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Conceptual Problems

*1 • Determine the Concept Yes. Because the center of charge of the positive Na ion does not coincide with the center of charge for the negative Cl ion, the NaCl molecule has a permanent dipole moment. Hence, it is a polar molecule. 2 • Determine the Concept Because a N2 molecule has no permanent dipole moment, it is a non-polar molecule. 3 • Determine the Concept No. Neon occurs naturally as Ne, not Ne2. Neon is a rare gas atom with a closed shell electron configuration. 4 • Determine the Concept (a) Because an electron is transferred from the H atom to the F atom, the bonding mechanism is ionic. (b) Because an electron is transferred from the K atom to the Br atom, the bonding mechanism is ionic. (c) Because the atoms share two electrons, the bonding mechanism is covalent. (d) Because each valence electron is shared by many atoms, the bonding mechanism is metallic bonding. *5 •• Determine the Concept The diagram would consist of a non-bonding ground state with no vibrational or rotational states for ArF (similar to the upper curve in Figure 37-4) but for ArF* there should be a bonding excited state with a definite minimum with respect to inter-nuclear separation and several vibrational states as in the excited state curve of Figure 37-13. 6 • Determine the Concept Elements similar to carbon in outer shell configurations are silicon, germanium, tin, and lead. We would expect the same hybridization for these as

1225

1226

Chapter 37

for carbon, and this is indeed the case for silicon and germanium whose crystal structure is the diamond structure. Tin and lead, however, are metallic and here the metallic bond is dominant. 7 • Determine the Concept The effective force constant from Example 37-4 is 1.85×103 N/m. This value is about 25% larger than the given value of the force constant of the suspension springs on a typical automobile. 8 • Determine the Concept As the angular momentum increases, the separation between the nuclei also increases (the effective force between the nuclei is similar to that of a stiff spring). Consequently, the moment of inertia also increases. 9 • Determine the Concept For H2, the concentration of negative charge between the two protons holds the protons together. In the H + ion, there is only one electron that is shared 2 by the two positive charges such that most of the electronic charge is again between the two protons. However, the negative charge in the H + ion is not as effective as the larger 2 charge in the H2 molecule, and the protons should be farther apart. The experimental values support this argument. For H2, r0 = 0.074 nm, while for H + , r0 = 0.106 nm. 2 10 • Determine the Concept The energy of the first excited state of an atom is orders of magnitude greater than kT at ordinary temperatures. Consequently, practically all atoms are in the ground state. By contrast, the energy separation between the ground rotational state and nearby higher rotational states is less than or roughly equal to kT at ordinary temperatures, and so these higher states are thermally excited and occupied. 11 •• Determine the Concept With more than two atoms in the molecule there will be more than just one frequency of vibration because there are more possible relative motions. In advanced mechanics these are known as normal modes of vibration.

**Estimation and Approximation
**

12 •• Picture the Problem We can estimate the value of the quantum number ν for which the improved formula corrects the original formula by 10 percent by setting the ratio of the correction term to the first term equal to 10 percent and solving for ν.

Molecules

Express the ratio of the correction term to the first term of the expression for Eν and simplify to obtain: For a correction of 10 percent: Solve for ν to obtain:

1227

(ν + 1 )2 hfα = (ν + 1 )α 2 2 (ν + 1 )hf 2

(ν + 1 )α = 0.1 2

ν= ν=

1 1 − 10α 2 1 1 − = 12.7 ≈ 13 −3 10 7.6 × 10 2

**Substitute numerical values and evaluate ν :
**

13 ••

(

)

Picture the Problem We can solve Equation 37-12 for l and substitute for the moment of inertia and rotational kinetic energy of the baseball to estimate the quantum number l and spacing between adjacent energy levels for a baseball spinning about its own axis. The rotational energy levels are given by Equation 37-12:

l(l + 1) h 2 E= 2I

where l = 0, 1, 2, … is the rotational quantum number and I is the moment of inertia of the ball.

Solve for l(l+1):

l(l + 1) =

2 IE h2

Factor l from the parentheses to obtain: The result of our calculation of l will show that l >> 1. Assuming for the moment that this is the case: Because the energy of the ball is rotational kinetic energy: Substitute for E in the expression for l to obtain: The moment of inertia of a ball about an axis through its diameter is (see Table 9-1): Substitute for I to obtain:

⎛ 1 ⎞ 2 IE l 2 ⎜1 + ⎟ = 2 ⎝ l⎠ h

l2 ≈

2 IE and l ≈ h2

2 IE h

E = K rot = 1 Iω 2 2

l≈

2I

(

1 2

Iω 2

h

) = (I ω ) = Iω

2 2

h

h

I = 2 mr 2 5

l≈

2mr 2ω 5h

1228 Chapter 37

Substitute numerical values and evaluate l:

2π rad 1 min ⎞ 2 ⎛ 20 rev ⎟ × × 2(0.3 kg )(0.03 m ) ⎜ ⎜ min rev 60 s ⎟ ⎝ ⎠ = 2.15 ×1030 l≈ −34 5 1.05 ×10 J ⋅ s

(

)

Set l = 0 to express the spacing between adjacent energy levels: Substitute numerical values and evaluate E0r:

h2 5h 2 E0 r = = 2 I 4mr 2

5 1.05 × 10 −34 J ⋅ s E0 r = 2 4(0.3 kg )(0.03 m ) = 5.10 ×10 −65 J

(

)

2

Remarks: Note that our value for l justifies our assumption that l >> 1. Picture the Problem We can solve Equation 37-18 for ν and substitute for the frequency of the mass-and-spring oscillator to estimate the quantum number ν and spacing between adjacent energy levels for this system. The vibrational energy levels are given by Equation 37-18: Solve for ν :

*14 ••

Eν = (ν + 1 )hf 2 where ν = 0, 1, 2, … Eν 1 − hf 2 or, because ν >> 1, E ν≈ ν hf

ν=

The vibrational energy of the object attached to the spring is: Substitute for Eν in the expression for ν to obtain: The frequency of oscillation f of the mass-and-spring oscillator is given by:

Eν = 1 kA2 2

where A is the amplitude of its motion.

ν=

f =

kA2 2hf 1 2π k m m πA2 = mk k h

ν=

πkA2

h

Molecules 1229

Substitute numerical values and evaluate ν :

ν=

π (0.02 m )2

6.63 ×10

−34

J ⋅s

(5 kg )(1500 N/m ) =

E0ν =

1.64 ×1032

Set ν = 0 in Equation 37-18 to express the spacing between adjacent energy levels: Substitute numerical values and evaluate E0ν:

1 h hf = 2 4π

k m

E0ν =

6.63 × 10 −34 J ⋅ s 1500 N/m 4π 5 kg

= 9.14 × 10 −34 J

Remarks: Note that our value for ν justifies our assumption that ν >> 1.

