13

Foundations of
CHAPTER Chemical Spectroscopy

LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition

Problems and Solutions

Chapter 13: Foundations of Chemical Spectroscopy Absorption of Radiation

Chapter 13
Absorption of Radiation
13.1. The molar absorption coefficient of human hemoglobin (molecular weight 64 000) is 532 dm3 cm–1 mol–1 at 430 nm. A solution of
hemoglobin in a cuvette having a light path of 1 cm was found at that wavelength to have a transmittance of 76.7%. Calculate the
concentration in mol dm–3 and in g dm–3.
Solution
13.2. A spectrophotometer has a meter that gives a reading directly proportional to the amount of light reaching the detector. When the
light source is off, the reading is zero. With pure solvent in the light path, the meter reading is 78; with a 0.1 M solution of a solute
in the same solvent, the meter reading is 55. The light path is 0.5 cm. Calculate the absorbance, the transmittance, and the molar
absorption coefficient.
Solution
13.3. The transmission of a potassium chromate solution was measured at a wavelength of 365 nm using a cell with a 1.0-cm path length.
The data are as follows:
Transmission 0.357 0.303 0.194 0.124
Conc. × 104/mol dm–3 0.90 1.10 1.50 1.90

Calculate the molar Naperian absorbance and the molar decadic absorbance.
Solution
13.4. An aqueous solution containing 0.95 g of oxygenated myoglobin (Mr = 18 800) in 100 cm3 gave a transmittance of 0.87 at 580 nm,
with a path length of 10.0 cm. Calculate the molar absorption coefficient.
Solution
13.5. A substance in aqueous solution at a concentration of 0.01 M shows an optical transmittance of 28% with a path length of 2 mm.
Calculate the molar absorption coefficient of the solute. What would be the transmittance in a cell 1-cm thick?
Solution
13.6. The molar absorption coefficient of hemoglobin at 430 nm is 532 dm3 mol–1 cm–1. A solution of hemoglobin was found to have an
absorbance of 0.155 at 430 nm, with a light path of 1.00 cm. Calculate the concentration.
Solution

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Chapter 13: Foundations of Chemical Spectroscopy Atomic Spectra

13.7. A 10 μM solution of a substance gave an absorbance of 0.1028 with a light path of 1 cm. Calculate the molar absorption coefficient.
What would be the percentage light transmittance of a 1-μm solution with the same light path?
Solution
13.8. Two substances of biological importance, NAD+ and NADH, have equal absorption coefficients, 1.8 × 104 dm3 mol–1 cm–1, at 260
nm (a wavelength at which absorption coefficients are equal is known as the isosbestic point 6). At 340 nm, NAD+ does not absorb at
all, but NADH has an absorption coefficient of 6.22 × 103 dm3 mol–1 cm–1. A solution containing both substances had an absorbance
of 0.215 at 340 nm and of 0.850 at 260 nm. Calculate the concentration of each substance.
Solution
13.9. The transmittance of a 0.01 M solution of bromine in carbon tetrachloride, with a path length of 2 mm, is 28%. Calculate the molar
absorption coefficient of bromine at that wavelength. What would the percentage transmittance be in a cell 1-cm thick?
Solution
13.10. An acid HA ionizes in aqueous solution into H+ and A– ions. At a wavelength of 430 nm HA does not absorb light, but A– does so
with an absorption coefficient of 458 dm3 cm–1 mol–1. A solution of the acid at a concentration of 0.1 M was found to have a
transmittance of 1.47% at 430 nm with a path length of 1 cm and at 25 °C. Calculate the dissociation constant of HA at 25 °C, and
ΔG° for the dissociation process.
Solution
Atomic Spectra
13.11. In the Balmer series of the hydrogen atom, the first emission line is observed at 656.3 nm. Calculate the value of the Rydberg
constant. What is the energy of the light quanta emitted during the transition?
Solution
13.12. The ground state of the Li atom has the electronic configuration 1s22s1. What is its spectroscopic term? If the 2s electron is excited
to the 2p state, what terms are then possible?
Solution
13.13. Suppose that an excited state of the carbon atom has the electronic configuration 1s22s22p13p1. What are the possible spectroscopic
terms?
Solution

6
From the Greek prefix iso-, the same, and sbestos, quench. This word is sometimes incorrectly written as “isobestic.”

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Chapter 13: Foundations of Chemical Spectroscopy Atomic Spectra

13.14. What are the terms for the following electronic configurations?
a. Na (1s22s22p63p1)
b. Sc (1s22s22p63s23p64s23d1)
Solution
13.15. What values of J may arise in the following terms?
1
P, 3P, 4P, 1D, 2D, 3D, 4D
Solution
*13.16. Calculate the Landé-g-factor for a 2P1/2 level. What would be the anomalous Zeeman splitting for this level in a magnetic field of
4.0 T?
Solution
*13.17. Calculate the spacing between the lines for a 3D1 → 3P0 transition, in an anomalous Zeeman experiment with a magnetic field of 4.0
T.
Solution
Rotational and Microwave Spectra
35
13.18. The separation between neighboring lines in the pure rotational spectrum of Cl19F is found to be 1.023 cm–1. Calculate the
interatomic distance.
Solution
13.19. The lines in the pure rotational spectrum of HF are 41.9 cm–1 apart. Calculate the interatomic distance. Predict the separation
between the lines for DF and TF.
Solution
13.20. In the microwave spectrum of 12C16O the separation between lines has been measured to be 115270 MHz. Calculate the interatomic
distance.
Solution
*13.21. The J = 0 → J = 1 line in the microwave absorption spectrum of 12C16O and of 13C16O was measured by Gillam et al., [Phys. Rev.
78, 140(1950)]. In its ground vibrational state, the former has the value 3.842 35 cm–1 and the latter, the value 3.673 37 cm–1.
Calculate
a. the bond length of the 12C16O molecule,
b. the relative atomic mass of 13C,
c. the bond length of the 13C16O molecule.
Solution

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Chapter 13: Foundations of Chemical Spectroscopy Vibrational-Rotational and Raman Spectra

13.22. The microwave spectrum of 16O12C32S shows absorption lines separated by 12.163 GHz. That of 16O12C34S shows lines separated by
11.865 GHz. The determination of the bond distances involves solving two simultaneous quadratic equations, which is best done by
successive approximations. To avoid all that labor, simply confirm that the results are consistent with r(O—C) = 116 pm and r(C—
S) = 156 pm.
Solution
Vibrational-Rotational and Raman Spectra

1 2
13.23. The maximum potential energy that a diatomic molecule can store is kx , where x is the amplitude of vibration. If the force
2
constant k is 1.86 × 103 N m–1, calculate the maximum amplitude of vibration for the CO molecule in the v = 0 vibrational state.
Compare this to the bond length obtained in Problem 13.21. Use the value of ur in that problem.
Solution
13.24. Consider the following molecules: H2, HCl, CO2, CH4, H2O, CH3Cl, CH2Cl2, H2O2, NH3, and SF6. Which of them will give
a. a pure rotational spectrum,
b. a vibrational-rotational spectrum,
c. a pure rotational Raman spectrum,
d. a vibrational Raman spectrum?
Solution
13.25. Analysis of the vibrational-rotational spectrum of the H35Cl molecule shows that its fundamental vibrational frequency ν0 is 2988.9
cm–1. Calculate the force constant of the H—Cl bond.
Solution
13.26. A few transitions in the P and R branches of the infrared spectrum of H35Cl spectrum are identified below.
J″ 0 1 2 3 4 5 6
–1
P (cm ) 2865.10 2843.62 2821.56 2798.94 2775.76 2752.04
–1
R (cm ) 2906.24 2925.90 2944.90 2963.29 2981.00 2998.04

Using Eqs. 13.134 or 13.135 as appropriate, calculate ν0 and the rotational constant B .
Solution

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Chapter 13: Foundations of Chemical Spectroscopy Vibrational-Rotational and Raman Spectra

13.27. Comparison of the results of Problem 13.26 to experimental values for H35Cl (ν0 = 2990 cm–1, and B = 10.59 cm–1) shows that Eqs.
13.134 and 13.135 do not accurately relate the observed transitions to the rotational quantum numbers. Much of the error results
1
from not taking the anharmonicity of the potential energy curve into account. Using the definition (see Eq. 13.138) Tv,J = (ν + )ν0
2
1 2
– (v + ) ν0 xe + J(J + 1) B , derive a more accurate expression for ΔTv,J for the v″ = 0 → v′ = 1 transitions of a diatomic molecule.
2
[Even this is an approximate treatment because we are ignoring the coupling of rotations with vibrations.]
Solution

13.28. From the results of Problems 13.26 and 13.27 and the experimental value of ν0 for H35Cl given in Problem 13.27, estimate the value
of the anharmonicity constant xe. Use the average of the P and R branch values for ν0 from Problem 13.26.
Solution
13.29. The vibrational Raman spectrum of 35Cl2 shows series of Stokes and anti-Stokes lines; the separation between the lines in each of
the two series is 0.9752 cm–1. Estimate the bond length in Cl2.
Solution
13.30. The dissociation energy of H2 is 432.0 kJ mol–1 and the fundamental vibrational frequency of the molecule is 1.257 × 1014 s–1.
Calculate the classical dissociation energy. Estimate the zero-point energies of HD and D2 and their dissociation energies.
Solution
13.31. A molecule AB2 is known to be linear but it is not known whether it is B—A—B or A—B—B. Its infrared spectrum is found to
show bands corresponding to three normal modes of vibration. Which is the structure?
Solution
13.32. The frequency of the O—H stretching vibration in CH3OH is 3300 cm–1. Estimate the frequency of the O—D stretching vibration in
CH3OD.
Solution

13.33. The spectroscopic constants for the OH radical are ν0 = 3737.76 cm–1, ν0 xe = 84.8813 cm–1, B = 18.9108 cm–1. Predict the
frequencies at which (a) the P branch transitions ending in, and (b) the R branch beginning in, J = 0, 1, 2 will be observed.
Solution
13.34. Irradiation of acetylene with mercury radiation at 435.83 nm gives rise to a Raman line at 476.85 nm. Calculate the vibrational
frequency that corresponds to this shift.
Solution

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Chapter 13: Foundations of Chemical Spectroscopy Vibrational-Rotational and Raman Spectra

13.35. The fundamental vibrational frequency of H127I is 2309.5 cm–1. Calculate the force constant of the bond.
Solution
*13.36. The following are some normal modes of vibration for several molecules:
[[Image]]
In each case, determine the point group and refer to Appendix E on p. 1028 to determine whether the vibration is active in the
infrared and in the Raman spectrum. Then check your conclusions by reference to the appendix to this chapter (p. 707).
Solution
*13.37. Prove that the force constant k corresponding to the Morse potential function (Eq. 13.146) at small bond extensions is
k = 2Dea2
Calculate the vibration frequency v0 on the basis of the following Morse parameters for H35Cl:
De = 4.67 eV
a = 1.85 × 108 cm–1
Solution
*13.38. The Morse function is only one of several models used to describe the behavior of the potential energy of diatomic molecules. A
popular and very accurate model introduced by Murrell and Sorbie [J. Chem. Soc., Faraday Trans. 2, 70, 1552(1974)] is the so-
called “Extended Rydberg function,” which is written as
E p ( x) = − De (1 + a1 x + a2 x 2 + a3 x 3 )e − a1x ,
where x = r – re, as in the case of the Morse potential of Eq. 13.146, and the ai are constants for a given molecule.
a. Derive an expression for the force constant in terms of the parameters De and ai.
b. Show that in order for a function of this form to have a minimum at r = re, a1 must be both the coefficient of x and the exponential
parameter.
Solution
*13.39. Yet another model for a diatomic potential is the Bond Order function used by Garcia and Laganá [Mol. Phys. 56, 621(1985)],
which is given as
N
E p ( x ) = − De ∑ cn exp ( − n β x ).
n =1

