Grau de Química 102531 – Espectroscòpia Curs 2014-15

Spectroscopy
First Partial Exam – April 8, 2015 – Exam Model 1

Name: .............................................................................. NIU: ............................ Group: ..........

Please READ:
The exam consists of four different sections: (1) Section I, a test section worth a maximum of 14
points, (2) Section II, a multiple choice section worth a maximum of 36 points, and (3) Section III, a
problem section worth a maximum of 50 points. Section IV is an OPTIONAL multiple choice section,
worth a maximum of 10 points. Specific instructions and scoring details for each section are at the
header of each section. Maximum overall grade is 110 points, or 100 if Section IV is waived. Points in
excess of 100 will be lost before the global average of the topic.

DO NOT REMOVE THE STAPLES

Section I
Section I consists of 14 test questions. Possible answers are True, False, or Blank. Scoring
details: Every correct answer is worth +1 points, every incorrect answer –1 points, blank
answers are worth 0 points. Maximum score: 14 points. Answer in the “Full d’Examen” using
the following key: a=TRUE; b=FALSE; anything else is interpreted as BLANK.

1. When temperature tends to infinity the population of each of the two states of a two
energy level system tends to 0.5.
2. Doppler broadening is mainly important in solid samples.
3. The polarizability of a spherical object is anisotropic.
4. Population inversion is only obtained for two energy level systems at long pumping
times.
5. The line of maximum intensity (Jmax) of a given rotational spectrum can be shifted by
means of the working temperature.
6. The rotational spectrum of a given diatomic molecule will be shifted to higher
frequencies when going from the rigid to the non-rigid rotator model.
7. A tetrahedral (spherical) polyatomic rotor does not present rotational spectrum given
its null dipolar moment.
8. Linear polyatomic molecules have two different moments of inertia and the third
equal to 0.
9. At large displacements from the bond length (Re), the harmonic oscillator model
predicts better the elongation than the compression of the molecule.
10. The ZPE is independent of the oscillator model (harmonic/anharmonic) used to
compute it.
11. Vibrational overtones start at vibrational quantum numbers larger than 0.
12. The methane molecule contains three S4 axes.
13. Dihedral symmetry planes (σd) do not contain the principal symmetry axis.
14. S63 = i (e.g. think of staggered ethane).
 Section II
Section II consists of 12 mulltiple choice questions. Scoring Details: Every correct
c answer is
worth +3 points, every inccorrect answer –1 point, blank answers are worth 0 points.
Maximum score: 36 pointss. Answer in the “Full d’Examen” marking the th box with the
appropriate answer (a, b, c and
a d); anything else, including multiple answerss, is interpreted as
BLANK.

Re2Cl8]2- anion (in

15. Which of the followingg considerations about the symmetry of the [R
eclipsed conformation in
n the figure) are correct:

1) The principal axis of

o rotation is a C4, only containing the
two Re atoms
2) Belongs to the D4h symmetry
s point group
3) The molecule conttains two vertical and two dihedral
symmetry planes
4) The molecule has an inversion center but no improper
symmetry axes

a) 2, 3 and 4 b) 1, 2 c) 1, 2 and 3 d) none of the previous a), b) or c)

ollowing statements about the interaction of EM

16. Indicate which of the fo M radiation with a
two-energy level (1 and 2,
2 with E1 < E2) material system are correct:

1) The system reachess equilibrium when the rates of population (ind duced absorption)
and depopulation (sppontaneous + induced emission) of the ground sttate 1 balance.
oefficient A determines the rate at which state 2 is depopulated
2) Only the Einstein co
through Spontaneou us Emission.
3) The lower the frequ uency of a transition between 1 and 2, the higher
h the rate of
depopulation of statte 2 through spontaneous emission.
4) Temperature is a keyy parameter that influences the initial rates of th
he absorption and
emission processes taking
t place.

a) 1, 2 and 4 b) 1,
1 4 c) 3, 4 d) none of the previous a), b)
b or c)

17. In a spectrum we obserrve the transitions from the ground state of th he system to two
excited states A and B.B If the full-width at half-maximum (FWHM) of the peak that
corresponds to the tran nsition to the B state is two times larger than that of the peak
corresponding to the traansition to the A state, we can affirm that:

a) The lifetime of B is shorter

s than that of A.
b) The lifetime of A is shorter
s than that of B.
c) The energy of the trransition to A is two times the one of the transitio
on to B.
d) None of the previou us answers is correct.
18. Indicate which of the following statements about the rotational spectra of a mixture of
H35Cl and H37Cl are correct, when considering the rigid-rotor model:

