Molecular Spectroscopy and Structure

by

Peter F. Bernath

Departments of Chemistry and Physics University of Waterloo Waterloo, Ontario Canada N2L 3G1

-215.1 INTRODUCTION 15.2 ROTATIONAL SPECTROSCOPY 15.2.1 Diatomics 15.2.2 Linear Molecules 15.2.3 Symmetric Tops 15.2.4 Asymmetric Tops 15.2.5 Spherical Tops 15.3 VIBRATIONAL SPECTROSCOPY 15.3.1 Diatomics 15.3.2 Linear Molecules 15.3.3 Symmetric Tops 15.3.4 Asymmetric Tops 15.3.5 Spherical Tops 15.3.6 Raman Spectroscopy 15.4 ELECTRONIC SPECTROSCOPY 15.4.1 Diatomics 15.4.2 Polyatomics 15.5 STRUCTURE DETERMINATION 15.6 REFERENCES

-315.1 INTRODUCTION Our understanding of rotational-vibrational-electronic (rovibronic) spectra of molecules is based on the non-relativistic Schrdinger equation [1], (15.1) The Born-Oppenheimer approximation is used to separate electronic and nuclear motion and then the nuclear motion is further assumed to be separable into vibrational and rotational motion, leading to the simple equations (15.2) and (15.3) For molecules with net electronic spin and net electronic orbital angular momentum, additional terms such as spin-orbit coupling need to be added to the Hamiltonian of equation (15.1). The manifold of energy levels described by equation (15.2) are connected by transitions as determined by selection rules. More generally [2], an absorption line between energy levels E1 and E0 is represented by Beers law (15.4) where I0 is the initial radiation intensity, F is the cross-section (in m2), N0-N1 is the population density difference (m-3) and R is the path length (m). The intrinsic line strength of a transition is thus measured by a cross-section, which is proportional to the square of a transition moment integral, i.e. (15.5) where p is a transition moment operator and A is the Einstein A factor for emission. Selection rules and line strengths are obtained by a detailed examination of equation (15.5).

15.2 ROTATIONAL SPECTROSCOPY All gas phase molecules have quantized rotational energy levels and pure rotational transitions are possible. A molecule can, in general, rotate about three geometric axes and can have three different moments of inertia relative to these axes. The moment of inertia about an axis is

-4defined as (15.6)

where mi is the mass of the atom i and riz is the perpendicular (shortest) distance between this atom and the axis. The internal axis system of a molecule is chosen to have its origin at the center of mass and is rotated so that the moment-of-inertia tensor is diagonal [2]. This is the principal-axis system for a rigid molecule. The three moments of inertia Ix, Iy and Iz can be used to classify molecules into four different types of tops: 1. Linear molecule (including diatomics), Ix = Iy ; Iz = 0, e.g. CO, HCCH. 2. Spherical top, Ix = Iy = Iz, e.g. CH4, SF6. 3. Symmetric top, Ix = Iy Iz, e.g. BF3, CH3Cl. 4. Asymmetric top, Ix Iy Iz, e.g. H2O, CH3OH. The internal molecular axes x, y, and z are labeled according to a certain set of rules based on molecular symmetry [3]. An additional labeling scheme is also used that is based on the size of the moments of inertia. In particular, the axis labels A, B, and C are chosen to make the inequality IA #IB # IC true. Thus molecular symmetry determines the x, y and z labels but it is the size of the moments of inertia that set the A, B and C labels. In terms of the A, B and C labels, it is conventional to classify molecules into five categories: 1. Linear molecules, IA = 0, IB = IC. 2. Spherical tops, IA = IB = IC. 3. Prolate symmetric tops, IA<IB=IC, e.g. CH3Cl. 4. Oblate symmetric tops, IA=IB<IC, e.g. BF3. 5. Asymmetric tops, IA<IB<IC. Underlying all of these considerations is the assumption that the concept of a molecular structure is useful. Floppy species such as Van der Waals molecules or molecules with internal rotors do not always have a well-defined molecular structure when zero-point motions are considered. Clearly all molecules have a hypothetical equilibrium structure, but vibrational motion even in the zero-point level can destroy the concept of a molecular structure with well-defined bond lengths and bond angles. Fluxional molecules are best handled using concepts based on permutation-inversion group theory [4].