Show that for N = 2, with appropriate choices for the coefficients c1 and c2, this is identical to the Morse potential of Eq. 13.146
expressed as Ep = De(1 – e–βx)2 – De.
Solution

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Chapter 13: Foundations of Chemical Spectroscopy Electronic Spectra

*13.40. The parameters for the bond order (see Problem 13.39) potential of the 35Cl16O radical with N = 4 are (in atomic units) c1 = 2.691
042, c2 = –2.545 521, c3 = 1.017 916, c4 = –0.163437, De = 0.10302, and β = 1.763 768. What is the vibrational frequency (in cm–1)
predicted by this model? [Note that the force constant can be expressed in units of energy area–1.]
Solution
*13.41. A model for the 14N–14N–16O+ ion assigns the following force constants for the two stretching frequencies: k12 = 1092.8 N m–1, and
k23 = 890.68 N m–1. Use Eqs. 13.171–13.174 to calculate the two stretch frequencies obtained from the model.
Solution

*13.42. The fundamental and a few successive overtones of the H +2 molecule lie at 2191, 2064, 1941, 1821, 1705, 1591, 1479 and 1368 cm–
1
, respectively.
a. Starting from Eq. 13.139, derive an expression that can be used to obtain both ν0 and xe by a suitable analysis of the data.
b. Perform the analysis and calculate both ν0 and xe.
Solution
Electronic Spectra
13.43. Sketch potential energy curves for a diatomic molecule in its ground electronic state and n an excited state, consistent with the
following observations:
a. There is a strong 0 ← 0 absorption band, and strong 0 → 0, 1 → 1, and 2 → 2 emission bands.
b. The strongest absorption band is 4 ← 0, and the strongest emission band is 0 → 2.
c. There is no sharp rotational fine structure in absorption, but there is a sharp emission spectrum.
d. The absorption spectrum shows a well-defined fine structure for the 0 ← 0, 1 ← 0, 2 ← 0, 3 ← 0, and 4 ← 0 transitions and for
the 6 ← 0 and 7 ← 0, but not in between.
Solution
*13.44. Using the data in Example 13.12 on p. 702, determine the area under the curve in a plot of Δv against v. Extrapolate to zero Δv to
obtain v′max, since the Birge-Sponer extrapolation shows that at that point v′ = v′max. A better value may be obtained by a nonlinear
extrapolation. What are the values of v′ not given in the table?
Solution

13.45. Calculate the dissociation energy of the hydrogen molecule ion from the vibrational energy level separations of H +2 . The values for
the transitions 1 ← 0, 2 ← 1, …, are, respectively, 2191, 2064, 1941, 1821, 1705, 1591, 1479, 1368, 1257, 1145, 1033, 918, 800,
677, 548, 411, with all values given in cm–1. Use both a linear plot and a curve to obtain answers.
Solution

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Chapter 13: Foundations of Chemical Spectroscopy Electronic Spectra

13.46. The electronic spectra of diatomic molecules in the gas phase typically show extensive vibrational structure superimposed on the
broader electronic transition. Taking the equilibrium geometry of the ground electronic state to be the zero energy, the G (ν″) of Eq.
13.138 can be used to express the energies of the vibrational states v″ (in cm–1) of this electronic state. Denoting the minimum
energy of the excited electronic state as Te (in cm–1), the vibrational energy levels v′ of the excited state can be expressed as
T + G (ν ′ ) . Derive an expression for the frequencies ν of the transitions ν″ → ν′ between the vibrational levels of the ground and
e

excited electronic states. (Note that the vibrational frequencies and anharmonicity constants are not the same for the ground and
excited electronic states.)
Solution
13.47. An easy and reliable way to analyze the electronic spectrum of a diatomic molecule is to use the equation derived in Problem 13.46
as the model for a multiple regression analysis (several plotting packages and mathematics packages such as Mathcad can perform
this task) to simultaneously identify the five unknowns, Te ,ν0′ ,ν0′ xe′ ,ν0′′, and ν0′′xe′′ [McNaught, J. Chem. Ed. 57, 101(1980)]. The
following data are from the electronic spectrum of iodine.
0 → ν′ λ (nm) 1 → ν′ λ (nm) 2 → ν′ λ (nm)
17 567.2 15 581.0 10 607.3
18 564.2 16 577.8 11 603.1
19 561.5 17 574.2 12 599.1
20 558.5 18 571.3 13 595.5
21 555.8 19 568.3 14 591.8
22 553.0 20 565.2 15 588.1
23 550.1 21 559.6 16 584.8
24 547.8 22 556.9 17 581.2
25 542.7 23 554.2 18 578.1
26 540.7 24 551.8 19 575.1
27 538.5 25 549.0 20 572.4

Perform a multiple regression analysis and identify the spectroscopic parameters of the ground and excited electronic states.
Literature values are (in cm–1) Te = 15730, ν0′ = 132.1, ν0′ xe′ = 1.051, ν0′′ = 214.5, and ν0′′xe′′ = 0.614.
Solution

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Chapter 13: Foundations of Chemical Spectroscopy Essay Questions

13.48. The dissociation energy (from the zero-point level) of the ground state O2 (3 Σ g− ) molecule is 5.09 eV. There exists an electronically
excited 3 Σ −u state of O2, whose zero-point level lies 6.21 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into two ground-state O(3P) atoms, while the 3 Σ −u species dissociates into one ground-state O(3P) atom and an
O*(1D) atom that lies 1.97 eV above the ground state. Sketch the potential-energy curves and calculate the dissociation energy of
O2 (3 Σ u− ) into O + O*(1D).
Solution
13.49. The spectroscopic dissociation energy D0 is the energy required to dissociate the molecule in its ground vibrational state. This is
always slightly smaller than the actual depth of the electronic potential energy because of the zero-point energy of the molecule (see
Figure 13.22). Given that for HCl, De = 4.6173 eV, ν0 = 2989 cm–1, and ν0 xe = 52.82 cm–1, calculate the value of D0 for HCl.
Solution
13.50. The dissociation energy (from the zero-point level) of the ground state NO(X2π) molecule is 6.6 eV. There exists an electronically
excited B2Π state of NO whose zero-point level lies at 5.7 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into ground state N(4S) + O(3(P)), while the B2Π species dissociates into two ground-state atoms N(2D) + O(3P)
that lie 3.3 eV above its ground state. Sketch the potential energy curves and calculate the dissociation energy of NO into N(2D) +
O(3P).
Solution
13.51. Sodium vapor, which consists mainly of Na2 molecules, has a system of absorption bands in the green, the origin of the 0, 0 band
being at 20 302.6 cm–1. From the spacing of the vibrational levels it can be deduced that the dissociation energy of the upper state is
0.35 eV. The dissociation of the excited Na2 gives a normal atom and an atom that emits the yellow sodium D line at 589.3 nm.
Calculate the energy of dissociation of Na2 in its ground state.
Solution
For additional problems, see the books listed at the end of the problems in Chapter 12 (pp. 634-635).

Essay Questions
13.52. State the laws of Lambert and Beer, and write an equation comprising the two laws.
13.53. Explain clearly what is meant by absorbance and transmittance, and derive a relationship between them.
13.54. Give an account of the fundamental origins of ultraviolet and infrared spectra.
13.55. Explain the selection rules for infrared spectra, with examples.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

Solutions
13.1. The molar absorption coefficient of human hemoglobin (molecular weight 64 000) is 532 cm–1 mol–1 at 430 nm. A solution of
hemoglobin in a cuvette having a light path of 1 cm was found at that wavelength to have a transmittance of 76.7%. Calculate the
concentration in mol dm–3 and in g dm–3.

Solution:

Given: MW = 64 000, ε = 532 cm –1 mol –1 λ = 430 nm, l = 1 cm, T = 76.7%

Required: c in mol dm–3 and in g dm–3

To determine the concentration of the hemoglobin solution, we use the Beer-Lambert Law, given by Eq. 13.45. This is one of the most
important laws in understanding the foundation of chemical spectroscopy.

I0
A = log10 = ε cl
I

Since ∈ cl is dimensionless, the molar absorption coefficient then has the units dm3 mol–1 cm–1

Eq. 13.39 defines the transmittance as,

I
T≡
I0
Using the above and rearranging Eq. 13.45, we can obtain an expression that can be used to solve the problem.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

I
= 0.767
I0
I0
= ( 0.767 ) = 1.303 780 965
−1

I
I
log10 0 = ε cl
I
I
log10 0
c= I
εl
log10 1.303 780 965
c=
( )(
532 dm3 cm –1 mol –1 1 cm )
c = 0.000 215 739 mol dm −3
c = 2.16 ×10−4 mol dm −3

Converting to g dm-3 we use the molecular weight given in the problem

c = 0.000 215 739 mol dm −3 × 64 000 g mol−1
c = 13.807 297 2 g dm −3
c = 13.8 g dm −3

Back to Problem 13.1 Back to Top

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.2. A spectrophotometer has a meter that gives a reading directly proportional to the amount of light reaching the detector. When the
light source is off, the reading is zero. With pure solvent in the light path, the meter reading is 78; with a 0.1 M solution of a solute
in the same solvent, the meter reading is 55. The light path is 0.5 cm. Calculate the absorbance, the transmittance, and the molar
absorption coefficient.

Solution:

I 0 78
Given: = , c = 0.1 M , l = 0.5 cm
I 55

Required: A, T , ε
I0
To find the absorbance, we use the value given for and substitute it into Eq. 13.45,
I
I0
A = log10 = ε cl
I
78
A = log10 = 0.151 731 913
55
A = 0.152

The transmittance is defined in Eq. 13.39 as,

I
T≡
I0
⎛ 55 ⎞
T =⎜ ⎟
⎝ 78 ⎠
T = 0.705128 205
T = 0.705

To find the molar absorption coefficient, we simply use Eq. 13.45 once more.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

A = ε cl
A
ε=
cl
0.151 731 913
ε=
0.1 mol dm −3 × 0.5 cm
ε = 3.034 638 264 dm3 cm −1 mol−1
ε = 3.03 dm3 cm −1 mol−1

Back to Problem 13.2 Back to Top

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.3. The transmission of a potassium chromate solution was measured at a wavelength of 365 nm using a cell with a 1.0-cm path length.
The data are as follows:
Transmission 0.357 0.303 0.194 0.124
Conc. × 104/mol dm–3 0.90 1.10 1.50 1.90

Calculate the molar Naperian absorbance and the molar decadic absorbance.