1) A calculation of the rotational constants will show that Be (H37Cl) is smaller than Be
(H35Cl).
2) The intensity of the bands observed is independent of the relative proportions of the
two isotopologues.
3) The spacing between equivalent bands of each isotopologue increases with J.
4) A frequency downshift is observed for the heavier isotope due to its higher
centrifuge distortion.

a) 1, 2 b) 1, 2 and 4 c) 1, 3 d) none of the previous a), b) or c)

19. Indicate which of the following statements about the rotational spectra of a 1:1 mixture
of HCl (r = 1.279 Å) and CO (r = 1.128 Å) are correct:

1) Based on the bonding types, the rigid rotor will be as good model for HCl as for CO.
2) The most intense line (Jmax) is higher for HCl than for CO.
3) CO will give bands at higher energies than HCl.
4) The centrifugal distortion constant (D) is the same for both gases.

a) 1, 2 b) 3 and 4 c) 2 d) none of the previous a), b) or c)

20. Consider the scattering of microwave LASER light by a rotating fluorine molecule and
indicate which of the following statements are correct:

1) Stokes Raman lines arise from fluorine molecules increasing their rotational state in
two units.
2) Anti-Stokes Raman lines follow ΔJ = +2 as selection rule.
3) Anti-Stokes Raman lines will be slightly more intense than their Stokes counterparts.
4) The molecule will give Raman spectrum.

a) 3, 4 b) 1, 4 c) 1, 3 and 4 d) none of the previous a), b) or c)

21. Consider that the energy levels of a given motion of the O2 molecule are well described by
the following equation:
= ̅ + − ̅ +
Indicate which of the following statements are correct:
1) The considered motion corresponds to the anharmonic vibration of the O 2 molecule.
2) The O2 molecule does not have vibrational spectrum.
3) The wavenumber of a transition between the ground and a given excited vibrational
state is given by the expression ̅ − ̅ ( + ).
4) The first overtone is the most intense band.

a) 1, 2 b) 1 , 4 c) 2, 3 d) none of the previous a), b) or c)

22. Consider the rotation of the SF6 (octahedral) molecule and indicate which of the following
statements are correct:

1) The molecule is classified as a spherical rotor given that the three perpendicular
moments of inertia defined about its center of mass are not equivalent.
2) The molecule is classified as a symmetric rotor.
3) Low intensity rotational bands can be observed due to the weak dipolar moment
generated by centrifugal distortion.
4) No rotational bands are observed due to its zero dipolar moment.

a) 1, 4 b) 2, 3 c) 2, 4 d) none of the previous a), b) or c)

23. Indicate which of the following statements about LASERs is correct:

a) Two-energy level LASERs are the most common.

b) Small stimulated emission and population inversion are required for their generation.
c) Population inversion is easier to attain in energy states of high frequency.
d) None of the previous answers is correct.

24. Consider the following molecules and indicate which of the statements are correct:

A B C

1) Only one of the compounds does not have symmetry axis of rotation.
2) The three compounds contain an inversion center.
3) One of the molecules does not contain any symmetry element.
4) A belongs to the C2h symmetry point group.

a) 1, 4 b) 2, 3 and 4 c) 2, 4 d) none of the previous a), b) or c)

25. Considering the harmonic oscillator model and that the fundamental bands of HF and NO
appear at 12.4 x 1013 Hz and 5.63 x 1013 Hz, respectively, indicate which of the following
statements are correct:

1) The force constant of NO is of 1552 N/m.

2) The potential energy curve is more steeped in NO than in HF.
3) The first overtone of both compounds will be observed at 24.8x10 13 Hz (HF) and
11.26x1013 Hz (NO).
4) The fundamental bands of their respective heavier isotopes (N18O and DF) appear at
lower frequencies.

a) 1, 4 b) 3 and 4 c) 1, 2 and 4 d) none of the previous a), b) or c)

26. Which of the following statements on general principles of spectroscopy are correct?

1) The number of signals observed is normally less than the number of potential
transitions. This is because of the selection rules.
2) The intensity of a given band depends on the population of the starting quantum
level.
3) Reducing the temperature will cause the width of the band to increase.
4) The absorption observed is proportional to the optical path through the sample and
its concentration.

a) 1, 2 and 4 b) 2 and 4 c) 1, 3 and 4 d) all of them

Section IV – OPTIONAL

Section IV is OPTIONAL. It contains 7 multiple choice questions which refer to the areas of the
syllabus marked as “advanced”. Each right answer scores 3 points, a wrong answer scores -1,
and a blank answer 0 points. Answer in the “Full d’Examen” marking the box with the
appropriate answer (a, b, c and d); anything else, including multiple answers, is interpreted
as BLANK. The grade you obtain in this section will be scaled to a maximum of 10 points and
added to the rest of your scores in this exam. Note points in excess of 100 will be lost before
the average to obtain your final grade on the topic.