Molecular Bonding

15 • Picture the Problem The electrostatic potential energy with U at infinity is given by

U = − ke2 r.

Relate the electrostatic potential energy of the ions to their separation: Solve for r:

Ue = −

ke 2 r

r=−

ke 2 Ue

Substitute numerical values and evaluate r:

(8.99 ×10 r=−

N ⋅ m 2 / C 2 1.6 × 10 −19 C (− 1.52 eV ) 1.6 ×10−19 J/eV

9

(

)(

)

)

2

= 0.946 nm

16 • Picture the Problem We can find the energy absorbed or released per molecule by computing the difference between dissociation energy of Cl and the binding energy of NaCl.

1230 Chapter 37

Noting that the dissociation energy per Cl atom is 1.24 eV, express the net energy change per molecule ∆E: The binding energy of NaCl is (see page 1210): Substitute and evaluate ∆E:

∆E = 1.24 eV − Ebinding, NaCl

4.27 eV

∆E = 1.24 eV − 4.27 eV = − 3.03 eV

**Because ∆E < 0, energy is released. The reaction is exothermic.
**

17 • Picture the Problem We can use conversion factors to convert eV/molecule into kcal/mol.

1

(a)

eV eV 1kcal 6.02 ×10 23 molecules 1.60 × 10−19 J =1 × × × molecule molecule 4184 J mole eV

= 23.0 kcal/mol

(b) The dissociation energy of NaCl, in eV/molecule, is (see page 1205): Using the conversion factor in (a), express this energy in kcal/mol: 4.27 eV/molecule

4.27 eV 23.0 kcal × = 98.2 kcal/mol molecule mol

*18 • Picture the Problem The percentage of the bonding that is ionic is given by

**⎛p ⎞ 100⎜ meas ⎟. ⎜ p ⎟ ⎝ 100 ⎠
**

Express the percentage of the bonding that is ionic: Express the dipole moment for 100% ionic bonding:

⎛p ⎞ Percent ionic bonding = 100⎜ meas ⎟ ⎜ p ⎟ ⎝ 100 ⎠

p100 = er

Molecules 1231

Substitute to obtain:

⎛p ⎞ Percent ionic bonding = 100⎜ meas ⎟ ⎝ er ⎠

Substitute numerical values and evaluate the percent ionic bonding:

⎡ ⎤ 6.40 × 10 −30 C ⋅ m Percent ionic bonding = 100 ⎢ ⎥ = 43.6% −19 ⎣ 1.60 × 10 C (0.0917 nm )⎦

(

)

19 •• Picture the Problem If we choose the potential energy at infinity to be ∆E, the total potential energy is Utot = Ue + ∆E + Urep, where Urep is the energy of repulsion, which is found by setting the dissociation energy equal to −Utot. Express the total potential energy of the molecule: The core-repulsive energy is : Calculate the energy ∆E needed to form Rb+ and F− ions from neutral rubidium and fluorine atoms: Express the electrostatic potential energy is: Substitute numerical values and evaluate Ue:

U tot = U e + ∆E + U rep U rep = −(∆E + U e + Ed )

∆E = 4.18 eV − 3.40 eV = 0.78 eV

Ue = −

ke 2 r

Ue = −

(8.99 ×10

**N ⋅ m 2 / C 2 1.60 × 10 −19 C (0.227 nm ) 1.60 ×10−19 J/eV
**

9

(

)(

)

)

2

= −6.34 eV

Substitute numerical values and evaluate Urep:

U rep = −(0.78 eV − 6.34 eV + 5.12 eV ) = 0.44 eV

20 •• Picture the Problem The potential energy of attraction of the ions is U e = − ke 2 r . We can find the dissociation energy from the negative of the sum of the potential energy of attraction and the difference between the ionization energy of potassium and the electron

1232 Chapter 37

affinity of chlorine. (a) The potential energy of attraction of the ions is given by:

Ue = −

ke 2 r

where ke2 = 1.44 eV⋅nm Substitute numerical values and evaluate Ue: (b) Express the total potential energy of the molecule:

Ue = −

1.44 eV ⋅ nm = − 5.39 eV 0.267 nm

U tot = U e + ∆E + U rep

or, neglecting any energy of repulsion,

U tot = U e + ∆E

The dissociation energy is the negative of the total potential energy: ∆E is the difference between the ionization energy of potassium and the electron affinity of Cl: Substitute numerical values and evaluate Ed,calc:

Ed,calc = −U tot = −(U e + ∆E )

∆E = 4.34 eV − 3.62 eV = 0.72 eV

Ed,calc = −(− 5.39 eV + 0.72 eV ) = 4.67 eV U rep = Ed,calc − Ed,meas

The energy due to repulsion of the ions at equilibrium separation is given by: Substitute numerical values and evaluate Urep:

U rep = 4.67 eV − 4.49 eV = 0.18 eV

21 •• Picture the Problem Assume that U(r) is of the form given in Problem 24 with n = 6.

Molecules 1233

The potential energy curve is shown in the figure. The turning points for vibrations of energy E1 and E2 are at the values of r, where the energies equal U(r). It is apparent that the average value of r depends on the energy and that r2,av is greater than r1,av.

22 •• Picture the Problem We can use U e = − ke 2 r0 to calculate the potential energy of attraction between the Na+ and Cl− ions at the equilibrium separation r0 = 0.236 nm. We can find the energy due to repulsion of the ions at the equilibrium separation from U rep = −(U e + Ed + ∆E ) . The potential energy of attraction between the Na+ and Cl− ions at the equilibrium separation r0 is given by: Substitute numerical values and evaluate Ue: From Figure 37-1: The ratio of the magnitude of the potential energy of attraction to the dissociation energy is: Urep is related to Ue, Ed, and ∆E according to: From Figure 37-1: Substitute numerical values and evaluate Urep:

Ue = −

ke 2 r0

where ke2 = 1.44 eV⋅nm.

Ue = −

1.44 eV ⋅ nm = − 6.10 eV 0.236 nm

Ed = 4.27 eV U e 6.10 eV = = 1.43 Ed 4.27 eV U rep = −(U e + Ed + ∆E )

∆E = 1.52 eV

U rep = −(− 6.10 eV + 4.27 eV + 1.52 eV ) = 0.310 eV

23 •• Picture the Problem The potential energy of attraction of the ions is U e = − ke 2 r . We can find the dissociation energy from the negative of the sum of the potential energy of

1234 Chapter 37

attraction and the difference between the ionization energy of potassium and the electron affinity of fluorine. (a) The potential energy of attraction between the K+ and F− ions at the equilibrium separation r0 is given by: Substitute numerical values and evaluate Ue: (b) Express the total potential energy of the molecule:

Ue = −

ke 2 r0

where ke2 = 1.44 eV⋅nm.