Solution:

Given: λ = 365 nm, l = 1.0 cm, c

Required: Naperian and decadic absorbance

I −ε cl
To solve this problem, we use Eq. 13.45 and form a plot of logT against concentration. log10 =
I 0 2.303
−ε l
This should give a straight line with a slope of . See the plot below.
2.303

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

The values used the create the plot are:

Transmission 0.357 0.303 0.194 0.124

Conc. × 104/mol 0.9 1.1 1.5 1.9

dm–3

logT -0.44733 -0.51856 -0.7122 -0.90658

−1
The slope of the plot obtained is m = −0.4653 ×10 dm mol .
3 3

−ε l
Since = −0.4653 × 103 dm3 mol−1 we can then solve for the molar absorption coefficient.
2.303
εl
= 0.4653 ×103 dm3 mol−1
2.303
0.4653 × 103 dm3 mol−1 × 2.303
ε=
l
l = 1.0 cm = 0.1 dm
0.4653 × 103 dm3 mol−1 × 2.303
ε=
0.1 dm
ε = 10 715.859 dm 2 mol−1
ε = 1071.585 9 m 2 mol−1

The decadic absorbance coefficient for a 10 M solution is then,

A = ε cl
A = 10 715.859 dm3 mol−1 cm −1 ×10 × 10−6 mol dm −3 × 1 cm
A = 0.107 158 59
A = 0.107

Back to Problem 13.3 Back to Top

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.4. An aqueous solution containing 0.95 g of oxygenated myoglobin (Mr = 18 800) in 100 cm3 gave a transmittance of 0.87 at 580 nm,
with a path length of 10.0 cm. Calculate the molar absorption coefficient.

Solution:

Given: m = 0.95 g, M r = 18 800, V = 100 cm3 , T = 0.87, λ = 580nm, l = 10.0 cm

Required: ε

To calculate ε we use the Beer-Lambert Law in Eq. 13.45.

I
A = log10 0 = ε cl
I
The absorbance is first calculated by taking the inverse log of the transmittance.
A = log10 T −1
A = log10 ( 0.87 )
−1

A = 0.060 480 747

We then calculate the concentration of the hemoglobin.

1dm3 = 1000 cm3
100 cm3 = 0.1 dm3
n m⎛1⎞
c= = ⎜ ⎟
V M ⎝V ⎠
0.95 g ⎛ 1 ⎞
c= ⎜ −1⎟
18 800 g mol ⎝ 0.1 dm3 ⎠
c = 0.000 505 319 mol dm −3
c = 5.05319 ×10−4 mol dm −3

Solving for ε we obtain,

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

A
ε=
cl
0.060 480 747
ε=
5.05319 ×10−4 mol dm −3 ×10.0 cm
ε = 11.968 821 59 dm3 cm −1 mol−1
ε = 12.0 dm3 cm −1 mol−1

Back to Problem 13.4 Back to Top

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.5. A substance in aqueous solution at a concentration of 0.01 M shows an optical transmittance of 28% with a path length of 2 mm.
Calculate the molar absorption coefficient of the solute. What would be the transmittance in a cell 1-cm thick?

Solution:

Given: c = 0.01 M , T = 0.28, l = 2 mm

Required: ε , Tl =1 cm

To calculate ε we use the Beer-Lambert Law in Eq. 13.45. We can solve in a similar manner to problem 13.4.
The absorbance is first calculated by taking the inverse log of the transmittance.
I
A = log10 0 = ε cl
I
A = log10 T −1
A = log10 ( 0.28 )
−1

A = 0.552 841 969

Rearranging Eq. 13.45, we can solve for ε

A
ε=
cl
0.552 841 969
ε=
0.01 mol dm −3 × 0.2 cm
ε = 276.420 984 3 dm3 cm −1 mol−1
ε = 276 dm3 cm −1 mol−1

To determine the transmittance when the path length is 1.0 cm, we use the molar absorption coefficient obtained above and solve for the
absorbance.
A = ε cl
A = 276.420 984 3 dm3 cm −1 mol−1 × 0.01 mol dm −3 ×1.0 cm
A = 2.764 209 843

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

From Eq. 13.43 we can find the transmittance,

log10T % = 2 − A
log10T % = 2 − 2.764 209 843
log10T % = −0.764 209 843
T % = 10−0.764 209 843
T = 0.172 103 68 %
T = 0.17 %

Back to Problem 13.5 Back to Top

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.6. The molar absorption coefficient of hemoglobin at 430 nm is 532 dm3 mol–1 cm–1. A solution of hemoglobin was found to have an
absorbance of 0.155 at 430 nm, with a light path of 1.00 cm. Calculate the concentration.

Solution:

Given: ε = 532 cm –1 mol –1 λ = 430 nm, l = 1.00 cm, A = 0.155

Required: c

This problem is similar to problem 13.1, however is much simpler to solve. By rearranging Eq. 13.45, we can obtain the concentration

A = ε cl
A
c=
εl
0.155
c=
532 dm3 mol –1 cm –1 × 1.00 cm
c = 0.000 291 353 mol dm −3
c = 2.91×10−4 mol dm −3

Back to Problem 13.6 Back to Top

13-21
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.7. A 10 μM solution of a substance gave an absorbance of 0.1028 with a light path of 1 cm. Calculate the molar absorption coefficient.
What would be the percentage light transmittance of a 1-μm solution with the same light path?

Solution:

Given: c = 10 μ M , A = 0.1028, l = 1 cm
Required: ε , Tc =1 μ M

To calculate ε we rearrange the Beer-Lambert Law, Eq. 13.45.

A = ε cl
A
ε=
cl
0.1028
ε=
10 × 10 mol dm −3 ×1 cm
−6

ε = 10 280 dm3 cm −1 mol−1

ε = 1.028 ×104 dm3 cm −1 mol−1

To determine the transmittance when the concentration is 1 μM, we use the molar absorption coefficient obtained above and solve for the
absorbance.
A = ε cl
A = 1.028 × 104 dm3 cm −1 mol−1 × 10−6 mol dm −3 × 1.0 cm
A = 1.028 × 10−2

From Eq. 13.43 we can find the transmittance,

13-22
Chapter 13: Foundations of Chemical Spectroscopy Solutions

log10T % = 2 − A
log10T % = 2 − 1.028 ×10−2
log10T % = 1.989 72
T % = 101.989 72
T = 97.660 737 6 %
T = 97.66 %

Back to Problem 13.7 Back to Top

13-23
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.8. Two substances of biological importance, NAD+ and NADH, have equal absorption coefficients, 1.8 × 104 dm3 mol–1 cm–1, at 260
nm (a wavelength at which absorption coefficients are equal is known as the isosbestic point 6). At 340 nm, NAD+ does not absorb at
all, but NADH has an absorption coefficient of 6.22 × 103 dm3 mol–1 cm–1. A solution containing both substances had an absorbance
of 0.215 at 340 nm and of 0.850 at 260 nm. Calculate the concentration of each substance.

Solution:

Given: λ = 260 nm; ε both = 1.8 × 104 dm3 mol –1cm –1 , A = 0.850
λ = 340 nm; ε NADH = 6.22 ×103 dm3 mol –1cm –1 , A = 0.215
Required: cNAD + , cNADH

Since we are told that at 340 nm, NAD+ does not absorb at all, we can find the concentration for NADH by applying the Beer-Lambert law
at 340 nm. We can assume the path length, l = 1.00 cm which is the standard value.

A = ε cl
A
c=
εl
0.215
cNADH =
6.22 ×10 dm mol –1 cm –1 × 1.00 cm
3 3

cNADH = 3.456 59 × 10−5 mol dm −3

cNADH = 3.46 × 10−5 mol dm −3

To find the concentration of NAD+, we first calculate the absorbance of NADH at 260 nm.
A = ε cl
A = 1.8 ×104 dm3 cm −1 mol−1 × 3.456 59 × 10−5 mol dm −3 ×1.00 cm
A = 0.622 186 495

The remaining absorbance at 260 nm will be purely the absorbance of NAD+,

6
From the Greek prefix iso-, the same, and sbestos, quench. This word is sometimes incorrectly written as “isobestic.”

13-24
Chapter 13: Foundations of Chemical Spectroscopy Solutions

ANAD+ = 0.850 − 0.622 186 495

ANAD+ = 0.227 813 505

Now we can solve for concentration in a similar manner as above.

A
c=
εl
0.227 813 505
cNAD+ =
1.80 × 104 dm3 mol –1 cm –1 ×1.00 cm
cNAD+ = 1.265 63 × 10−5 mol dm −3
cNAD+ = 1.27 ×10−5 mol dm −3

Back to Problem 13.8 Back to Top

13-25
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.9. The transmittance of a 0.01 M solution of bromine in carbon tetrachloride, with a path length of 2 mm, is 28%. Calculate the molar
absorption coefficient of bromine at that wavelength. What would the percentage transmittance be in a cell 1-cm thick?

Solution:

Given: c = 0.01 M , T = 0.28, l = 2 mm

Required: ε , Tl =1 cm
This problem is parallel to problem 13.5. To calculate ε we use the Beer-Lambert Law in Eq. 13.45.

The absorbance is first calculated by taking the inverse log of the transmittance.
I
A = log10 0 = ε cl
I
A = log10 T −1
A = log10 ( 0.28 )
−1

A = 0.552 841 969

Rearranging Eq. 13.45, we can solve for ε

A
ε=
cl
0.552 841 969
ε=
0.01 mol dm −3 × 0.2 cm
ε = 276.420 984 3 dm3 cm −1 mol−1
ε = 276 dm3 cm −1 mol−1

To determine the transmittance when the path length is 1.0 cm, we use the molar absorption coefficient obtained above and solve for the
absorbance.
A = ε cl
A = 276.420 984 3 dm3 cm −1 mol−1 × 0.01 mol dm −3 × 1.0 cm
A = 2.764 209 843

From Eq. 13.43 we can find the transmittance,

13-26
Chapter 13: Foundations of Chemical Spectroscopy Solutions

log10T % = 2 − A
log10T % = 2 − 2.764 209 843
log10T % = −0.764 209 843
T % = 10−0.764 209 843
T = 0.172 103 68 %
T = 0.17 %
Back to Problem 13.9 Back to Top

13-27
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.10. An acid HA ionizes in aqueous solution into H+ and A– ions. At a wavelength of 430 nm HA does not absorb light, but A– does so
with an absorption coefficient of 458 dm3 cm–1 mol–1. A solution of the acid at a concentration of 0.1 M was found to have a
transmittance of 1.47% at 430 nm with a path length of 1 cm and at 25 °C. Calculate the dissociation constant of HA at 25 °C, and
ΔG° for the dissociation process.

Solution:

Given: λ = 430 nm, ε = 458 dm3 cm –1 mol –1 , c = 0.01 M , T = 1.47% = 0.0147, l = 1 cm, T = 25 °C
Required: K c , ΔG°

To calculate the dissociation constant and Gibbs free energy, we need to recall the principles we learned in chapter 4.

The dissociation of the acid is given by,

HA U H+ + A−

⎡H+ ⎤ ⎡A − ⎤
Kc = ⎣ ⎦ ⎣ ⎦
[ HA ]
And therefore Kc is calculated by determining the concentration of the anion A- which is equal to c. This value is also the same
concentration of H+.