27. If the polarizability ellipsoid has two large and equal-length semiaxes, and a shorter third
semiaxis (e.g. shaped like a very thick round pizza…), then
a) Induced dipole moment will be closer to the shorter semiaxis
b) Induced dipole moment will be closer to the plane defined by the two equal semiaxes
c) Induced dipole moment will be directed parallel to the incident electrical field
d) None of a, b and c

28. A method to estimate the dissociation energy equates the latter to the area under the
plot of what magnitude as a function of the quantum number v?
a) The excitations of type v←0
b) The excitations of type v+1←v
c) The excitations of type v+1←0
d) No such method exists
29. In rovibrational spectroscopy, what is meant with a Rx line?
a) In the fundamental band, a transition where rotational state changes x+1←x
b) In the fundamental band, a transition where vibrational state changes x+1←x
c) In the fundamental band, a transition where rotational state changes x←x-1
d) In the fundamental band, a transition where vibrational state changes x←x-1

30. Concerning the Q band in standard IR rovibrational spectroscopy of diatomics, what is

true?
a) It is observed, always
b) It is observed, provided that the molecule is heteronuclear
c) It is not observed, because it would imply violating the Δv=±1 selection rule
d) It is not observed, because it would imply violating the ΔJ=±1 selection rule

31. If there is rotation-vibration interaction and anharmonicity is present, what is true of the
following statements on rovibrational spectroscopy?
a) R lines get more spread out, as do P lines.
b) R lines get closer together, as do P lines.
c) R lines get closer together and P lines get more distant among themselves
d) R lines get separated and P lines get closer together

32. In symmetric rotors the energy of a given allowed transition between rotational states is a
function of the initial state’s…
a) J, K and M quantum numbers
b) J and M quantum numbers
c) J and K quantum numbers
d) J quantum number

33. Consider rovibrational spectroscopy within the harmonic oscillator and rigid rotor models.
Under these circumstances, which of the rotational constants , and is the largest?
a)
b)
c)
d) The three constants are equal
Grau de Química 102531 – Espectroscòpia Curs 2014-15

Spectroscopy
First Partial Exam – April 8, 2015 – Exam Model 2

Name: .............................................................................. NIU: ............................ Group: ..........

Please READ:
The exam consists of four different sections: (1) Section I, a test section worth a maximum of 14
points, (2) Section II, a multiple choice section worth a maximum of 36 points, and (3) Section III, a
problem section worth a maximum of 50 points. Section IV is an OPTIONAL multiple choice section,
worth a maximum of 10 points. Specific instructions and scoring details for each section are at the
header of each section. Maximum overall grade is 110 points, or 100 if Section IV is waived. Points in
excess of 100 will be lost before the global average of the topic.

DO NOT REMOVE THE STAPLES

Section I
Section I consists of 14 test questions. Possible answers are True, False, or Blank. Scoring
details: Every correct answer is worth +1 points, every incorrect answer –1 points, blank
answers are worth 0 points. Maximum score: 14 points. Answer in the “Full d’Examen” using
the following key: a=TRUE; b=FALSE; anything else is interpreted as BLANK.

1. S63 = i (e.g. think of staggered ethane).

2. Dihedral symmetry planes (σd) do not contain the principal symmetry axis.
3. The methane molecule contains three S4 axes.
4. Vibrational overtones start at vibrational quantum numbers larger than 0..
5. The ZPE is independent of the oscillator model (harmonic/anharmonic) used to
compute it.
6. At large displacements from the bond length (Re), the harmonic oscillator model
predicts better the elongation than the compression of the molecule.
7. Linear polyatomic molecules have two different moments of inertia and the third
equal to 0.
8. A tetrahedral (spherical) polyatomic rotor does not present rotational spectrum given
its null dipolar moment.
9. The rotational spectrum of a given diatomic molecule will be shifted to higher
frequencies when going from the rigid to the non-rigid rotator model.
10. The line of maximum intensity (Jmax) of a given rotational spectrum can be shifted by
means of the working temperature.
11. Population inversion is only obtained for two energy level systems at long pumping
times
12. The polarizability of a spherical object is anisotropic.
13. Doppler broadening is mainly important in solid samples.
14. When temperature tends to infinity the population of each of the two states of a two
energy level system tends to 0.5.
 Section II
Section II consists of 12 multiple choice questions. Scoring Details: Every correct answer is
worth +3 points, every incorrect answer –1 point, blank answers are worth 0 points.
Maximum score: 36 points. Answer in the “Full d’Examen” marking the box with the
appropriate answer (a, b, c and d); anything else, including multiple answers, is interpreted as
BLANK.