-515.2.1 Diatomics For a rigid diatomic molecule in a 1E+ electronic state (no net spin or orbital angular momentum) the rotational energy levels are given by , (15.7)

where B is the rotational constant and J, the rotational quantum number, has values 0, 1, 2, ... The units of (15.7) are determined by the units chosen for B, which are generally cm-1, MHz or (rarely) J (joules). Various equations for B are:

B (joules) =

(15.8)

B (MHz) =

10-6 =

(15.9)

B (cm-1) = in which I, the moment of inertia, is defined by

(15.10)

(15.11) and the masses mA and mB are separated by a distance r. The reduced mass : of the AB molecule (15.12)

is conventionally calculated using atomic (not nuclear) masses [5]. The use of a single symbol B for three separate physical quantities (energy, frequency and wavenumber) is clearly confusing but is the spectroscopic custom. Thus spectroscopists talk about energy levels but locate them using cm-1 units. A real molecule is not a rigid rotor because the bond between atoms A and B can stretch at

-6the same time as the molecule rotates. As rotation increases, the centrifugal force stretches the bond, increasing r and decreasing the effective B value. The bond length also depends, in an average sense, on the vibrational state v. The non-rigid rotor energy level equation for vibrational state v is, Fv(J) = BvJ(J + 1) - Dv[J(J + 1)]2 + Hv[J(J + 1)]3 + Lv[J(J + 1)]4+ ... (15.13) where Dv, Hv and Lv are centrifugal distortion constants. The vibrational dependence of the rotation and distortion constants is parameterized by , , (15.14) (15.15)

where "e, $e and (e are vibration-rotation interaction constants, and the Be and De values refer to the extrapolated equilibrium values at the bottom of the potential energy curve. Much of the conventional notation for spectroscopic constants is based upon Herzbergs three books [6-8], the work of Mulliken [3] and recent updates [5]. Each vibration state, v, has an effective internuclear separation, rv, defined by the equations

(15.16)

and

(15.17)

There is a useful relationship (due to Kratzer [6]) for estimating the centrifugal distortion constant:

(15.18) where Te is the equilibrium vibrational constant, eq. (15.60). A typical potential energy curve is often approximated (for semi-quantitative work) as that for a Morse oscillator, viz. , (15.19)

-7in which De is the equilibrium dissociation energy, [not the equilibrium centrifugal distortion constant appearing in equation (15.14)]. For the Morse oscillator, the main vibration-rotation interaction term, "e, is given by the Pekeris relationship [6],

(15.20) with the vibrational constants Te and Texe given by equation (15.60). The selection rules for a pure rotational transition are )J = 1 so that the frequencies for a J + 1 7 J transition are given by vJ+17J = 2Bv(J + 1) - (4Dv - 2Hv)(J + 1)3 + 6Hv(J + 1)5 + ... (15.21)

Thus the pure rotational transitions are a series of lines separated by approximately 2B. Excited vibrational levels create a similar series of vibrational satellites near the main transitions for the v=0 vibrational level. The cross-section for an absorption transition E1 7 E0 is given by [2]

(15.22) and the Einstein A coefficient for emission is

(15.23a)

(15.23b) where g0 is the permittivity of the vacuum, M10 is the transition dipole moment and g(<-<10) is the normalized lineshape function. In the numerical expression for A (15.23b), is in cm-1 and M10 is in debye C m).

The most common lineshape functions (normalized) are Lorenztian (for pressure and natural lifetime broadening) and Doppler broadening [2],

(15.24)

-8-

(15.25)

where )<1/2 is the Lorentian full width at half maximum and )<D the Doppler full width at half maximum. A convenient formula for the Doppler width is given by

(15.26)

In the numerical formula (15.26) )<D and molecule in amu.

are in cm-1, T in K and M is the total mass of the

For pure rotational transitions of a diatomic molecule, the square of the transition dipole moment integral M10 is [6] (M10)2= :2 SJ = :2(J + 1) (15.27)

and the 2J + 1 M-degeneracy of each rotational level needs to be included so that the absorption coefficient " , eq. (15.4), for the J + 1 7 J transition becomes

(15.28)

In equations (15.27) and (15.28) : is the permanent dipole moment of the molecule and SJ(=J+1) is a Hnl-London factor (see below). Thus, for homonuclear molecules such as Cl2 : = 0 and there are no allowed pure rotational transitions. For emission work for the transition J + 1 6 J the expression for the Einstein A factor is

(15.29)

The dipole moment of a diatomic molecule can be measured by the application of an electric field. The Stark effect partly lifts the MJ rotational degeneracy and each level splits into J +1, |M J|components. The Stark effect adds the term [9,10]

(15.30)