Ue = −

1.44 eV ⋅ nm = − 6.64 eV 0.217 nm

U tot = U e + ∆E + U rep

or, neglecting any energy of repulsion,

U tot = U e + ∆E

The dissociation energy is the negative of the total potential energy: ∆E is the difference between the ionization energy of potassium and the electron affinity of fluorine: Substitute numerical values and evaluate Ed,calc:

Ed,calc = −U tot = −(U e + ∆E )

∆E = 4.34 eV − 3.40 eV = 0.94 eV

Ed,calc = −(− 6.64 eV + 0.94 eV ) = 5.70 eV U rep = Ed,calc − Ed,meas

The energy due to repulsion of the ions at equilibrium separation is given by: Substitute numerical values and evaluate Urep:

U rep = 5.70 eV − 5.07 eV = 0.63 eV

*24 ••• Picture the Problem U(r) is the potential energy of the two ions as a function of separation distance r. U(r) is chosen so U(∞) = −∆E, where ∆E is the negative of the energy required to form two ions at infinite separation from two neutral atoms also at infinite separation. Urep(r) is the potential energy of the two ions due to the repulsion of the two closed-shell cores. Ed is the disassociation energy, the energy required to separate the two ions plus the energy ∆E required to form two neutral atoms from the two ions at

Molecules 1235

infinite separation. The net force acting on the ions is the sum of Frep and Fe. We can find Frep from Urep and Fe from Coulomb’s law and then use dU/dr = Fnet = 0 at r = r0 to solve for n. Express the net force acting on the ions: Find Frep from Urep:

Fnet = Frep + Fe

(1)

Frep =

dU rep

dr nC = − n+1 r

=

d Cr −n = −nCr −n−1 dr

[

]

The electrostatic potential energy of the two ions as a function of separation distance is given by: Find the electrostatic force of attraction Fe from Ue:

ke 2 Ue = − r

Fe =

dU e d ⎡ ke 2 ⎤ ke 2 = − = dr dr ⎢ r ⎥ r 2 ⎣ ⎦

Substitute for Frep and Fe in equation (1) to obtain: Because dU/dr = Fnet = 0 at r = r0: Multiply both sides of this equation by r0 to obtain: Solve for n to obtain:

Fnet

nC ke 2 = − n+1 + 2 r r nC ke 2 + r0n+1 r02 nC ke 2 + = −nU rep (r0 ) + U e (r0 ) r0n r0

0=−

0=−

n=

U e (r0 ) U rep (r0 )

25 ••• Picture the Problem Urep at r = r0 is related to Ue, Ed, and ∆E through U rep = −(U e + Ed + ∆E ) . The net force is the sum of Frep and Fe. We can find Frep from Urep and Fe from Coulomb’s law. Because Fnet = 0 at r = r0, we can obtain simultaneous equations in C and n that we can solve for each of these quantities. (a) Urep is related to Ue, Ed, and ∆E according to:

U rep = −(U e + Ed + ∆E )

where ∆ENaCl = 1.52 eV

1236 Chapter 37

Ue(r0) is given by:

ke 2 Ue = − r0

where ke2 = 1.44 eV⋅nm

Substitute numerical values and evaluate Ue: Substitute numerical values and evaluate Urep:

Ue = −

1.44 eV ⋅ nm = −6.10 eV 0.236 nm

**U rep = −(− 6.10 eV + 4.27 eV + 1.52 eV ) = 0.31eV Fnet = Frep + Fe
**

(1)

(b) Express the net force acting on the Na+ and Cl− ions: Find Frep from Urep:

Frep =

dU rep

dr nC = − n+1 r

=

d Cr −n = −nCr −n−1 dr

[

]

The electrostatic force of attraction is: Substitute for Frep and Fe in equation (1) to obtain: Because Fnet = 0 at r = r0:

ke 2 Fe = 2 r Fnet = − nC ke 2 + r n+1 r 2

0=−

or

nC ke 2 + r0n+1 r02 C = nU rep (r0 ) r0n

U e (r0 ) = n

Solve for n and C to obtain:

n=

and

U e (r0 ) U rep (r0 )

C = U rep (r0 )r0n

From (a):

U e (r0 ) = −6.10 eV U rep (r0 ) = 0.31eV

and, from Figure 37-1,

Molecules 1237

r0 = 0.236 nm

Substitute for Ue(r0) and Urep(r0) and evaluate n and C:

n=

and

6.10 eV = 19.7 0.31eV

19.7

C = (0.31eV )(0.236 nm )

= 1.37 × 10 −13 eV ⋅ nm19.7

**Energy Levels of Spectra of Diatomic Molecules
**

26 • Picture the Problem We can relate the characteristic rotational energy E0r to the moment of inertia of the molecule and model the moment of inertia of the N2 molecule as two point objects separated by a distance r. The characteristic rotational energy of a molecule is given by: Express the moment of inertia of the molecule: Substitute for I to obtain:

h2 E0 r = 2I

⎛r⎞ I = 2M N ⎜ ⎟ = 1 M N r 2 2 ⎝2⎠ E0 r =

2

h2 h2 h2 = = 2 1 M Nr 2 M N r 2 14mp r 2 2

(

)

Solve for r:

r=h

1 14 E0 r mp

Substitute numerical values and evaluate r:

r = 1.055 × 10 −34 J ⋅ s = 0.109 nm

(

) 14(2.48 ×10

−4

1 eV 1.602 × 10 −19 J/eV 1.673 × 10 −27 kg

)(

)(

)

*27 • Picture the Problem We can relate the characteristic rotational energy E0r to the moment of inertia of the molecule and model the moment of inertia of the O2 molecule as two point objects separated by a distance r.

