1.10. Standing waves are then excited in the string so that λ/L « 1. The wave velocity in the string is v = λν.

Fig. 1.10

(a) Obtain an expression for the number of vibrational modes dn that have wavelengths between λ and λ + dλ.

(b) Obtain an expression for the number of vibrational modes that have frequencies between ν and ν + dν.

Solution:

(a) Waves in the string have the form

with the boundary conditions,

ψ(0) = ψ(L) = 0

These conditions are met by setting φ 0 and requiring that

(2πL/λ) = nπ

where n is an integer. Therefore, the number of half wavelengths in the distance L is n = 2L/λ and each value of n specifies a mode of vibration. The number of modes which occur in the range λ to λ + dλ is given by

dn = 2L|d(1/λ)| = (2L/λ²)dλ

where n has been treated as a continuous variable since dn/n is assumed to be vanishingly small.

(b) From part (a) we have

dn = (2L/v)|d(v/λ)| = (2L/v)dv

for the number of modes in the range ν to ν + dν.

1.11 Consider a cavity of volume V which contains black-body radiation. Show that the number of modes of the radiation field with frequencies between ν and ν + dν is given by:

In counting the number of modes it is convenient to use a three dimensional k space with axes: kx = (1/λx), ky = (1/λy), and kz = (1/λz). The number of modes is proportional to a volume in this space and the calculation proceeds easily in spherical polar coordinates.

Solution: Ref. S4,225; S3,254

From Problem 1.10 we have that

dnx = 2Lxd(1/λx) 2Lxdkx

Now consider a cavity with dimensions Lx, Ly, and Lz so that LxLyLz = V. For three dimensions we write

dnxdnydnz 8(LxLyLz)dkxdkydkz

Since ν = c/λ = ck and dν = cdk, we need to determine the number of modes in the range k to k + dk.

It is convenient to work in k-space with the quantity

which is invariant to the orientation of the coordinate system. In spherical polar coordinates we can immediately write

dkxdkydkz = k²sinθdθdφdk

The total number of modes in the range k to k + dk is then given by

arises because we only want positive values of the components kx, ky, and kz (see Fig. 1.11).

Fig. 1.11

Converting to frequency we can write

An extra factor of 2 has appeared in this step to take into account the two directions of polarization for photons. In a classical treatment this factor arises because there are two transverse waves associated with electromagnetic radiation.

1.12 The Stefan-Boltzmann law states that the total energy density in blackbody radiation at all frequencies is proportional to the fourth power of the temperature.

Use the Planck radiation equation to obtain this result and determine the constant σ.

Solution: Ref. P11,3; PA1,576; LI,137

Inserting Planck’s equation for ρ(ν) from Problem 1.9 we obtain

For convenience let x = hv/kBT. Then

(1)

The integral can be written as

Then integration by parts or use of a table of integrals shows that

The integral becomes

In this step we have used the definition of the Bernoulli numbers:

Finally from Eq. (1) we obtain

and

σ = 7.565•10–16J•m–3•K–4

The rate of emission from a surface at the temperature T is given by

Here σ’ = 5.669x10–8Wm–2K–4. This is the Stefan–Boltzmann constant that is often quoted in the literature.

1.13 A plot of the energy density ρ(λ) of the radiation in equilibrium with a blackbody versus λ shows a maximum at λ = λmax. The Wien displacement law states that λmax = A/T where A is a constant and T is the absolute temperature. Show that Planck’s radiation equation is consistent with this law and determine the constant A.

Solution: Ref. MM1,492

Planck’s radiation law (Problem 1.9) can be written as

The maximum in ρ(λ) is then located by setting dρ(λ)/dλ equal to zero.

Letting x = hc/λkBT this equation becomes

5 = xex/(ex–1), ex = 5/(5–x)

This transcendental equation can be solved by numerical methods to obtain x = 4.965.

Therefore,

1.14 An Einstein crystal is defined to be a collection of N three dimensional oscillators in thermal equilibrium at temperature T. Use the equation for the average energy of an oscillator to derive an equation for the heat capacity Cv of such a crystal. Determine the high and low limits of Cv and plot Cv versus kBT/hv.

Solution: Ref. DA3,354; RU,30

The average energy of an oscillator from Problem 1.9 is

For 3N oscillators we have E = 3N<ε>. By definition the heat capacity at constant volume is

If NA = Avogadro’s number = N so that kBNA = R, the ideal gas constant, then

where

u = hv/kBT

(see Figure 1.14).

High Temperature Limit

Low Temperature Limit

The high and low temperature limits agree with the experimental findings. However, an extension of the theory to allow for a distribution of frequencies is needed to improve the fit to experimental data over the entire temperature range.

Fig. 1.14

1.15 Consider a molecule having the two low lying energy levels ε1 and ε2 with the degeneracies g1 and g2, respectively, i.e. there are g1 states having the energy ε1 and g2 states having the energy ε2. Show that the specific heat for a collection of N such molecules at thermal equilibrium is given by:

in the range 0 to 2 for g = 1.

Solution: Ref. RU,97

From Problem 1.9 we have the total energy

We choose to measure the energy from the level ε1 (i.e. let ε1 = 0). Therefore

By definition the heat capacity at constant volume is Cv = dE/dT or

Multiplying numerator and denominator by e–2ε/kT we obtain

A plot of Cv versus kBT/ε is shown in Fig. 1.15. The significant feature of this plot is that the maximum heat capacity occurs when the energy separation between the levels is about equal to kBT. This behavior should be compared with that of the harmonic oscillator where an infinite number of levels are available (see Problems 1.9 and 1.14).

Fig. 1.15

1.16 mv² by finding the minimum voltage Vo necessary to stop the electrons. Show how Planck’s constant may be measured from a plot of stopping voltage versus v.

Solution: Ref. SE,110

From Fig. 1.16 we see that energy balance gives

(impingent photon) (kinetic energy) (work function)

Thus

The repeller potential energy necessary to just stop all of the electrons (stopping voltage) must be equal in magnitude to the kinetic energy of the ejected electron. Thus

mv² = hv–eφ, if eφ is the same for the collector and the emitter.

This equation is then in slope-intercept form. A plot of eVo versus v gives a straight: line, the slope of which is h and the intercept on the v axis gives the work function eφ = hvo (vo is the threshold frequency). See: J. Rudnick and D. S. Tannhauser, Am. J. Phys. 44, 796(1976).

Fig. 1.16

1.17 Bohr’s theory for a hydrogen-like atom is based on the classical planetary model with the following additional assumptions:

The atom can exist only in stationary states having one of the discrete energies E1, E2 , ...

Only radiation having a frequency v = (En–Em)/h can be emitted or absorbed by the atom where Em and En are the energies associated with the stationary states n and m.

The theory correctly predicts that the lines in the absorption and emission spectra of the hydrogen atom