-9to the usual energy level expression. This is a second-order Stark effect because it depends upon the square of the electric field, E, and the energy level expression is derived using second-order perturbation theory. The measurement of Stark splittings in rotational transitions is one of the primary methods for measuring dipole moments. We have ignored the possibility of a net electron spin and/or a net orbital angular momentum. If either one is present, all of the energy level expressions are modified and each rotational transition will have fine structure. For example, if a molecule has a single unpaired electron, S= (2E+ state), then all of the energy levels and transitions will be doubled [6]. The presence of nuclear spins in a molecule will also split the energy levels into components and hyperfine structure will appear in the rotational transitions. In general, a nuclear spin vector couple with the rotational angular moment , viz. , (15.31) will

to give a total angular moment . The hyperfine structure can split a line into a maximum of 2I + 1 components (J $ I) each labeled by an F value. The study of the fine and hyperfine structure of rotational transitions is often a complicated, but well understood, task [9,10,11]. 15.2.2 LINEAR MOLECULES The rotational energy level expressions for diatomic molecules apply directly to linear molecules in 1E+ electronic states. The only change is that each subscript v, e.g. in Bv, is to be interpreted as a collection of vibrational quantum numbers and there is the possibility of new effects for the excited vibrational states. Such an effect is R-type doubling [12], which adds a term

(15.32) to the energy level expression in the case of doubly-degenerate bending vibrational levels. The Rtype doubling constant q measures the splitting of the rotational line into two R-doublet components. It is the presence of vibrational angular momentum that is responsible for this effect.

The 3N-5 vibrational modes in a linear molecule also modify the vibration-rotation interaction terms and the expression for Bv becomes , where di is the degeneracy of the ith vibrational mode. (15.33)

-1015.2.3 SYMMETRIC TOPS Symmetric top molecules have an additional rotational quantum number K which measures the component of along the top (molecular symmetry) axis. Thus the rotational angular momentum vector has components along the top axis and along the laboratory z-axis. The rotational energy level expression for a rigid molecule is given by EJK = BJ(J + 1) + (A - B)Ka2 (prolate top) EJK = BJ(J + 1) + (C - B)Kc2 (oblate top) (15.34) (15.35)

with subscripts a and c added to K in order to distinguish the prolate and oblate cases. The rotational constants A, B and C are defined by analogy with eq. (15.8),

(15.36)

(15.37)

(15.38)

in energy units. The numerical formulae for B (equations 15.9 and 15.10) are also applicable for A and C. Each energy level defined by the quantum numbers J and K has a (2J + 1)-fold MJdegeneracy and a 2-fold K-degeneracy (K>0), in the absence of electric or magnetic fields. By custom the quantum number K is positive, with the symbol k occasionally being used when a signed quantum number is needed (i.e., K = |k|, k = -J, ..,0,..J). For a non-rigid symmetric top the energy level expression becomes Fv(J,K) = BJ(J + 1) - DJ [J(J + 1)]2 + (A - B) K2 - DKK4 - DJK J(J + 1) K2 + ...(15.39) for the prolate case and C replaces A in the oblate case. The centrifugal distortion constants DJ, DK, and DJK and the rotational constants, A, B and C also depend on the vibrational state by analogy with the diatomic case. The intensity of a pure rotational transition is proportional to the square of the permanent dipole moment, which (by symmetry) can only lie along the symmetry axis of the top. The selection

-11rules are )K = 0 and )J = 1, which result in rotational transitions spaced by approximately 2B. For the non-rigid molecule the rotational transition frequencies for the transition J+1, K 7 J, K are given by . (15.40)

Thus, centrifugal distortion causes each line to split into J + 1 components for K = 0, 1, .... J. Since each set of constants applies to a particular vibrational level, vibrational satellites can also arise from population in an excited vibrational level. The application of an electric field results in a lifting of the MJ degeneracy with an additional energy level term E(1), to first order:

(15.41)

The 2-fold K-degeneracy for K>0 results in a first order Stark effect with energy splittings directly proportional to the product of the electric field strength, E, and the dipole moment, :, for small fields. A good collection of dipole moments of molecules as determined by the Stark effect and other methods can be found in the Handbook of Chemistry and Physics [13]. 15.2.4 ASYMMETRIC TOPS There is no general energy level formula available for an asymmetric top molecule. The rigid rotor Hamiltonian (15.42) commutes with 2 and z in the laboratory coordinates system so that J and MJ remain good quantum numbers. The Hamiltonian , however, does not commute with the components of (a, b, c) in the molecular coordinate system. This means that the 2-fold K-degeneracy of the symmetric top is lifted and each J splits into 2J + 1 components. In the asymmetric top case each of these levels is labeled by an index J = J, ..., 0, ... -J (cf. k for a symmetric top) in order of decreasing energy. The energy levels of the asymmetric top are most easily derived using symmetric top basis functions, first deriving the matrix elements of and then diagonalizing to find the energy eigenvalues and eigenvectors. For each value of J, a (2J + 1) x (2J + 1) matrix results and the 2J + 1 eigenvalues are easily labeled by J. The J labeling scheme, however, is not as popular as one based on a correlation diagram between the energy levels of a prolate symmetric top and an oblate symmetric top. The degree of