1238 Chapter 37

The characteristic rotational energy of a molecule is given by: Express the moment of inertia of the molecule: Substitute for I to obtain:

h2 E0 r = 2I

⎛r⎞ I = 2M O ⎜ ⎟ = 1 M O r 2 2 ⎝2⎠ E0 r =

h2 h2 h2 = = 2 1 M Or 2 M O r 2 16mp r 2 2

2

(

)

Solve for r:

r=

h 1 4 E0 r mp

Substitute numerical values and evaluate r:

⎛ 1.055 × 10 −34 J ⋅ s ⎞ 1 ⎟ r =⎜ ⎜ ⎟ 1.78 × 10 −4 eV 1.6 × 10 −19 J/eV 1.67 × 10 −27 kg 4 ⎝ ⎠

(

)(

)(

)

= 0.121 nm

28 •• Picture the Problem We can use the definition of the reduced mass to show that the reduced mass is smaller than either mass in a diatomic molecule. Express the reduced mass of a twobody system: Divide the numerator and denominator of this expression by m2 to obtain: Divide the numerator and denominator of this expression by m1 to obtain: Because the denominator is greater than 1 in equations (1) and (2): (a) For H2, m1 = m2 = 1 u:

µ=

µ=

m1m2 m1 + m2

m1 m 1+ 1 m2

(1)

µ=

m2 m 1+ 2 m1

(2)

µ < m1 and µ < m2

µH =

2

(1u )(1u ) =

1u + 1u

0.500 u

Molecules 1239

(b) For N2, m1 = m2 = 14 u:

µN =

2

(14 u )(14 u ) =

14 u + 14 u

7.00 u

(c) For CO, m1 = 12 u and m2 = 16 u: (d) For HCl, m1 = 1 u and m2 = 35.5 u:

µCO =

(12 u )(16 u ) =

12 u + 16 u

6.86 u

µ HCl =

(1u )(35.5 u ) =

1 u + 35.5 u

0.973 u

29 •• Picture the Problem We can solve Equation 37-18 for ν and substitute for the frequency of the CO molecule (see Example 37-4) and its binding energy to estimate the quantum number ν . The vibrational energy levels are given by Equation 37-18: Solve for ν :

Eν = (ν + 1 )hf 2 where ν = 0, 1, 2, …

ν=

Eν 1 − hf 2

11eV ×

Substitute numerical values and evaluate ν :

1.60 × 10−19 J 1 eV ν= − −34 13 6.63 × 10 J ⋅ s 6.42 × 10 Hz 2

(

)(

)

= 40.8 ≈ 41

*30 •• Picture the Problem We can use the expression for the rotational energy levels of the diatomic molecule to express the energy separation ∆E between the l = 3 and l = 2 rotational levels and model the moment of inertia of the LiH molecule as two point objects separated by a distance r0. The energy separation between the l = 3 and l = 2 rotational levels of this diatomic molecule is given by: Express the rotational energy levels El = 3 and El = 2 in terms of E0r:

∆E = El=3 − El=2

El=3 = 3(3 + 1)E0 r = 12 E0 r

and

El=2 = 2(2 + 1)E0 r = 6 E0 r

Substitute for El = 3 and El = 2 to

∆E = 12 E0 r − 6 E0 r = 6 E0 r

1240 Chapter 37

obtain: or

E0 r = 1 ∆E 6

The characteristic rotational energy of a molecule is given by: Express the moment of inertia of the molecule:

E0 r =

h2 1 3h 2 = 6 ∆E ⇒ ∆E = 2I I

I = µ r02

where µ is the reduced mass of the molecule.

Substitute for I to obtain:

∆E =

µ r02

3h 2

=

3h 2 m Li m H m Li + m H

r02

=

3h 2 (m Li + m H ) m Li m H r02

Substitute numerical values and evaluate ∆E:

**3 1.055 × 10 −34 J ⋅ s (6.94 u + 1 u ) ∆E = = 5.61 meV (6.94 u )(1u )(0.16 nm )2 1.602 ×10−19 J/eV 1.660 ×10−27 kg/u
**

2

(

(

)

)(

)

*31 •• Picture the Problem Let the origin of coordinates be at the point mass m1 and point mass m2 be at a distance r0 from the origin. We can express the moment of inertia of a diatomic molecule with respect to its center of mass using the definitions of the center of mass and the moment of inertia of point particles. Express the moment of inertia of a diatomic molecule: The r coordinate of the center of mass is: The distances of m1 and m2 from the center of mass are:

I = m1r12 + m2 r22

(1)

rCM =

m2 r0 m1 + m2

r1 = rCM

and

r2 = r0 − rCM = r0 − = m1 r0 m1 + m2

m2 r0 m1 + m2

Molecules 1241

Substitute for r1 and r2 in equation (1) to obtain:

⎛ m2 ⎞ ⎛ m1 ⎞ I = m1 ⎜ ⎜ m + m r0 ⎟ + m2 ⎜ m + m r0 ⎟ ⎟ ⎜ ⎟ 2 2 ⎝ 1 ⎠ ⎝ 1 ⎠ I=

or

2

2

Simplifying this expression leads to:

m1m2 2 r0 m1 + m2

36-14

I = µ r02

where

µ=

m1m2 m1 + m2

36-15

32 •• Picture the Problem We can relate the characteristic rotational energy E0r to the moment of inertia of the molecule and model the moment of inertia of the KCl molecule as two point objects of reduced mass µ separated by a distance r. The characteristic rotational energy of a molecule is given by: Express the moment of inertia of the molecule:

E0 r =

h2 2I

I = µ r02

where µ =

mK mCl mK + mCl

Substitute for I to obtain:

h2 h 2 (mK + mCl ) = E0 r = 2µ r02 2mk mCl r02

Substitute numerical values and evaluate E0r:

**J ⋅ s (39.1 u + 35.5 u ) E0 r = 2 2(39.1 u )(35.5 u )(0.267 nm ) 1.660 ×10 −27 kg/u 1 = 2.53 × 10−24 J × = 0.0158 meV 1.602 ×10 −19 J/eV
**

−34 2

(1.055 ×10

)

(

)

33 •• Picture the Problem We can use the expression for the vibrational energies of a molecule to find the lowest vibrational energy. Because the difference in the vibrational energy levels depends on both ∆f and the moment of inertia I of the molecule, we can relate these quantities and solve for I. Finally, we can use I = µ r 2 , with µ representing

1242 Chapter 37

the reduced mass of the molecule, to find the equilibrium separation of the atoms. (a) The vibrational energy levels are given by: The lowest vibrational energy corresponds to ν = 0: Substitute numerical values and evaluate E0:

Eν = (ν + 1 )hf, ν = 0,1, 2, ... 2 E0 = 1 hf 2

E0 =

1 2

(6.63 ×10

−34

J ⋅ s 8.66 ×1013 Hz = 2.87 × 10 −20 J ×

)(

)

1 1.6 × 10 −19 J/eV

= 0.179 eV

(b) For ∆l = ±1:

∆El =

I=

lh 2 = lh∆f I

Solve for I:

h2 h2 h = = 2 h∆f 4π h∆f 4π 2 ∆f

Substitute numerical values and evaluate I:

6.63 × 10−34 J ⋅ s I= 4π 2 6 × 1011 Hz

(

)