15. Which of the following statements on general principles of spectroscopy are correct?

1) The number of signals observed is normally less than the number of potential
transitions. This is because of the selection rules.
2) The intensity of a given band depends on the population of the starting quantum
level.
3) Reducing the temperature will cause the width of the band to increase.
4) The absorption observed is proportional to the optical path through the sample and
its concentration.

a) 1, 2 and 4 b) 2 and 4 c) 1, 3 and 4 d) all of them

16. Considering the harmonic oscillator model and that the fundamental bands of HF and NO
appear at 12.4 x 1013 Hz and 5.63 x 1013 Hz, respectively, indicate which of the following
statements are correct:

1) The force constant of NO is of 1552 N/m.

2) The potential energy curve is more steeped in NO than in HF.
3) The first overtone of both compounds will be observed at 24.8x10 13 Hz (HF) and
11.26x1013 Hz (NO).
4) The fundamental bands of their respective heavier isotopes (N18O and DF) appear at
lower frequencies.

a) 1, 4 b) 3 and 4 c) 1, 2 and 4 d) none of the previous a), b) or c)

17. Consider the following molecules and indicate which of the statements are correct:

A B C

1) Only one of the compounds does not have symmetry axis of rotation.
2) The three compounds contain an inversion center.
3) One of the molecules does not contain any symmetry element.
4) A belongs to the C2h symmetry point group.

a) 1, 4 b) 2, 3 and 4 c) 2, 4 d) none of the previous a), b) or c)

18. Indicate which of the following statements about LASERs is correct:

a) Two-energy level LASERs are the most common.

b) Small stimulated emission and population inversion are required for their generation.
c) Population inversion is easier to attain in energy states of high frequency.
d) None of the previous answers is correct.

19. Consider the rotation of the SF6 (octahedral) molecule and indicate which of the following
statements are correct:

1) The molecule is classified as a spherical rotor given that the three perpendicular
moments of inertia defined about its center of mass are not equivalent.
2) The molecule is classified as a symmetric rotor.
3) Low intensity rotational bands can be observed due to the weak dipolar moment
generated by centrifugal distortion.
4) No rotational bands are observed due to its zero dipolar moment.

a) 1, 4 b) 2, 3 c) 2, 4 d) none of the previous a), b) or c)

20. Consider that the energy levels of a given motion of the O2 molecule are well described by
the following equation:
= ̅ + − ̅ +
Indicate which of the following statements are correct:
1) The considered motion corresponds to the anharmonic vibration of the O 2 molecule.
2) The O2 molecule does not have vibrational spectrum.
3) The wavenumber of a transition between the ground and a given excited vibrational
state is given by the expression ̅ − ̅ ( + ).
4) The first overtone is the most intense band.

a) 1, 2 b) 1 , 4 c) 2, 3 d) none of the previous a), b) or c)

21. Consider the scattering of microwave LASER light by a rotating fluorine molecule and
indicate which of the following statements are correct:

1) Stokes Raman lines arise from fluorine molecules increasing their rotational state in
two units.
2) Anti-Stokes Raman lines follow ΔJ = +2 as selection rule.
3) Anti-Stokes Raman lines will be slightly more intense than their Stokes counterparts.
4) The molecule will give Raman spectrum.

a) 3, 4 b) 1, 4 c) 1, 3 and 4 d) none of the previous a), b) or c)

22. Indicate which of the following statements about the rotational spectra of a 1:1 mixture
of HCl (r = 1.279 Å) and CO (r = 1.128 Å) are correct:

1) Based on the bonding types, the rigid rotor will be as good model for HCl as for CO.
2) The most intense line (Jmax) is higher for HCl than for CO.
3) CO will give bands at higher energies than HCl.
4) The centrifugal distortion constant (D) is the same for both gases.

a) 1, 2 b) 3 and 4 c) 2 d) none of the previous a), b) or c)

23. Indicate which of the following statements about the rotational spectra of a mixture of
H35Cl and H37Cl are correct, when considering the rigid-rotor model:

1) A calculation of the rotational constants will show that Be (H37Cl) is smaller than Be
(H35Cl).
2) The intensity of the bands observed is independent of the relative proportions of the
two isotopologues.
3) The spacing between equivalent bands of each isotopologue increases with J.
4) A frequency downshift is observed for the heavier isotope due to its higher
centrifuge distortion.