The absorbance is first calculated by taking the inverse log of the transmittance.
I
A = log10 0 = ε cl
I
A = log10 T −1
A = log10 ( 0.0147 )
−1

A = 1.832 682 665

To find c, we rearrange Eq. 13.45,

13-28
Chapter 13: Foundations of Chemical Spectroscopy Solutions

A = ε cl
A
c=
εl
1.832 682 665
c=
458 dm mol –1 cm –1 × 1.00 cm
3

c = 4.001 491× 10−3 mol dm −3

At equilibrium we have the following situation,

HA U H+ + A−
cinitial 0.1 M 0 0
−3 −3
cequilibrium 0.1 − 4.001 491× 10 M 4.001 491×10 M 4.001 491× 10−3 M
Solving for Kc we obtain,

⎡ 4.001 491×10−3 mol dm −3 ⎤ ⎡ 4.001 491× 10−3 mol dm −3 ⎤

Kc = ⎣ ⎦⎣ ⎦
⎡1 − 4.001 491×10 mol dm ⎤
− 3 − 3
⎣ ⎦
−5 −3
K c = 1.607 63 ×10 mol dm
K c = 1.607 × 10−5 mol dm −3

To find the Gibbs free energy we use Eq. 4. 27

ΔG° = − RT ln K c°
(
ΔG° = −8.3145 J K −1 mol−1 × 298.15 K × ln 1.607 63 ×10−5 mol dm −3 )
ΔG° = 27 363.26517 J mol−1
ΔG° = 27.4 kJ mol−1

Back to Problem 13.10 Back to Top

13-29
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.11. In the Balmer series of the hydrogen atom, the first emission line is observed at 656.3 nm. Calculate the value of the Rydberg
constant. What is the energy of the light quanta emitted during the transition?

Solution:

Given: λ = 656.3 nm , Balmer series,

Required: R, ε

To find Rydberg’s constant, we use the principles we learned in Chapter 11. We can find R using Eq. 11.50 and the fact that for the Balmer
series, n = 3. n1 = 2.

1 ⎛ 1 1 ⎞
ν = = R⎜ 2 − 2 ⎟
λ ⎝ n1 n2 ⎠
1 ⎛ 1 1⎞
−9
= R⎜ 2 − 2 ⎟
656.3 ×10 m ⎝2 3 ⎠
35 ⎛ 1 ⎞
R=− ⎜ −9 ⎟
4 ⎝ 656.3 ×10 m ⎠
R = 10 970 592.63 m −1
R = 1.097 ×107 m −1

To find the energy we use,

hc
E=
λ
6.626 × 10−34 J s × 2.998 ×108 m s −1
E=
656.3 ×10−9 m
E = 3.026 78 × 10−19 J
E = 3.027 ×10−19 J

Back to Problem 13.11 Back to Top

13-30
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.12. The ground state of the Li atom has the electronic configuration 1s22s1. What is its spectroscopic term? If the 2s electron is excited
to the 2p state, what terms are then possible?

Solution:

Given: Li, 1s22s1

Required: spectroscopic terms for 2s1 and 2p1 states

The 1s2 electrons form a closed shell and need not be considered.

Back to Problem 13.12 Back to Top

13-31
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.13. Suppose that an excited state of the carbon atom has the electronic configuration 1s22s22p13p1. What are the possible spectroscopic
terms?

Solution:

Back to Problem 13.13 Back to Top

13-32
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.14. What are the terms for the following electronic configurations?
a. Na (1s22s22p63p1)
b. Sc (1s22s22p63s23p64s23d1)

Solution:

Back to Problem 13.14 Back to Top

13-33
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.15. What values of J may arise in the following terms?

1
P, 3P, 4P, 1D, 2D, 3D, 4D

Solution:

Back to Problem 13.15 Back to Top

13-34
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.16. Calculate the Landé-g-factor for a 2P1/2 level. What would be the anomalous Zeeman splitting for this level in a magnetic field of
4.0 T?

Solution:

Back to Problem 13.16 Back to Top

13-35
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.17. Calculate the spacing between the lines for a 3D1 → 3P0 transition, in an anomalous Zeeman experiment with a magnetic field of 4.0
T.

Solution:

Given: 3D1 → 3P0, B = 4.0 T

Required: ΔE

This problem is very similar to example 13.8 given in the text, and can be solved in a similar manner.

For the 3P0 level, gJ = 0. The splitting of the line is therefore entirely due to the splitting of 3D1 level. For this level, gJ is,

gJ = 1+
(1× 2 ) + (1× 2 ) − ( 2 × 3)
( 2 × 2)
1
gJ =
2

It will be split into three levels with MJ = 1, 0, -1, and the separation between the levels is given by Eq. 13.88,
ΔE = g J μ B B
1
ΔE = × 9.273 × 10−24 J T −1 × 4.0 T
2
ΔE = 1.854 6 × 10−23 J

Converting this energy level difference to the spacing in cm we get,

1.854 6 ×10−23 J
ΔE =
6.626 × 10−34 J s × 2.998 ×1010 cm s −1
ΔE = 0.933 613 656 cm
ΔE = 0.93 cm

Back to Problem 13.17 Back to Top

13-36
Chapter 13: Foundations of Chemical Spectroscopy Solutions

35
13.18. The separation between neighboring lines in the pure rotational spectrum of Cl19F is found to be 1.023 cm–1. Calculate the
interatomic distance.

Solution:

Given: 35Cl19F, 2 B = 1.023 cm −1

Required: r

Eq. 13.93 gives the relationship between interatomic distance, inertia and reduced mass.
mm
I = 1 2 r02 = μ r02
m1 + m2

To solve for interatomic distance, we first calculate the moment of inertia from Eq. 13.100 since we already have the value of the rotational
constant, B.
h
B = 2
8π Ic
h
I= 2
8π cB
6.626 ×10−34 J s
I= 2
8π 2.998 × 1010 cm s −1 × 0.5115 cm −1
I = 5.472 48 × 10−46 J

The reduced mass is calculated using Eq.13.94,

mm
μ= 1 2
m1 + m2
35 g mol−1 ×19 g mol−1
μ=
( 35 + 19 ) g mol−1 × 6.022 ×1023 mol−1
μ = 2.044 97 ×10−23 g
μ = 2.044 97 ×10−26 kg

Rearranging Eq. 13.93 and solving for r we obtain,

13-37
Chapter 13: Foundations of Chemical Spectroscopy Solutions

I = μ r02
I
r=
μ
5.472 48 × 10−46 J
r=
2.044 97 × 10−26 kg
r = 1.635 87 ×10−10 m
r = 164 pm

Back to Problem 13.18 Back to Top

13-38
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.19. The lines in the pure rotational spectrum of HF are 41.9 cm–1 apart. Calculate the interatomic distance. Predict the separation
between the lines for DF and TF.

Solution:

Given: HF, 2 B = 41.9 cm −1

Required: r, 2BDF, 2BTF

This problem can be solved in a similar manner as problem 13.18.

Eq. 13.93 gives the relationship between interatomic distance, inertia and reduced mass.
mm
I = 1 2 r02 = μ r02
m1 + m2

To solve for interatomic distance, we first calculate the moment of inertia from Eq. 13.100 since we already have the value of the rotational
constant, B.
h
B = 2
8π Ic
h
I= 2
8π cB
6.626 × 10−34 J s
I= 2
8π 2.998 × 1010 cm s −1 × 20.95 cm −1
I = 1.336 12 × 10−47 J

The reduced mass is calculated using Eq.13.94,

mm
μ= 1 2
m1 + m2
1 g mol−1 ×19 g mol−1
μ=
(1 + 19 ) g mol−1 × 6.022 ×1023 mol−1
μ = 1.577 55 ×10−24 g
μ = 1.577 55 ×10−27 kg

13-39
Chapter 13: Foundations of Chemical Spectroscopy Solutions

Rearranging Eq. 13.93 and solving for r we obtain,

I = μ r02
I
r=
μ
1.336 12 × 10−47 J
r=
1.577 55 × 10−27 kg
r = 9.203 05 × 10−11 m
r = 92 pm

To find the separation, we take a look at Eq. 13.93 and 13.100 and notice that the separation B is inversely proportional to I and therefore, to
the reduced mass μ. The interatomic separations are assumed to be the same. The reduced mass for HF, DF and TF are in the ratio:

HF DF TF
1× 19 2 × 19 3 × 19
: :
20 21 22
= 1 : 1.90 : 2.72

Using the ratios, the predicted separations are,

2 BDF = 41.9 cm −1 ÷ 1.90
2 BDF = 21.997 5 cm −1
2 BDF = 22.0 cm −1
2 BTF = 41.9 cm −1 ÷ 2.72
2 BTF = 15.363 33 cm −1
2 BTF = 15.4 cm −1

Back to Problem 13.19 Back to Top

13-40
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.20. In the microwave spectrum of 12C16O the separation between lines has been measured to be 115270 MHz. Calculate the interatomic
distance.

Solution:

Given: 12C16O, 2 B = 115 270 MHz

Required: r

This problem can be solved in a similar manner as problem 13.18.

Eq. 13.93 gives the relationship between interatomic distance, inertia and reduced mass.
mm
I = 1 2 r02 = μ r02
m1 + m2

To solve for interatomic distance, we first calculate the moment of inertia from Eq. 13.100 since we already have the value of the rotational
constant, B.
h
B = 2
8π Ic
h
I= 2
8π cB
6.626 × 10−34 J s
I=
1
8π 2 × ×115 270 ×106 s −1
2
I = 1.456 05 × 10−46 J

The reduced mass is calculated using Eq.13.94,

mm
μ= 1 2
m1 + m2
12.000 g mol−1 × 15.995 g mol−1
μ=
(12.000 + 15.995 ) g mol−1 × 6.022 ×1023 mol−1
μ = 1.138 53 ×10−23 g
μ = 1.138 53 × 10−26 kg

13-41
Chapter 13: Foundations of Chemical Spectroscopy Solutions

Rearranging Eq. 13.93 and solving for r we obtain,

I = μ r02
I
r=
μ
1.456 05 ×10−46 J
r=
1.138 53 × 10−26 kg
r = 1.130 88 ×10−10 m
r = 113pm

Back to Problem 13.20 Back to Top

13-42
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.21. The J = 0 → J = 1 line in the microwave absorption spectrum of 12C16O and of 13C16O was measured by Gillam et al., [Phys. Rev.
78, 140(1950)]. In its ground vibrational state, the former has the value 3.842 35 cm–1 and the latter, the value 3.673 37 cm–1.
Calculate
a. the bond length of the 12C16O molecule,
b. the relative atomic mass of 13C,
c. the bond length of the 13C16O molecule.

Solution:

Given:
12
C16 O; ν j = 3.842 35 cm –1 , 13 C16 O; ν j = 3.673 37 cm –1

Required: r ( 12
)
C16 O , M r , r ( 13
C16 O )
a. This problem can be solved in a similar manner as problem 13.18 since interatomic distance is the same as bond length.