= 2.80 × 10 −47 kg ⋅ m 2

(c) The moment of inertia of a HCL molecule is given by: Replace µ by the reduced mass of a HCl molecule and r by r0 to obtain: Solve for r0:

I = µ r2

I=

**mH mCl 2 r0 mH + mCl
**

mH + mCl I mH mCl

r0 =

Substitute numerical values and evaluate r0:

⎡ 1 u + 34.453 u ⎤ 2.80 × 10 −47 kg ⋅ m 2 r0 = ⎢ = 0.132 nm ⎥ − 27 ⎣ (1 u )(34.453 u ) ⎦ 1.66 × 10 kg/u

(

)

Molecules

1243

34 •• Picture the Problem Let the numeral 1 refer to the H+ and the numeral 2 to the Cl− ion. For a two-mass and spring system on which no external forces are acting, the center of mass must remain fixed. We can use this condition to express the net force acting on either the H+ or Cl− ion. Because this force is a linear restoring force, we can conclude that the motion of the object whose mass is m1 will be simple harmonic with an angular frequency given by ω = K eff m1 . Substitution for Keff will lead us to the result given in (b). If the particle whose mass is m1 moves a distance r1 from (or toward) the center of mass, then the particle whose mass is m2 must move a distance: Express the force exerted by the spring: Substitute for ∆r2 to obtain:

∆r2 =

m1 ∆r1 from (or toward) the center m2

of mass.

F = − K∆r = − K (∆r1 + ∆r2 )

**⎛ ⎞ m F = − K ⎜ ∆r1 + 1 ∆r1 ⎟ ⎜ ⎟ m2 ⎝ ⎠ ⎛ m + m2 ⎞ = −K ⎜ 1 ⎜ m ⎟∆r1 ⎟ 2 ⎝ ⎠
**

⎛ m + m2 ⎞ ⎟∆r1 = − K eff ∆r1 F = −K ⎜ 1 ⎟ ⎜ m 2 ⎠ ⎝ ⎛ m + m2 ⎞ where K eff = K ⎜ 1 ⎟ ⎜ m ⎟ 2 ⎠ ⎝

A displacement ∆r1 of m1 results in a restoring force:

Because this is a linear restoring force, we know that the motion will be simple harmonic with:

ω=

or

K eff m1

f =

1 ω = 2π 2π

K eff m1

Substitute for Keff and simplify to obtain:

⎛ m + m2 ⎞ K⎜ 1 ⎟ ⎜ mm ⎟ ⎝ 1 2 ⎠ m1 m2 or, because µ = is the reduced m1 + m2 f =

ω 1 = 2π 2π

1244 Chapter 37

mass of the two-particle system,

f =

1 2π

K

µ

mH mCl mH + mCl

Solve for K:

K = 4π 2 f 2 µ = 4π 2 f 2

Substitute numerical values and evaluate K:

**4π 2 8.66 × 1013 Hz (1 u )(35.453 u ) 1.66 × 10 −27 kg/u K= = 478 N/m (1u + 35.453 u )
**

2

(

)

(

)

35 •• Picture the Problem We’re given the population of rotational states function:

f (l ) = (2l + 1)e − El / kT

where

El = l(l + 1) E0 r and E0 r =

The moment of inertia I of an oxygen molecule is given by:

h2 2I

I = 1 mr02 2

where m is the reduced mass and r0 is the separation of the atoms in a molecule.

We’ll assume, as in Example 37-3, that:

r0 = 0.1 nm

A spreadsheet program to plot f(l) is shown below. The formulas used to calculate the quantities in the columns are as follows: Cell B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 A13 Formula/Content 1.00E−10 16 2.66E−26 1.05E−34 1.38E−23 4.15E−23 100 200 300 500 0 Algebraic Form r0 m (u) m (kg) h k E0r T (K) T (K) T (K) T (K) l

Molecules

B13 A13*(A13+1)*$B$6

1245

l(l + 1)E0r

f(l, T = 100 K) f(l, T = 200 K) f(l, T = 300 K) f(l, T = 500 K) E F

C13 (2*A13 + 1)*EXP(−B13/($B$5*$B$7)) D13 (2*A13 + 1)*EXP(−B13/($B$5*$B$8)) E13 (2*A13 + 1)*EXP(−B13/($B$5*$B$9)) F13 (2*A13 + 1)*EXP(−B13/($B$5*$B$10)) A 1 r_0= 2 m= 3 m= 4 h_bar= 5 k= 6 E_0r= 7 T= 8 T= 9 T= 10 T= 11 12 l 13 0.0 14 0.5 15 1.0 16 1.5 17 2.0 29 30 31 32 33 8.0 8.5 9.0 9.5 10.0 B 1.00E−10 16 2.656E−26 1.05E−34 1.38E−23 4.15E−23 100 200 300 500 E_l 0.00E+00 3.11E−23 8.30E−23 1.56E−22 2.49E−22 2.99E−21 3.35E−21 3.74E−21 4.14E−21 4.57E−21 C m u kg J.s J/K eV K K K K D

E_100 K E_200 K E_300 K E_500 K 1.00 1.00 1.00 1.00 1.96 1.98 1.99 1.99 2.82 2.91 2.94 2.96 3.57 3.78 3.85 3.91 4.17 4.57 4.71 4.82 1.95 1.59 1.27 1.00 0.77 5.76 5.34 4.91 4.46 4.02 8.26 8.01 7.71 7.36 6.97 11.02 11.07 11.06 10.98 10.83

1246 Chapter 37

**The following graph shows f(l) as a function of temperature.
**

12 T = 100 K T = 200 K 10 T = 300 K T = 500 K 8

f (l )

6

4

2

0 0 2 4 6 8 10 rotational quantum number l

*36 •• Picture the Problem For a two-mass and spring system on which no external forces are acting, the center of mass must remain fixed. We can use this condition to express the net force acting on either object. Because this force is a linear restoring force, we can conclude that the motion of the object whose mass is m1 will be simple harmonic with an angular frequency given by ω = given in (b). (a) If the particle whose mass is m1 moves a distance ∆r1 from (or toward) the center of mass, then the particle whose mass is m2 must move a distance: Express the force exerted by the spring: Substitute for ∆r2 to obtain:

keff . Substitution for keff will lead us to the result m1

∆r2 =

m1 ∆r1 from (or toward) the center m2

of mass.