a) 1, 2 b) 1, 2 and 4 c) 1, 3 d) none of the previous a), b) or c)

24. In a spectrum we observe the transitions from the ground state of the system to two
excited states A and B. If the full-width at half-maximum (FWHM) of the peak that
corresponds to the transition to the B state is two times larger than that of the peak
corresponding to the transition to the A state, we can affirm that:

a) The lifetime of B is shorter than that of A.

b) The lifetime of A is shorter than that of B.
c) The energy of the transition to A is two times the one of the transition to B.
d) None of the previous answers is correct.

25. Indicate which of the following statements about the interaction of EM radiation with a
two-energy level (1 and 2, with E1 < E2) material system are correct:

1) The system reaches equilibrium when the rates of population (induced absorption)
and depopulation (spontaneous + induced emission) of the ground state 1 balance.
2) Only the Einstein coefficient A determines the rate at which state 2 is depopulated
through Spontaneous Emission.
3) The lower the frequency of a transition between 1 and 2, the higher the rate of
depopulation of state 2 through spontaneous emission.
4) Temperature is a key parameter that influences the initial rates of the absorption and
emission processes taking place.

a) 1, 2 and 4 b) 1, 4 c) 3, 4 d) none of the previous a), b) or c)

 Re2Cl8]2- anion (in
26. Which of the followingg considerations about the symmetry of the [R
eclipsed conformation in
n the figure) are correct:

1) The principal axis of

o rotation is a C4, only containing the
two Re atoms
2) Belongs to the D4h symmetry
s point group
3) The molecule conttains two vertical and two dihedral
symmetry planes
4) The molecule has an inversion center but no improper
symmetry axes

a) 2, 3 and 4 b) 1, 2 c) 1, 2 and 3 d) none of the previous a), b) or c)

Section IV – OPTIONAL

Section IV is OPTIONAL. It co
ontains 7 multiple choice questions which refer to the areas of the
syllabus marked as “advanced d”. Each right answer scores 3 points, a wrong answer scores -1,
and a blank answer 0 poin nts. Answer in the “Full d’Examen” marking the t box with the
appropriate answer (a, b, c and
a d); anything else, including multiple answeers, is interpreted
as BLANK. The grade you obttain in this section will be scaled to a maximumm of 10 points and
added to the rest of your sco
ores in this exam. Note points in excess of 100 will
w be lost before
the average to obtain your fiinal grade on the topic.

pectroscopy within the harmonic oscillator and rigid

27. Consider rovibrational sp r rotor models.
Under these circumstancces, which of the rotational constants , andd is the largest?
a)
b)
c)
d) The three constantss are equal

28. In symmetric rotors the energy

e of a given allowed transition between rottational states is a
function of the initial staate’s…
a) J, K and M quantum m numbers
b) J and M quantum nu umbers
c) J and K quantum nu umbers
d) J quantum number
29. If there is rotation-vibration interaction and anharmonicity is present, what is true of the
following statements on rovibrational spectroscopy?
a) R lines get more spread out, as do P lines.
b) R lines get closer together, as do P lines.
c) R lines get closer together and P lines get more distant among themselves
d) R lines get separated and P lines get closer together

30. Concerning the Q band in standard IR rovibrational spectroscopy of diatomics, what is

true?
a) It is observed, always
b) It is observed, provided that the molecule is heteronuclear
c) It is not observed, because it would imply violating the Δv=±1 selection rule
d) It is not observed, because it would imply violating the ΔJ=±1 selection rule

31. In rovibrational spectroscopy, what is meant with a Rx line?

a) In the fundamental band, a transition where rotational state changes x+1←x
b) In the fundamental band, a transition where vibrational state changes x+1←x
c) In the fundamental band, a transition where rotational state changes x←x-1
d) In the fundamental band, a transition where vibrational state changes x←x-1

32. A method to estimate the dissociation energy equates the latter to the area under the
plot of what magnitude as a function of the quantum number v?
a) The excitations of type v←0
b) The excitations of type v+1←v
c) The excitations of type v+1←0
d) No such method exists

33. If the polarizability ellipsoid has two large and equal-length semiaxes, and a shorter third
semiaxis (e.g. shaped like a very thick round pizza…), then
a) Induced dipole moment will be closer to the shorter semiaxis
b) Induced dipole moment will be closer to the plane defined by the two equal semiaxes
c) Induced dipole moment will be directed parallel to the incident electrical field
d) None of a, b and c