Eq. 13.93 gives the relationship between interatomic distance, inertia and reduced mass.
mm
I = 1 2 r02 = μ r02
m1 + m2

First, we calculate the moment of inertia from Eq. 13.99 and Eq. 13.100. For the transition J = 0 → J = 1, Δν = 2B and therefore
ν j = 2 ( J + 1) B
h
ν j = 2 ( J + 1)
8π 2 Ic
2h
I=
8π 2 cν j
2 × 6.626 ×10−34 J s
I=
8π 2 × 2.998 ×1010 cm s −1 × 3.842 35 cm –1 s −1
I = 1.457 01× 10−46 J s
I = 1.457 01× 10−46 kg m 2

The reduced mass is calculated using Eq.13.94,

13-43
Chapter 13: Foundations of Chemical Spectroscopy Solutions

m1m2
μ=
m1 + m2
12.000 g mol−1 × 15.994 914 g mol−1
μ= × 10−3 kg g −1
(12.000 + 15.994 914 ) g mol × 6.022 ×10 mol
−1 23 −1

μ = 1.138 53 ×10−26 kg

Rearranging Eq. 13.93 and solving for r we obtain,

I = μ r02
I
r=
μ
1.457 01×10−46 kg m 2
r=
1.138 53 ×10−26 kg
r = 1.131 25 × 10−10 m
r = 113.1pm = 0.1131 nm

b. To find the reduced mass, we take a look at Eq. 13.93 and 13.100 and notice that the separation B is inversely proportional to the
reduced mass μ.
If Mr is the relative mass of 13C, and subscript 1 refers to 12C16O and, subscript 2 refers to 13C16O, we have,

13-44
Chapter 13: Foundations of Chemical Spectroscopy Solutions

B1 μ1
=
B2 μ2
3.842 35 cm –1 12.000 × 15.994 914 M r ×15.994 914
= ×
3.673 37 cm –1
12.000 + 15.994 914 M r + 15.994 914
⎛ M × 15.994 914 ⎞
1.046 001 356 = 0.145 853 207 × ⎜ r ⎟
⎝ M r + 15.994 914 ⎠
M × 15.994 914
7.171 603 411 = r
M r + 15.994 914
7.171 603 411( M r + 15.994 914 ) = 15.994 914M r
114.709 179 8 = 8.823 310 589M r
M r = 13.000 696 13

c. This problem can be solved in a similar manner as part a.

Eq. 13.93 gives the relationship between interatomic distance, inertia and reduced mass.
mm
I = 1 2 r02 = μ r02
m1 + m2

First, we calculate the moment of inertia from Eq. 13.99 and Eq. 13.100. For the transition J = 0 → J = 1, Δν = 2B and therefore
ν j = 2 ( J + 1) B
h
ν j = 2 ( J + 1)
8π 2 Ic
2h
I=
8π 2 cν j
2 × 6.626 × 10−34 J s
I=
8π 2 × 2.998 ×1010 cm s −1 × 3.673 37 cm –1 s −1
I = 1.524 04 × 10−46 J s
I = 1.524 04 × 10−46 kg m 2

13-45
Chapter 13: Foundations of Chemical Spectroscopy Solutions

The reduced mass is calculated using Eq.13.94,

mm
μ= 1 2
m1 + m2
13.003 35 g mol−1 ×15.994 914 g mol−1
μ= × 10−3 kg g −1
(13.003 35 + 15.994 914 ) g mol × 6.022 ×10 mol
−1 23 −1

μ = 1.191 03 ×10−26 kg

Rearranging Eq. 13.93 and solving for r we obtain,

I = μ r02
I
r=
μ
1.524 04 × 10−46 kg m 2 kg m 2
r=
1.191 03 × 10−26 kg
r = 1.13119 × 10−10 m
r = 113.1pm = 0.1131 nm

Therefore, there is essentially no difference in the bond length with the 13C isotope.

Back to Problem 13.21 Back to Top

13-46
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.22. The microwave spectrum of 16O12C32S shows absorption lines separated by 12.163 GHz. That of 16O12C34S shows lines separated by
11.865 GHz. The determination of the bond distances involves solving two simultaneous quadratic equations, which is best done by
successive approximations. To avoid all that labor, simply confirm that the results are consistent with r(O—C) = 116 pm and r(C—
S) = 156 pm.

Solution:

Given: 16 O12 C32S; 2 B = 12.163 GHz, 16 O12 C34S, 2 B = 11.865 GHz

Required: confirm that the results are consistent with r ( O − C ) = 116 pm, r ( C − S ) = 156 pm

To confirm that the bond distances are consistent with r ( O − C ) = 116 pm, r ( C − S ) = 156 pm , we can calculate and compare the moments
of inertia based on the absorption line separations and the bond distances.

The B values are half the separations,

O C S; B = 6.081 5 × 109 s −1
16 12 32

16
O12 C34S, B = 5.932 5 ×109 s −1

We can then calculate the moment of inertia from Eq. 13.100 since we already have the value of the rotational constant, B.
h
B = 2
8π Ic
h
I= 2
8π cB
6.626 ×10−34 J s
I ( O C S) = 2
16 12 32

8π × 6.081 5 × 109 s −1
I ( 16 O12 C32S) = 1.379 91× 10−45 J
6.626 × 10−34 J s
I ( 16 O12 C34S) =
8π 2 × 5.932 5 × 109 s −1
I ( 16 O12 C34S) = 1.414 57 ×10−45 J

The moment of inertial of a linear triatomic molecule is given by Eq. 13.103

13-47
Chapter 13: Foundations of Chemical Spectroscopy Solutions

( m r − m3r23 )
2

I =m r +m r
2
1 12
2
3 23 − 1 12
m
We can write x for r12 and y for r23, and M1, M2 and M3 for the molar masses. We then obtain the following quadratic equations,
1⎛ ( M1 x − M 3 y ) ⎞
2

I ( O C S) = ⎜ M 1 x + M 3 y −
16 12 32 2 2
⎟
L ⎜⎝ M ⎟
⎠
−45 −42
= 1.379 91×10 J = 1.379 91×10 g m 2
⎛
( )′y ⎞
2

1⎜ M x − M ⎟
I ( 16 O12 C34S)
1 3
= ⎜ M 1 x 2 + M 3′ y 2 − ⎟
L⎜ M ⎟
⎝ ⎠
−45 −42
= 1.414 57 ×10 J = 1.414 57 × 10 g m 2

Insertion of L = 6.022 ×1023 mol−1 , M 1 = 16 g mol−1 , M 3 = 32 g mol−1 , M 3′ = 34 g mol−1 , M = 60 g mol−1 , x = 116 pm, and y = 156 pm into
the left hand side (LHS) and right hand side (RHS) of these equations gives,

I ( 16 O12 C32S) ;
LHS:
= 1.379 91× 1042 g m 2
RHS:
⎛ (16 g mol−1 × 116 pm − 32 g mol−1 ×156 pm ) ⎞
2

= ⎜16 g mol × (116 pm ) + 32 g mol × (156 pm ) − ⎟

−1 2 −1 2

⎜ 60 g mol−1 ⎟
⎝ ⎠
−1
6.022 × 10 mol
23

2
830 139.733 3 g pm 2 mol−1 ⎛ 10−12 m ⎞
= ×⎜ ⎟
6.022 ×1023 mol−1 ⎝ pm ⎠
= 1.378 51×1042 g m 2
LHS ≈ RHS = 1.38 ×1042 g m 2

13-48
Chapter 13: Foundations of Chemical Spectroscopy Solutions

I ( 16 O12 C34S ) ;
LHS:
= 1.414 57 × 1042 g m 2
RHS:

⎜16 g mol−1 × (116 pm )2 + 34 g mol−1 × (156 pm )2 − (

⎛ 16 g mol−1 ×116 pm − 34 g mol −1 × 156 pm ) ⎞
2

⎟
⎜ 60 g mol−1 ⎟
=⎝ −1
⎠
6.022 ×10 mol
23

2
844 574.933 3 g pm 2 mol−1 ⎛ 10−12 m ⎞
= ×⎜ ⎟
6.022 × 1023 mol−1 ⎝ pm ⎠
= 1.402 48 × 10−42 g m 2
LHS ≈ RHS = 1.4 ×1042 g m 2

Back to Problem 13.22 Back to Top

13-49
Chapter 13: Foundations of Chemical Spectroscopy Solutions

1 2
13.23. The maximum potential energy that a diatomic molecule can store is kx , where x is the amplitude of vibration. If the force
2
constant k is 1.86 × 103 N m–1, calculate the maximum amplitude of vibration for the CO molecule in the v = 0 vibrational state.
Compare this to the bond length obtained in Problem 13.21. Use the value of ur in that problem.

Solution:

Given: k = 1.86 ×103 N m –1 , vCO = 0 , Problem 13.21

Required: x, compare with r in Problem 13.21

To solve for amplitude of vibration, x, we substitute using Eq. 13.123 and rearrange the equation given above to get,

1 2 h k
kx =
2 4π μ
h 1
x2 =
2π kμ
1
⎛ h 1 ⎞2
x = ⎜⎜ ⎟⎟
⎝ 2π kμ ⎠

We use μ = 1.191 03 ×10−26 kg from Problem 13.21, substitute and solve to obtain,
1
⎛ 6.626 ×10−34 J s 1 ⎞2
x = ⎜⎜ ⎟
⎝ 2π 1.86 ×103 N m –1 × 1.191 03 ×10−26 kg ⎟⎠
1
x = ( 2.240 54 ×10 −23
m )
2 2

1
x = ( 2.240 54 ×10−23 m 2 ) 2
x = 4.733 44 ×10−12 m = 4.733 44 ×10−3 nm = 0.047 334 4Å

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

In Problem 13.21, the bond length for the CO molecule was found as r = 0.1131 nm .
Compared to x,

4.733 44 ×10−3 nm
% change = ×100%
0.1131 nm
% change = 4.184 474 8%
% change = 4.2%
The extension therefore represents about a 4% change.
Back to Problem 13.23 Back to Top

13-51
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.24. Consider the following molecules: H2, HCl, CO2, CH4, H2O, CH3Cl, CH2Cl2, H2O2, NH3, and SF6. Which of them will give
a. a pure rotational spectrum,
b. a vibrational-rotational spectrum,
c. a pure rotational Raman spectrum,
d. a vibrational Raman spectrum?

Solution:

Given: H2, HCl, CO2, CH4, H2O, CH3Cl, CH2Cl2, H2O2, NH3, and SF6
Required: see above

a. pure rotational b. vibrational- c. pure rotational d. vibrational

spectrum rotational spectrum Raman spectrum Raman spectrum
H2 9 9
HCl 9 9 9 9
CO2 9 9 9
CH4 9 9
H2O 9 9 9 9
CH3Cl 9 9 9 9
CH2Cl2 9 9 9 9
H2O2 9 9 9 9
NH3 9 9 9 9
SF6 9 9

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13-52
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.25. Analysis of the vibrational-rotational spectrum of the H35Cl molecule shows that its fundamental vibrational frequency ν0 is 2988.9
cm–1. Calculate the force constant of the H—Cl bond.

Solution:

Given: H35Cl, ν0 = 2988.9 cm–1

Required: k

The force constant is defined in terms of the fundamental frequency in Eq. 13.122,
k = 4π 2ν 02 μ

The frequency, in terms of inverse seconds is given by,

v = v0 c
v = 2.998 × 1010 cm s –1 × 2 988.9 cm –1
v = 8.990 7 × 1013 s –1

The reduced mass is calculated using Eq.13.94,

m1m2
μ=
m1 + m2
34.968 85 g mol−1 ×1.007 825 g mol−1
μ= ×10−3 kg g −1
( 34.968 85 + 1.007 825 ) g mol −1
× 6.022 × 10 23
mol −1

μ = 1.626 69 ×10−27 kg

Solving for k we get,

k = 4π 2ν 02 μ
k = 4π 2 ( 8.990 7 ×1013 s –1 ) ×1.626 69 ×10−27 kg
2

k = 519.100 760 8 kg s – 2
k = 519.10 kg s – 2
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13-53
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.26. A few transitions in the P and R branches of the infrared spectrum of H35Cl spectrum are identified below.
J″ 0 1 2 3 4 5 6
P (cm–1) 2865.10 2843.62 2821.56 2798.94 2775.76 2752.04
R (cm–1) 2906.24 2925.90 2944.90 2963.29 2981.00 2998.04

Using Eqs. 13.134 or 13.135 as appropriate, calculate ν0 and the rotational constant B .