F = −k∆r = −k (∆r1 + ∆r2 )

⎞ ⎛ m F = −k ⎜ ∆r1 + 1 ∆r1 ⎟ ⎟ ⎜ m2 ⎠ ⎝ ⎛ m + m2 ⎞ = − k⎜ 1 ⎟ ⎜ m ⎟∆r1 2 ⎠ ⎝

Molecules

(b) A displacement ∆r1 of m1 results in a restoring force:

1247

⎛ m + m2 ⎞ F = −k ⎜ 1 ⎟ ⎜ m ⎟∆r1 = −keff ∆r1 2 ⎠ ⎝ ⎛ m + m2 ⎞ where keff = k ⎜ 1 ⎟ ⎜ m ⎟ 2 ⎠ ⎝

Because this is a linear restoring force, we know that the motion will be simple harmonic with:

ω=

or

keff m1

f =

ω 1 = 2π 2π

keff m1

Substitute for keff and simplify to obtain:

f =

⎛ m + m2 ⎞ ω 1 = k⎜ 1 ⎜ mm ⎟ ⎟ 2π 2π ⎝ 1 2 ⎠ m1 m2 is the reduced m1 + m2

or, because µ =

mass of the two-particle system,

f =

1 2π

k

µ

.

37 ••• Picture the Problem We can use the definition of the reduced mass to find the reduced mass for the H35Cl and H37Cl molecules and the fractional difference ∆µ µ . Because the rotational frequency is proportional to 1/I, where I is the moment of inertia of the system, and I is proportional to µ, we can obtain an expression for f as a function of µ that we differentiate implicitly to show that ∆f f = − ∆µ µ . For H35Cl:

µ=

(35 u )(1u ) = 35 u =

35 u + 1 u 36

0.9722 u

For H37Cl:

µ=

(37 u )(1u ) = 37 u =

37 u + 1 u 38

0.9737 u

The fractional difference is:

37 35 36 × 37 − 35 × 38 u− u u ∆µ 36 36 × 38 = 38 = = 0.00150 1 ⎛ 35 37 ⎞ 35 × 38 + 36 × 37 µ u ⎜ u + u⎟ 2(36 )(38) 2 ⎝ 36 38 ⎠

1248 Chapter 37

The rotational frequency is proportional to 1/I, where I is the moment of inertia of the system. Because I is proportional to µ: Divide df by f to obtain:

f =

and

C

µ

**df = −Cµ −2 dµ df dµ ∆f ∆µ =− and ≈− f µ f µ ∆f ≈ 0.01× 1013 Hz = 1011 Hz
**

∆f 1011 Hz ≈ = 0.00119 f 8.40 × 1013 Hz

From Figure 36-17: For f = 8.40×1013 Hz:

This result is in fair agreement (about 21% difference) with the calculated result. Note that ∆f is difficult to determine precisely from Figure 36 - 17.

General Problems

38 • Picture the Problem We can use the definition of the reduced mass to show that when one atom in a diatomic molecule is much more massive than the other the reduced mass is approximately equal to the mass of the lighter atom. Express the reduced mass of a twobody system: Divide the numerator and denominator of this expression by m2 to obtain: If m2 >> m1, then:

µ= µ=

m1m2 m1 + m2 m1 m 1+ 1 m2

m1 << 1 and µ ≈ m1 m2

39 •• Picture the Problem The rotational energy levels are given by

E=

l(l + 1)h 2 , l = 0,1, 2, .... 2I

Express the energy difference between these rotational energy

∆E1, 2 = E2 − E1

Molecules

levels: Express E2 and E1:

1249

E2 =

and

2(2 + 1)h 2 3h 2 = 2I I 1(1 + 1)h 2 h 2 = 2I I 3h 2 h 2 2h 2 = − = I I I

E1 =

Substitute to obtain:

∆E1, 2

The moment of inertia of the molecule is:

I = µ r02

where µ is the reduced mass of the molecule.

Substitute for I to obtain:

∆E1, 2 =

=

2h 2 (mC + mO ) mC mO r02

2h 2 2h 2 = mC mO 2 µ r02 r0 mC + mO

Substitute numerical values and evaluate ∆E1,2:

∆E1, 2

**2 1.055 × 10 −34 J ⋅ s (12 u + 16 u ) 1.53 × 10 −22 J = = (16 u )(12 u )(0.113 nm )2 1.66 ×10−27 kg/u 1.6 ×10−19 J/eV
**

2

(

) (

)

= 0.955 meV

*40 •• Picture the Problem We can use the result of Problem 36 to find the frequency of vibration of the HF molecule. In Problem 36 it was established that: The reduced mass is:

f =

1 2π

k

µ

µ=

mH mF mH + mF

1250 Chapter 37

Substitute for µ to obtain:

f =

1 2π

k 1 = mH mF 2π mH + mF

k (mH + mF ) mH mF

Substitute numerical values and evaluate f:

f =

1 2π

(970 N/m )(1 u + 19 u ) = (1 u )(19 u )(1.66 ×10−27 kg/u )

1.25 × 1014 Hz

41 •• Picture the Problem We can use the result of Problem 36 to find the effective force constant for NO. In Problem 36 it was established that: Solve for k: The reduced mass is:

f =

1 2π

k

µ

k = 4π 2 f 2 µ

µ=

mN mO mN + mO

Substitute for µ to obtain:

4π 2 f 2 mN mO k= mN + mO

Substitute numerical values and evaluate k:

**4π 2 5.63 × 1013 s −1 (14 u )(16 u ) 1.66 × 10 −27 kg/u k= = 1.55 kN/m 14 u + 16 u
**

2

(

)

(

)

42 •• Picture the Problem We can use the expression for the vibrational energy levels of a molecule and the expression for the frequency of oscillation from Problem 36 to find the four lowest vibrational levels of the given molecules. The vibrational energy levels are given by: In Problem 36 we showed that the frequency of oscillation is:

Eν = (ν + 1 )hf,ν = 0,1, 2, ... 2

f =

1 2π

k

µ

Molecules

where

1251

µ=

Substitute for f and µ to obtain:

m1m2 m1 + m2

Eν = =

(ν + 1 )h (m1 + m2 )k 2

2π

m1m2 k

(ν + 1 )h 2

2π

(m1 + m2 )

m1m2

Substitute numerical values to obtain:

Eν

(ν + 1 )(4.136 ×10−15 eV ⋅ s ) 2 =

2π

= (ν + 1 )(0.389 eV ⋅ u ) 2

580 N/m 1.661× 10−27 kg/u

(m1 + m2 )

m1m2

(m1 + m2 )

m1m2

Substitute for m1 and m2 and evaluate E0 for H2:

E0 =

1 2

(0.389 eV ⋅ u ) (1u + 1u ) = 0.275 eV (1u )(1u )

H2 (eV) 0 1 2 3 HD (eV) D2 (eV)

Proceed similarly to complete the table to the right:

0.275 0.825 1.375 1.925

0.238 0.715 1.191 1.667

0.195 0.584 0.973 1.362

The energies of the photons resulting from transitions between adjacent vibrational levels of these molecules are given by: Solve for λ:

∆E = hf =

hc

λ

λ=

hc ∆E

1252 Chapter 37

Evaluate λ(H2):

λ (H 2 ) =

1240 eV ⋅ nm = 2.25 µm 0.550 eV 1240 eV ⋅ nm = 2.60 µm 0.477 eV

Evaluate λ(HD):

λ (HD ) = λ (D 2 ) =

Evaluate λ(D2):

1240 eV ⋅ nm = 3.19 µm 0.389 eV

43 •• Picture the Problem We can set the derivative of the potential energy function equal to zero to find the value of r for which it is either a maximum or a minimum. Examination of the second derivative of this function at the value for r obtained from setting the first derivative equal to zero will establish whether the function is a relative maximum or relative minimum at this point. Differentiate the potential energy function with respect to r:

12 6 dU d ⎧ ⎡⎛ a ⎞ ⎪ ⎪ ⎛ a ⎞ ⎤⎫ = ⎨U 0 ⎢⎜ ⎟ − 2⎜ ⎟ ⎥ ⎬ dr dr ⎪ ⎢⎝ r ⎠ ⎝ r ⎠ ⎥⎪ ⎦⎭ ⎩ ⎣ 11 5 U0 ⎡ ⎛ a ⎞ ⎛a⎞ ⎤ =− ⎢12⎜ ⎟ − 12⎜ ⎟ ⎥ r ⎢ ⎝r⎠ ⎝r⎠ ⎥ ⎣ ⎦

Set the derivative equal to zero:

11 5 ⎛a⎞ ⎤ dU U0 ⎡ ⎛ a ⎞ ⎢12⎜ ⎟ − 12⎜ ⎟ ⎥ =− ⎜r ⎟ dr r0 ⎢ ⎜ r0 ⎟ ⎝ 0⎠ ⎥ ⎣ ⎝ ⎠ ⎦ = 0 for extrema

Solve for r0 to obtain, as our candidate for r that minimizes the Lenard-Jones potential: To show that r0 = a corresponds to a minimum, differentiate U a second time to obtain:

r0 = a

11 5 d 2U d ⎧ U0 ⎡ ⎛ a ⎞ ⎪ ⎪ ⎛ a ⎞ ⎤⎫ = ⎢12⎜ ⎟ − 12⎜ ⎟ ⎥ ⎬ ⎨− 2 dr dr ⎪ r ⎢ ⎝ r ⎠ ⎝ r ⎠ ⎥⎪ ⎣ ⎦⎭ ⎩

=

U0 r2

4 ⎡ ⎛ a ⎞10 ⎛a⎞ ⎤ 132⎜ ⎟ − 60⎜ ⎟ ⎥ ⎢ ⎝r⎠ ⎥ ⎢ ⎝r⎠ ⎣ ⎦

Evaluate this second derivative of the potential at r0 = a:

d 2U dr 2

=

r =a

U0 [132 − 60] = 72U 0 > 0 2 a a2

Therefore, we can conclude that r0 = a

Molecules

minimizes the potential function. Evaluate Umin:

1253

U min

⎡⎛ a ⎞12 ⎛ a ⎞ 6 ⎤ = U (a ) = U 0 ⎢⎜ ⎟ − 2⎜ ⎟ ⎥ ⎝a⎠ ⎥ ⎢⎝ a ⎠ ⎣ ⎦ = −U0

From Figure 37-4:

r0 = 0.074 nm

and

U 0 = 4.52 eV

44 •• Picture the Problem We can use Equation 21-10 to establish the dependence of E on x and the dependence of an induced dipole on the field that induces it to establish the dependence of p and U on x. (a) In terms of the dipole moment, the electric field on the axis of the dipole at a point a great distance x away has the magnitude (see Equation 21-10):

E=

or

2kp

x

3

E∝

1 x

3

(b) Because the induced dipole moment is proportional to the field that induces it:

p∝

and

1 x3 1 x6

r r U = − p⋅ E ∝

(c) Differentiate U with respect to x to obtain:

Fx = −

1 dU ∝ 7 dx x

45 •• Picture the Problem the case of two polar molecules, p does not depend on the field E. Because p does not depend on the electric field in which the polar molecules find themselves:

U∝

1 x3

1254 Chapter 37

Differentiate U with respect to x to obtain:

Fx = −

dU 1 ∝ 4 dx x

46 •• Picture the Problem We can use the expression for the vibrational and rotational energies of a molecule, in conjunction with Figure 37-17 to find E0r, f, and hf. (a) Except for a gap of 4E0r/h at the vibrational frequency f, the absorption spectrum contains frequencies equally spaced at: Solve for E0r: From Figure 37-17: Substitute numerical values and evaluate E0r:

f =

2 E0 r h

E0 r = 1 hf 2 f = 8.66 × 1013 Hz

E0 r =

1 2

(6.63 ×10

−34

J ⋅ s 8.66 × 1013 Hz = 2.87 × 10 −20 J ×

)(

)

1 1.6 × 10−19 J/eV

= 0.179 eV

(b) The vibrational energy levels are given by: The lowest vibrational energy corresponds to ν = 0:

Eν = (ν + 1 )hf, 2 E0 = 1 hf 2

and

ν = 0,1, 2, ...

hf = 2E0

f = 8.66 × 1013 Hz

(1)

Determine f from Figure 37-17: Substitute for f and h and evaluate E0:

E0 =

1 2

(6.63 ×10

−34

J ⋅ s 8.66 × 1013 Hz = 2.87 × 10 −20 J ×

)(

)

1 1.6 × 10 −19 J/eV

= 0.179 eV

Substitute in equation (1) and evaluate hf:

hf = 2(0.179 eV ) = 0.358 eV

Molecules 1255

*47 •• Picture the Problem We can find the reduced mass of CO and the moment of inertia of a CO molecule from their definitions. The energy level diagram for the rotational levels for l = 0 to l = 5 can be found using ∆El ,l−1 = 2lE0 r . Finally, we can find the wavelength of the photons emitted for each transition using λl ,l−1 =

hc hc . = ∆El ,l−1 2l∆E0 r

(a) Express the moment of inertia of CO:

I = µ r02

where µ is the reduced mass of the CO molecule.