Solution:

Given: table above

Required: ν0 , B .

Equations 13.135 and 13.136,

ν =ν0 + 2 ( J ′′ + 1) B =ν0 + 2 J ′B and ν =ν0 − 2 ( J ′ + 1) B =ν0 − 2 J ′′B ,
Both show that a plot of the observed frequencies ν as a function of J ′′ will be a straight line with slope = ±2B and intercept ν0 .
A linear regression of the values in the P branch gives the following plot.

13-54
Chapter 13: Foundations of Chemical Spectroscopy Solutions

This gives,
ν = 2888.70 − 22.614J ′′

From which we obtain the fundamental vibrational frequency as,

ν0 = 2888.70 cm −1

And the value B as,

−22.614
B =
±2
B = 11.307 cm −1

Similarly, we can perform a linear regression of the values in the B branch to give the following results.

ν = 2907.3 − 18.363J ′′

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

From which we obtain the fundamental vibrational frequency as,

ν0 = 2907.3 cm −1

And the value B as,

−18.363
B =
±2
B = 9.181 5 cm −1

Back to Problem 13.26 Back to Top

13-56
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.27. Comparison of the results of Problem 13.26 to experimental values for H35Cl (ν0 = 2990 cm–1, and B = 10.59 cm–1) shows that Eqs.
13.134 and 13.135 do not accurately relate the observed transitions to the rotational quantum numbers. Much of the error results
1
from not taking the anharmonicity of the potential energy curve into account. Using the definition (see Eq. 13.138) Tv,J = (ν + )ν0
2
1 2
– (v + ) ν0 xe + J(J + 1) B , derive a more accurate expression for ΔTv,J for the v″ = 0 → v′ = 1 transitions of a diatomic molecule.
2
[Even this is an approximate treatment because we are ignoring the coupling of rotations with vibrations.]

Solution:

1 1
Given Tv,J = (ν + )ν0 – (v + )2 ν0 xe + J(J + 1) B ,
2 2
Required: expression for ΔTv,J for the v″ = 0 → v′ = 1 transitions of a diatomic molecule

To derive a more accurate expression for ΔTv,J, we first write the following expressions for
v = 0 and v = 1,
1 1
T0, J ′′ = ν0 − ν0 xe + J ′′ ( J ′′ + 1) B
2 4
3 9
T1, J ′ = ν0 − ν0 xe + J ′ ( J ′ + 1) B
2 4

This gives,
ΔT0, J ′′→1, J ′ = T1, J ′ − T0, J ′′
ΔT0, J ′′→1, J ′ = ν0 − 2ν0 xe + B ( J ′ ( J ′ + 1) − J ′′ ( J ′′ + 1) )

For ΔJ = J ′ − J ′′ = −1 (the P branch), this reduces to,

 ′′
ν = ν − 2ν x − 2 BJ
0 0 e

For ΔJ = J ′ − J ′′ = +1 (the R branch), this reduces to,

 ′′
ν = ν − 2ν x + 2 BJ
0 0 e

Back to Problem 13.27 Back to Top

13-57
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.28. From the results of Problems 13.26 and 13.27 and the experimental value of ν0 for H35Cl given in Problem 13.27, estimate the value
of the anharmonicity constant xe. Use the average of the P and R branch values for ν0 from Problem 13.26.

Solution:

Given: Problem 13.26, Problem 13.27

Required: xe

First we take the average of the P and R branch values for ν0 from Problem 13.26 to get,
1
ν0 = ( 2 888.70 cm −1 + 2 907.3 cm −1 )
2
ν0 = 2 898 cm −1

The more accurate treatment of Problem 13.27 shows that this is actually the value of ν0 − 2ν0 xe .
Therefore we can equate the two and solve for xe

ν = ν0 − 2ν0 xe
2990 cm −1 = 2 898 cm −1 − 2 × 2 898 cm −1 xe
xe = 0.015 873 016 cm −1
xe = 1.587 × 10−2 cm −1

Back to Problem 13.28 Back to Top

13-58
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.29. The vibrational Raman spectrum of 35Cl2 shows series of Stokes and anti-Stokes lines; the separation between the lines in each of
the two series is 0.9752 cm–1. Estimate the bond length in Cl2.

Solution:

Given: 4 B = 0.9752 cm –1
Required: r

From Figure 13.27, we know that the separation is 4B. Therefore the value of B is,
1
B = × 0.9752 cm –1
4
B = 0.2438 cm –1

This problem can be solved in a similar manner as problem 13.18.

Eq. 13.93 gives the relationship between interatomic distance, inertia and reduced mass.
mm
I = 1 2 r02 = μ r02
m1 + m2

We calculate the moment of inertia from Eq. 13.100

h
B = 2
8π Ic
h
I= 2
8π cB
6.626 × 10−34 J s
I= 2
8π × 0.2438 cm −1 × 2.998 ×1010 cm s −1
I = 1.14814 ×10−45 J

The reduced mass is calculated using Eq.13.94,

13-59
Chapter 13: Foundations of Chemical Spectroscopy Solutions

m1m2
μ=
m1 + m2
35 g mol−1 × 35 g mol−1
μ=
( 35 + 35) g mol−1 × 6.022 ×1023 mol−1
μ = 2.906 01×10−26 kg

Rearranging Eq. 13.93 and solving for r we obtain,

I = μ r02
I
r=
μ
1.14814 ×10−45 J
r=
2.906 01× 10−26 kg
r = 1.987 69 × 10−10 m
r = 199 pm

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13-60
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.30. The dissociation energy of H2 is 432.0 kJ mol–1 and the fundamental vibrational frequency of the molecule is 1.257 × 1014 s–1.
Calculate the classical dissociation energy. Estimate the zero-point energies of HD and D2 and their dissociation energies.

Solution:

Given: E p = 432.0 kJ mol –1 , ν 0 = 1.257 ×1014 s –1

Required: classical dissociation E , estimated zero point E , dissociation E ,

The zero point energy of H2 is given by

1
E = hν 0
2
1
E = × 6.626 × 10−34 J s × 1.257 × 1014 s –1
2
kJ
E = 4.164 44 × 10−20 J × 10−3 ××6.022 × 1023 mol−1
J
E = 25.078 263 7 kJ mol−1
E = 25.08 kJ mol−1

To find the classical dissociation energy, we add the zero point energy to the dissociation energy given above.
E = 25.08 kJ mol−1 + 432.0 kJ mol –1
E = 457.08 kJ mol−1

The reduced masses of H2, HD and D2 are in the ratio,

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

H2 HD D2
1× 1 1× 2 2× 2
: :
1+1 1+ 2 2+2
1 2
: : 1
2 3
4
= 1 : : 2
3

From Eq. 13.123,

1 k
ν0 =
2π μ
we know that frequency is inversely related to μ , therefore the estimated ν 0 for HD and D2 are,
4
ν 0 ( HD ) = 1.257 ×1014 s –1 ÷
3
ν 0 ( HD ) = 1.088 59 ×1014 s –1
ν 0 ( D 2 ) = 1.257 ×1014 s –1 ÷ 2
ν 0 ( D 2 ) = 8.888 33 ×1013 s –1

13-62
Chapter 13: Foundations of Chemical Spectroscopy Solutions

Therefore,

1
E ( HD ) = × 6.626 ×10−34 J s ×1.088 59 × 1014 s –1
2
kJ
E ( HD ) = 3.606 51×10−20 J ×10−3 ××6.022 × 1023 mol−1
J
E ( HD ) = 21.718 413 45 kJ mol −1
and
1
E ( D 2 ) = × 6.626 × 10−34 J s × 8.888 33 ×1013 s –1
2
kJ
E ( D 2 ) = 2.944 7 × 10−20 J ×10−3 ××6.022 ×1023 mol−1
J
E ( D 2 ) = 17.733 010 32 kJ mol−1

The estimated dissociation energies are therefore the difference between the dissociation energies above and the classical dissociation
energy,

HD;
E = 457.08 kJ mol−1 − 21.718 413 45 kJ mol−1
E = 435.361 586 6 kJ mol−1
E = 435.36 kJ mol−1
D2 ;
E = 457.08 kJ mol−1 − 17.733 010 32 kJ mol−1
E = 439.346 989 7 kJ mol−1
E = 439.35 kJ mol−1

Back to Problem 13.30 Back to Top

13-63
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.31. A molecule AB2 is known to be linear but it is not known whether it is B—A—B or A—B—B. Its infrared spectrum is found to
show bands corresponding to three normal modes of vibration. Which is the structure?
Solution:
Given: AB2, three normal modes of vibration in IR spectrum
Required: structure

The symmetric molecule, B—A—B, only has two modes that are active in the infrared region:

B →← A—B →

and
↑
B—A—B (two degenerate modes)
↓ ↓
The symmetric stretch is inactive.

The unsymmetrical molecule, A—B—B have three modes that are active in the infrared region:

← A—B—B →

and

A →← B—B

and

↑
A—B—B (two degenerate modes)
↓ ↓

Therefore the structure of the molecule is A—B—B.

Back to Problem 13.31 Back to Top

13-64
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.32. The frequency of the O—H stretching vibration in CH3OH is 3300 cm–1. Estimate the frequency of the O—D stretching vibration in
CH3OD.

Solution:

Given: νO − H = 3 300 cm –1

Required: νO −D

To calculate the frequency of the O—D stretching vibration, we rely on Eq. 13.123 which
1 k
ν0 =
2π μ
which shows that the frequency is inversely related to μ .

The reduced masses are calculated using Eq.13.94, and are in the following ratio

m1m2
μ=
m1 + m2
1 g mol−1 ×16 g mol−1 1×16
μOH = =
(1 + 16 ) g mol × 6.022 ×10 mol
−1 23 −1
17 L
2 g mol−1 ×16 g mol−1 2 ×16
μ OD = =
( 2 + 16 ) g mol × 6.022 ×10 mol
−1 23 −1
18 L

μ OD 2 × 16 17 L 17
= × =
μ OH 18 L 1× 16 9

The force constants are the same, and therefore the frequency of the O—D stretching vibration is given by,

13-65
Chapter 13: Foundations of Chemical Spectroscopy Solutions

17
νOD = νOH ÷
9
17
νOD = 3 300 cm –1 ÷
9
νOD = 2 401.102 688 cm –1
νOD = 2 401 cm –1

Back to Problem 13.32 Back to Top

13-66
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.33. The spectroscopic constants for the OH radical are ν0 = 3737.76 cm–1, ν0 xe = 84.8813 cm–1, B = 18.9108 cm–1. Predict the
frequencies at which (a) the P branch transitions ending in, and (b) the R branch beginning in, J = 0, 1, 2 will be observed.

Solution:

Given: ν0 = 3 737.76 cm –1 , ν0 xe = 84.881 3 cm –1 , B = 18.910 8 cm –1

Required: for the P branch and R branch; ν for J = 0, 1, 2

a. In problem 13.27, we derived an equation for the P branch transitions, given by,
 ′′
ν = ν0 − 2ν0 xe − 2 BJ

For this situation the equation becomes,

ν = 3 737.76 cm –1 − 2 × 84.881 3 cm –1 − 2 × 18.910 8 cm –1 × J ′′

The frequencies are then calculated by substituting the values of J ′′ into the equation.

J ′′ 0 1 2
ν ( cm −1 ) 3 567.997 3 530.176 3 492.354

b. For the R branch transitions, we use the second equation derived in problem 13.27,
 ′′
ν = ν0 − 2ν0 xe + 2 BJ
ν = 3 737.76 cm –1 − 2 × 84.881 3 cm –1 + 2 ×18.910 8 cm –1 × J ′′

J ′′ 0 1 2
(
ν cm −1 ) 3 567.997 3 605.819 3 643.641

Back to Problem 13.33 Back to Top

13-67
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.34. Irradiation of acetylene with mercury radiation at 435.83 nm gives rise to a Raman line at 476.85 nm. Calculate the vibrational
frequency that corresponds to this shift.

Solution:

Given: λ0 = 435.83 nm, λ1 = 476.85 nm

Required: ν

To calculate the vibrational frequency that corresponds to the shift, we first calculate the wavenumbers that correspond to each wavelength.

435.83 nm;
1
ν =
435.83 ×10−9 m
ν = 2 294 472.615 m −1 = 22 944.726 15 cm −1

476.85 nm;
1
ν =
476.85 ×10−9 m
ν = 2 097 095.523 m −1 = 20 970.955 23 cm −1

The frequency that corresponds to the vibration in the C2H2 molecule, (ie the C-C stretch) is the difference of the two,

ν = 22 944.726 15 cm −1 − 20 970.955 23 cm −1
ν = 1 973.770 928 cm −1
ν = 1 973.8 cm −1

Back to Problem 13.34 Back to Top

13-68
Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.35. The fundamental vibrational frequency of H127I is 2309.5 cm–1. Calculate the force constant of the bond.

Solution:

Given: H127I, ν0 = 2 309.5 cm–1

Required: k

This problem can be solved in a similar manner as problem 13.25.

The force constant is defined in terms of the fundamental frequency in Eq. 13.122,
k = 4π 2ν 02 μ

The frequency, in terms of inverse seconds is given by,

v = v0 c
v = 2.998 ×1010 cm s –1 × 2 309.5 cm –1
v = 6.923 88 × 1013 s –1

The reduced mass is calculated using Eq.13.94,

m1m2
μ=
m1 + m2
126.9 g mol−1 ×1.007 825 g mol−1
μ= ×10−3 kg g −1
(126.9 + 1.007 825) g mol × 6.022 ×10 mol
−1 23 −1

μ = 1.660 39 ×10−27 kg

Solving for k we get,

k = 4π 2ν 02 μ
k = 4π 2 ( 6.923 88 ×1013 s –1 ) ×1.660 39 ×10−27 kg
2

k = 314.244 591 kg s – 2
k = 314.24 kg s – 2

Back to Problem 13.35 Back to Top

13-69
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.36. The following are some normal modes of vibration for several molecules:

In each case, determine the point group and refer to Appendix E on p. 1028 to determine whether the vibration is active in the
infrared and in the Raman spectrum. Then check your conclusions by reference to the appendix to this chapter (p. 707).

Solution:

Given: image above

Required: determine point group, activity of vibration

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

cis-C2H2Cl2: C2v point group

Infrared Raman
a. a1 active active
b. b1 inactive active
c. a2 active active
d. a1 active active

trans-C2H2Cl2: C2h point group

Infrared Raman
e. ag inactive active
f. au active inactive
g. bu active inactive
h. ag inactive active

Benzene: D6h point group

Infrared Raman
i. a1g inactive active
j. a2u active inactive
k. b1u inactive inactive

Back to Problem 13.36 Back to Top

13-71
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.37. Prove that the force constant k corresponding to the Morse potential function (Eq. 13.146) at small bond extensions is
k = 2Dea2
Calculate the vibration frequency v0 on the basis of the following Morse parameters for H35Cl:
De = 4.67 eV
a = 1.85 × 108 cm–1
Solution:

Given: Morse potential, H 35Cl, De = 4.67 eV, a = 1.85 ×108 cm –1

Required: proof, v0

The Morse potential function is given by Eq. 13.146

( )
2
E p = De 1 − e – ax

At small x values the exponential may be expanded to 1 − ax , and the potential energy will therefore be given by,

13-72
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.38. The Morse function is only one of several models used to describe the behavior of the potential energy of diatomic molecules. A
popular and very accurate model introduced by Murrell and Sorbie [J. Chem. Soc., Faraday Trans. 2, 70, 1552(1974)] is the so-
called “Extended Rydberg function,” which is written as
E p ( x) = − De (1 + a1 x + a2 x 2 + a3 x 3 )e − a1x ,
where x = r – re, as in the case of the Morse potential of Eq. 13.146, and the ai are constants for a given molecule.
a. Derive an expression for the force constant in terms of the parameters De and ai.
b. Show that in order for a function of this form to have a minimum at r = re, a1 must be both the coefficient of x and the exponential
parameter.
Solution:

Given: Extended Rydberg function

Required: expression for k, proof

13-73
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.39. Yet another model for a diatomic potential is the Bond Order function used by Garcia and Laganá [Mol. Phys. 56, 621(1985)],
which is given as
N
E p ( x ) = − De ∑ cn exp ( − n β x ).
n =1

Show that for N = 2, with appropriate choices for the coefficients c1 and c2, this is identical to the Morse potential of Eq. 13.146
expressed as Ep = De(1 – e–βx)2 – De.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.40. The parameters for the bond order (see Problem 13.39) potential of the 35Cl16O radical with N = 4 are (in atomic units) c1 = 2.691
042, c2 = –2.545 521, c3 = 1.017 916, c4 = –0.163437, De = 0.10302, and β = 1.763 768. What is the vibrational frequency (in cm–1)
predicted by this model? [Note that the force constant can be expressed in units of energy area–1.]

Solution:

Given:
Required:

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.41. A model for the 14N–14N–16O+ ion assigns the following force constants for the two stretching frequencies: k12 = 1092.8 N m–1, and
k23 = 890.68 N m–1. Use Eqs. 13.171–13.174 to calculate the two stretch frequencies obtained from the model.

Solution:

Given: k12 = 1 092.8 N m –1 , and k23 = 890.68 N m –1

Required: ν1 , ν2

To solve for the stretching frequencies, we need to solve the quadratic equation given by Eq. 13.171. For the molar masses, we use
14.00 ×10−3 kg mol−1 16.00 ×10−3 kg mol−1
m1 = m2 = and m3 =
6.022 ×1023 mol−1 6.022 ×1023 mol−1

⎛ m1 + m2 m + m3 ⎞ k k ( m + m2 + m3 )
λ2 −⎜ k12 + 2 k23 ⎟ λ + 12 23 1 =0
⎝ m1m2 m2 m3 ⎠ m1m2 m3
λ 2 − ( 1.658 47 ×1029 ) λ + ( 4.952 45 ×1057 ) = 0

This resembles Eq. 131.172, λ2 – bλ + c = 0, and therefore the solutions are obtained by solving Eq. 13.173 and 13.174.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

λ 2 − ( 1.658 47 ×1029 ) λ + ( 4.952 45 ×1057 ) = 0

b − b 2 − 4c
λ1 =
2
1.658 47 × 1029 − ( 1.658 47 ×10 )
29 2
− 4 × 4.952 45 ×1057
λ=
2
λ1 = 3.906 18 ×10 s 28 −2

b + b 2 − 4c
λ2 =
2
1.658 47 × 1029 + ( 1.658 47 ×10 )
29 2
− 4 × 4.952 45 ×1057
λ=
2
λ2 = 1.267 85 ×10 s 29 −2

We then calculate the stretching frequencies from,

λ
ν=
2π c
3.906 18 ×1028 s −2
ν1 =
2π × 2.998 × 1010 cm s −1
ν 1 = 1 049.215 077 cm −1
ν 1 = 1 049.2 cm −1

1.267 85 × 1029 s −2
ν2 =
2π × 2.998 × 1010 cm s −1
ν 2 =1890.265 202 cm −1
ν 2 = 1890.3 cm −1

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13-77
Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.42. The fundamental and a few successive overtones of the H +2 molecule lie at 2191, 2064, 1941, 1821, 1705, 1591, 1479 and 1368 cm–
1
, respectively.
a. Starting from Eq. 13.139, derive an expression that can be used to obtain both ν0 and xe by a suitable analysis of the data.
b. Perform the analysis and calculate both ν0 and xe.

Solution:

Given: ν
Required: expression for ν0 and x, calculate ν0 and xe

a. Eq. 13.139 is given by

⎡ ⎛ 1 ⎞ ⎤⎛ 1⎞
G (ν ) =ν0 ⎢1 − xe ⎜ν + ⎟ ⎥ ⎜ν + ⎟
⎣ ⎝ 2⎠ ⎦⎝ 2⎠

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

Therefore, for a transition, ν ′′ → ν ′ , we can write,

⎡ ⎛ 1 ⎞ ⎤⎛ 1⎞ ⎡ ⎛ 1 ⎞⎤ ⎛ 1⎞
ΔGν ′ =ν0 ⎢1 − xe ⎜ν ′ + ⎟ ⎥ ⎜ν ′ + ⎟ −ν0 ⎢1 − xe ⎜ν ′′ + ⎟ ⎥ ⎜ν ′′ + ⎟
⎣ ⎝ 2 ⎠ ⎦⎝ 2⎠ ⎣ ⎝ 2 ⎠⎦ ⎝ 2⎠
⎡⎛ 1⎞ ⎛ 1⎞ ⎛
2
1⎞ ⎛ 1⎞ ⎤
2

ΔGν ′ =ν0 ⎢⎜ν ′ + ⎟ − xe ⎜ν ′ + ⎟ − ⎜ν ′′ + ⎟ + xe ⎜ν ′′ + ⎟ ⎥
⎢⎣⎝ 2⎠ ⎝ 2⎠ ⎝ 2⎠ ⎝ 2 ⎠ ⎥⎦
⎡ 1 ⎛ 1⎞
2
1 ⎛ 1⎞ ⎤
2

ΔGν ′ =ν 0 ⎢ν ′ + − xe ⎜ν ′ + ⎟ −ν ′′ − + xe ⎜ν ′′ + ⎟ ⎥

⎣⎢ 2 ⎝ 2⎠ 2 ⎝ 2 ⎠ ⎦⎥
⎡ ⎛ 1⎞
2
⎛ 1⎞ ⎤
2

ΔGν ′ =ν0 ⎢ν ′ −ν ′′ − xe ⎜ν ′ + ⎟ + xe ⎜ν ′′ + ⎟ ⎥
⎢⎣ ⎝ 2⎠ ⎝ 2 ⎠ ⎥⎦
⎡ ⎛ 1⎞ ⎛ 1 ⎞⎤
ΔGν ′ =ν0 ⎢ν ′ −ν ′′ − xe ⎜ν ′2 + ν ′ + ⎟ + xe ⎜ν ′′2 + ν ′′ + ⎟ ⎥
⎣ ⎝ 4⎠ ⎝ 4 ⎠⎦
⎡ ⎛ 1 1 ⎞⎤
ΔGν ′ =ν0 ⎢ν ′ −ν ′′ + xe ⎜ν ′2 +ν ′ − + −ν ′′2 −ν ′′ − ⎟ ⎥
⎣⎢ ⎝ 4 4 ⎠ ⎥⎦
ΔGν ′ =ν0 ⎡⎣ν ′ −ν ′′ + xe (ν ′2 −ν ′′2 + ν ′ −ν ′′ ) ⎤⎦