Find µ:

µ=

(12 u )(16 u ) = 6.86 u mC mO = mC + mO 12 u + 16 u

In Problem 39 it was established that r0 = 0.113 nm. Use this result to evaluate I:

**I = (6.86 u ) 1.66 × 10 −27 kg/u (0.113 nm ) = 1.45 × 10 −46 kg ⋅ m 2
**

2

(

)

The characteristic rotational energy E0r is given by: Substitute numerical values and evaluate E0r:

E0 r =

h2 2I

E0 r

(6.58 ×10 eV ⋅ s) (1.6 ×10 = 2(1.45 × 10 kg ⋅ m )

−16

2

−19

J/eV

−46

2

)=

0.239 meV

1256 Chapter 37

(b) The energy level diagram is shown to the right. Note that ∆El,l−1, the energy difference between adjacent levels for ∆l = −1, is

∆El ,l−1 = 2lE0 r .

(c) Express the energy difference ∆El.l−1 between energy levels in terms of the frequency of the emitted radiation: Because c = f l ,l−1λl ,l−1 :

∆El ,l−1 = hf l ,l−1

λl ,l−1 =

hc hc = ∆El ,l−1 2l∆E0 r

Substitute numerical values to obtain:

λl ,l−1 =

For l = 1:

(4.136 ×10

**eV ⋅ s 3 × 108 m/s 2596 µm = l 2l(0.239 meV)
**

−15

)(

)

λ1,0 = λ2,1 = λ3, 2 =

2596 µm = 2596 µm 1 2596 µm = 1298 µm 2 2596 µm = 865 µm 3

For l = 2:

For l = 3:

Molecules 1257

For l = 4:

λ4,3 = λ5, 4 =

2596 µm = 649 µm 4 2596 µm = 519 µm 5

For l = 5:

**These wavelengths fall in the microwave region of the spectrum.
**

*48 ••• Picture the Problem The wavelength resulting from transitions between adjacent harmonic oscillator levels of a LiCl molecule is given by λ =

2π c

ω

. We can find an

expression for ω by following the procedure outlined in the problem statement. The wavelength resulting from transitions between adjacent harmonic oscillator levels of this molecule is given by: From Problem 24 we have:

λ=

hc hc 2π c = = ∆E hω ω

(1)

U (r ) = −

ke 2 C + n , where ∆E is constant. r r

The Taylor expansion of U(r) about r = r0 is:

⎛ dU ⎞ U (r ) = U (r0 ) + ⎜ ⎟ (r − r0 ) ⎝ dr ⎠ r0 1 ⎛ d 2U ⎞ 2 + ⎜ 2 ⎟ (r − r0 ) + ... ⎜ dr ⎟ 2⎝ ⎠ r0

Because U(r0) is a constant, it can be dropped without affecting the physical results and because

1 ⎛ d 2U ⎞ 2 U (r ) ≈ ⎜ 2 ⎟ (r − r0 ) ⎜ dr ⎟ 2⎝ ⎠ r0

(2)

⎛ dU ⎞ ⎜ ⎟ = 0: ⎝ dr ⎠ r0

Differentiate U(r) twice to obtain: Because dU/dr = Fnet = 0 at r = r0:

d 2U ke 2 C = −2 3 + n(n − 1) n+2 2 dr r r 2 nC ke 0 = − n+1 + 2 r0 r0

1258 Chapter 37

Solving for C yields:

ke 2 r0n+1 ke 2 r0n−1 C= = nr02 n ⎛ d 2U ⎞ ke 2 n(n − 1) ke 2 r0n−1 ⎜ 2 ⎟ = −2 3 (n − 1) + n+2 ⎜ dr ⎟ r0 r0 n ⎝ ⎠ r0 = ke 2 (n − 1) r03

Substitute for C and evaluate

⎛ d 2U ⎞ ⎜ 2 ⎟ to obtain: ⎜ dr ⎟ ⎝ ⎠ r0

⎛ d 2U ⎞ Substitute for ⎜ 2 ⎟ in ⎜ dr ⎟ ⎝ ⎠ r0

equation (2): Because the potential energy of a simple harmonic oscillator is given 2 by U SHO = 1 mω 2 (r − r0 ) : 2 Solve for ω to obtain:

⎤ 1 ⎡ ke 2 2 U (r ) ≈ ⎢ 3 (n − 1)⎥ (r − r0 ) 2 ⎣ r0 ⎦

⎤ 1 1 ⎡ ke 2 2 2 mω 2 (r − r0 ) ≈ ⎢ 3 (n − 1)⎥ (r − r0 ) 2 2 ⎣ r0 ⎦

ω≈

(n − 1)ke2

mr03

Substitute µLiCl for m to obtain:

ω≈

(n − 1)ke2

mLi mCl 3 r0 mLi + mCl

(3)

2

=

(n − 1)(mLi + mCl )ke

mLi mCl r03 U e (r0 ) U rep (r0 )

From Problem 24:

n=

(4)

Urep is related to Ue, Ed, and ∆E according to: The energy needed to form Li+ and Cl− from neutral lithium and chlorine atoms is: Ue(r0) is given by:

U rep = −(U e + Ed + ∆E ) ∆E = Eionization − Eelectron affinity

(5)

= 5.39 eV − 3.62 eV = 1.77 eV

Ue = −

ke 2 1.44 eV ⋅ nm =− r0 r0

Molecules

1259

Substitute r0 and evaluate Ue:

Ue = −

1.44 eV ⋅ nm = −7.13 eV 0.202 nm

Substitute numerical values in equation (5) and evaluate Urep: Substitute for Urep(r0) and Ue(r0) in equation (4) and evaluate n:

U rep = −(− 7.13 eV + 4.86 eV + 1.77 eV ) = 0.500 eV n= − 7.13 eV = 14.3 0.500 eV

Substitute numerical values in equation (3) and evaluate ω:

ω≈

(14.3 − 1)(6.941u + 35.453 u )(1.44 eV ⋅ nm )(1.60 × 10 −19 J/eV ) (6.941u )(35.453 u )(1.66 ×10 −27 kg/u )(0.202 nm )3

= 1.96 × 1014 s −1

Substitute numerical values in equation (1) and evaluate λ:

λ=

2π 3 × 108 m/s = 9.62 µm 1.96 × 1014 s −1

(

)

1260 Chapter 37

- Ism Chapter 41
- Ism Chapter 40
- Ism Chapter 39
- Ism Chapter 38
- Ism Chapter 36
- Ism Chapter 35
- Ism Chapter 34
- Ism Chapter 33
- Ism Chapter 32
- Ism Chapter 31
- Ism Chapter 30
- Ism Chapter 29
- Ism Chapter 28
- Ism Chapter 27
- Ism Chapter 26
- Ism Chapter 25
- Ism Chapter 24
- Ism Chapter 23
- Ism Chapter 22
- Ism Chapter 21
- Ism Chapter 20
- Ism Chapter 19
- Ism Chapter 18
- Ism Chapter 17

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