ΔGν ′ =ν0 (ν ′ −ν ′′ ) −ν0 xe ⎣⎡( ν ′2 −ν ′′2 ) + (ν ′ −ν ′′ ) ⎦⎤

or we can simplify as,
ΔGν ′
=ν −ν x [ν ′ +ν ′′ + 1] = (ν0 −ν0 xe ) −ν0 xe (ν ′ +ν ′′ )
(ν ′ −ν ′′ ) 0 0 e

Therefore a plot of the left-hand side as a function of (ν ′ +ν ′′ ) will yield a straight line, from which ν0 and xe can be calculated. If we
consider the case where ν ′ −ν ′′ = 1 , the left hand side is simply the observed fundamental and overtone signals, and the analysis is
particularly simple.
b. From the data given above, we obtain the following plot.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.43. Sketch potential energy curves for a diatomic molecule in its ground electronic state and n an excited state, consistent with the
following observations:
a. There is a strong 0 ← 0 absorption band, and strong 0 → 0, 1 → 1, and 2 → 2 emission bands.
b. The strongest absorption band is 4 ← 0, and the strongest emission band is 0 → 2.
c. There is no sharp rotational fine structure in absorption, but there is a sharp emission spectrum.
d. The absorption spectrum shows a well-defined fine structure for the 0 ← 0, 1 ← 0, 2 ← 0, 3 ← 0, and 4 ← 0 transitions and for
the 6 ← 0 and 7 ← 0, but not in between.

Solution:

a.

b.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

c.

d.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

*13.44. Using the data in Example 13.12 on p. 702, determine the area under the curve in a plot of Δv against v. Extrapolate to zero Δv to
obtain v′max, since the Birge-Sponer extrapolation shows that at that point v′ = v′max. A better value may be obtained by a nonlinear
extrapolation. What are the values of v′ not given in the table?

Solution:

Given: Example 13.12

Required: area under the curve, values of v′ not given in the table

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.45. Calculate the dissociation energy of the hydrogen molecule ion from the vibrational energy level separations of H +2 . The values for
the transitions 1 ← 0, 2 ← 1, …, are, respectively, 2191, 2064, 1941, 1821, 1705, 1591, 1479, 1368, 1257, 1145, 1033, 918, 800,
677, 548, 411, with all values given in cm–1. Use both a linear plot and a curve to obtain answers.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.46. The electronic spectra of diatomic molecules in the gas phase typically show extensive vibrational structure superimposed on the
broader electronic transition. Taking the equilibrium geometry of the ground electronic state to be the zero energy, the G (ν″) of Eq.
13.138 can be used to express the energies of the vibrational states v″ (in cm–1) of this electronic state. Denoting the minimum
energy of the excited electronic state as Te (in cm–1), the vibrational energy levels v′ of the excited state can be expressed as
T + G (ν ′ ) . Derive an expression for the frequencies ν of the transitions ν″ → ν′ between the vibrational levels of the ground and
e

excited electronic states. (Note that the vibrational frequencies and anharmonicity constants are not the same for the ground and
excited electronic states.)

Solution:

Given: Eq. 13.138

Required: expression for ν

Eq. 13.138 is given by

⎡⎛ 1⎞ ⎛ 1⎞ ⎤
2

G (ν ) =ν0 ⎢⎜ν + ⎟ − xe ⎜ν + ⎟ ⎥
⎢⎣⎝ 2⎠ ⎝ 2 ⎠ ⎥⎦
The ground state vibrational energies are given by,
2
⎛ 1⎞ ⎛ 1⎞
Gν ′ = ⎜ν ′′ + ⎟ν0′′ − ⎜ν ′′ + ⎟ ν0′′ xe
⎝ 2⎠ ⎝ 2⎠
And the excited state energies are expressed as,
2
⎛ 1⎞ ⎛ 1⎞
Gν ′ = Te + ⎜ν ′ + ⎟ν0′ − ⎜ν ′ + ⎟ ν0′ xe
⎝ 2⎠ ⎝ 2⎠
Therefore, the energy difference for the ν ′′ → ν ′ transitions are given by,
⎡⎛ 1⎞ ′ ⎛ 1 ⎞ ′ ⎤ ⎡⎛
2
1 ⎞ ′′ ⎛ 1 ⎞ ′′ ⎤
2
  
ν = Gν ′ − Gν ′ = Te + ⎢⎜ν ′ + ⎟ν0 − ⎜ν ′ + ⎟ ν0 xe ⎥ − ⎢⎜ν ′′ + ⎟ν0 − ⎜ν ′′ + ⎟ ν0 xe ⎥
⎢⎣⎝ 2⎠ ⎝ 2⎠ ⎥⎦ ⎢⎣⎝ 2⎠ ⎝ 2⎠ ⎥⎦
This cannot be simplified any further.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.47. An easy and reliable way to analyze the electronic spectrum of a diatomic molecule is to use the equation derived in Problem 13.46
as the model for a multiple regression analysis (several plotting packages and mathematics packages such as Mathcad can perform
this task) to simultaneously identify the five unknowns, Te ,ν0′ ,ν0′ xe′ ,ν0′′, and ν0′′xe′′ [McNaught, J. Chem. Ed. 57, 101(1980)]. The
following data are from the electronic spectrum of iodine.
0 → ν′ λ (nm) 1 → ν′ λ (nm) 2 → ν′ λ (nm)
17 567.2 15 581.0 10 607.3
18 564.2 16 577.8 11 603.1
19 561.5 17 574.2 12 599.1
20 558.5 18 571.3 13 595.5
21 555.8 19 568.3 14 591.8
22 553.0 20 565.2 15 588.1
23 550.1 21 559.6 16 584.8
24 547.8 22 556.9 17 581.2
25 542.7 23 554.2 18 578.1
26 540.7 24 551.8 19 575.1
27 538.5 25 549.0 20 572.4

Perform a multiple regression analysis and identify the spectroscopic parameters of the ground and excited electronic states. Literature
values are (in cm–1) Te = 15730, ν0′ = 132.1, ν0′ xe′ = 1.051, ν0′′ = 214.5, and ν0′′xe′′ = 0.614.

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.48. The dissociation energy (from the zero-point level) of the ground state O2 (3 Σ g− ) molecule is 5.09 eV. There exists an electronically
excited 3 Σ −u state of O2, whose zero-point level lies 6.21 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into two ground-state O(3P) atoms, while the 3 Σ u− species dissociates into one ground-state O(3P) atom and an
O*(1D) atom that lies 1.97 eV above the ground state. Sketch the potential-energy curves and calculate the dissociation energy of
O2 (3 Σ u− ) into O + O*(1D).

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.49. The spectroscopic dissociation energy D0 is the energy required to dissociate the molecule in its ground vibrational state. This is
always slightly smaller than the actual depth of the electronic potential energy because of the zero-point energy of the molecule (see
Figure 13.22). Given that for HCl, De = 4.6173 eV, ν0 = 2989 cm–1, and ν0 xe = 52.82 cm–1, calculate the value of D0 for HCl.

Solution:

Given: HCl; De = 4.617 3 eV, ν0 = 2 989 cm –1 , ν0 xe = 52.82 cm –1

Required: D0

To find the spectroscopic dissociation energy, we first calculate G 0 from Eq. 13.138
⎡⎛ 1⎞ ⎛ 1⎞ ⎤
2

G (ν ) =ν 0 ⎢⎜ν + ⎟ − xe ⎜ν + ⎟ ⎥

⎣⎢⎝ 2⎠ ⎝ 2 ⎠ ⎦⎥
⎡⎛ 1⎞ ⎛ 1⎞ ⎤
2

G 0 =ν0 ⎢⎜ 0 + ⎟ − xe ⎜ 0 + ⎟ ⎥
⎢⎣⎝ 2⎠ ⎝ 2 ⎠ ⎥⎦
1 1
G 0 = ν0 − ν0 xe
2 4
1 1
G 0 = × 2 989 cm –1 − × 52.82 cm –1
2 4

G0 = 1 481.295 cm –1

1 481.295 cm –1 × 2.998 ×1010 cm s –1 × 6.626 ×10−34 J s

G 0 =
1.602 × 10−19 J ( eV )
−1

G = 0.183 680 1 eV
0

To solve for D0, we solve as follows,

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

⎛1 1 ⎞
D0 = De − ⎜ ν0 − ν0 xe ⎟
⎝ 2 4 ⎠
1 1
G 0 = ν0 − ν0 xe = 0.183 680 1 eV
2 4
D0 = 4.617 3 eV − 0.183 680 1 eV
D0 = 4.433 619 9 eV
D0 = 4.433 6 eV

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.50. The dissociation energy (from the zero-point level) of the ground state NO(X2π) molecule is 6.6 eV. There exists an electronically
excited B2Π state of NO whose zero-point level lies at 5.7 eV above the zero-point level of the ground state. The ground-state
molecule dissociates into ground state N(4S) + O(3(P)), while the B2Π species dissociates into two ground-state atoms N(2D) + O(3P)
that lie 3.3 eV above its ground state. Sketch the potential energy curves and calculate the dissociation energy of NO into N(2D) +
O(3P).

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

13.51. Sodium vapor, which consists mainly of Na2 molecules, has a system of absorption bands in the green, the origin of the 0, 0 band
being at 20 302.6 cm–1. From the spacing of the vibrational levels it can be deduced that the dissociation energy of the upper state is
0.35 eV. The dissociation of the excited Na2 gives a normal atom and an atom that emits the yellow sodium D line at 589.3 nm.
Calculate the energy of dissociation of Na2 in its ground state.

Solution:

Given: Na 2 ; ν0 = 20 302.6 cm –1 , De = 0.35 eV, λ = 589.3 nm

Required: D0

The wavenumber 20 302.6 cm –1 corresponds to a frequency of,

ν = 20 302.6 cm –1 × 2.998 ×1010 cm s –1
ν = 6.086 72 ×1014 s –1

And therefore an energy of,

E = hν
E = 6.626 × 10−34 J s × 6.086 72 ×1014 s –1
E = 4.033 06 ×10−19 J
4.033 06 × 10−19 J
E=
1.602 × 10−19 J ( eV )
−1

E = 2.517 515 81 eV

The wavelength at 589.3 nm corresponds to a frequency of,

2.998 × 108 m s –1
ν=
589.3 m × 10−9 m
ν = 5.087 39 ×1014 s –1

And therefore an energy of,

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Chapter 13: Foundations of Chemical Spectroscopy Solutions

E = hν
E = 6.626 × 10−34 J s × 5.087 39 × 1014 s –1
E = 3.370 91× 10−19 J
3.370 91×10−19 J
E=
1.602 ×10−19 J ( eV )
−1

E = 2.104 185 905 eV

The dissociation energy therefore becomes,

D0 = 2.517 515 81 eV + 0.35 eV − 2.104 185 905 eV
D0 = 0.763 329 904 eV
D0 = 0.763 329 904 eV × 1.602 ×10−19 J ( eV ) × 6.022 ×1023 mol−1
−1

D0 = 73 640.298 41 J mol−1
D0 = 73.6 kJ mol−1

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