-12asymmetry of a top is quantified by the asymmetry parameter 6 with

(15.43)

Values of 6 range from -1 for a prolate top (B = C) and +1 for an oblate top (A = B) with values near 0 for highly asymmetric tops. The correlation diagram is displayed as Figure 15.1 with prolate tops (J, Ka) on the left and oblate tops (J, Kc) on the right. The parameter 6 can be viewed as a continuous parameter with all asymmetric tops lying between these two extreme cases. The non-crossing rule is used to connect the energy levels, and the two limiting quantum numbers Ka and Kc serve to label each level. The relationship between the JJ and system of labels is J = Ka - Kc. Notice that Ka + Kc = J or J + 1. The energy levels for the rigid asymmetric top have exact analytical solutions for low values of J. A list of these energy levels for J = 0, 1, 2 and 3 are provided in Table 15.1. The energy levels for real molecules, however, require the addition of centrifugal distortion terms to the molecular Hamiltonian and are obtained by numerical solution of the resulting Hamiltonian matrices [10,11]. Fortunately, many asymmetric top molecules are close to either the oblate or prolate limits. The selection rules for asymmetric tops depend on the components (:a, :b, :c) of the permanent dipole moment vector, , along the a, b and c principal molecular axes. The selection rules can be divided into three general cases: 1. 2. 3. a-type transitions when :a 0, )Ka = 0 ( 2, 4, ... ), )Kc = 1 (3, 5, .... ) b-type transitions when :b 0, )Ka = 1 (3, ... ), )Kc = 1 (3, ... ) c-type transitions when :c 0, )Ka = 1 (3, 5, .... ), )Kc = 0 (2, 4 .... )

The transitions in brackets are weaker than the main transitions. A molecule of low symmetry can have :a :b :c 0 so that transitions of all three types can be found in its rotational spectrum. For very asymmetric tops, the pure rotational spectra have a very irregular appearance. We have ignored the complications of fine and hyperfine structure as well as internal rotor structure. Each vibrational level has a set of rotational constants whose vibrational dependence is parameterized by

(15.44)

-13(15.45)

(15.46)

with di the degeneracy of the ith mode. 15.2.5 SPHERICAL TOPS The energy levels of a rigid spherical rotor are given by F(J) = BJ(J + 1) (15.47)

Although this expression is identical to that for a rigid diatomic molecule, the degeneracy of each level is (2J + 1)2 rather than 2J + 1. There is a (2J + 1)-fold MJ-degeneracy and a (2J + 1)-fold Kdegeneracy because the spherical top molecule is quantized, like a symmetric top, in both the laboratory and the molecular coordinate systems. For a non-rigid spherical top, the K-degeneracy can be partly lifted so that cluster splittings of the energy levels can be seen [12]. Because its high degree of symmetry, a spherical top has no permanent dipole moment and thus no allowed pure rotational transitions. 15.3 VIBRATIONAL SPECTROSCOPY

A molecule must have a permanent dipole moment in order to have allowed pure rotational transitions. By contrast, a molecule needs to have its dipole moment change as it vibrates in order to have an allowed vibrational spectrum, i.e., vibrational spectra depend upon dipole moment derivatives. This condition is much less restrictive so that all molecules apart from homonuclear diatomics (which have both = 0 and ) have allowed vibrational spectra. For a polyatomic

molecule, however, not all of the 3N-6 vibrational modes (or 3N-5 for a linear molecule) will necessarily be infrared active. For a molecule of sufficiently low symmetry, such as water, the 3 vibrations all appear in the infrared spectrum. The classification of molecules using a set of symmetry operations requires the application of group theory [2,4,14] and cannot be succinctly summarized. We will use the results of this symmetry classification as labels for vibrational and electronic states [3]. It can be shown that these labels, which are based on the irreducible representations of the appropriate molecular point group, can be applied to the individual rotational, vibrational and electronic wavefunctions as well as to the overall product wavefunction, . (15.48)

-14It is not customary to use these labels for rotational energy levels and hence we have not done so. 15.3.1 DIATOMICS The potential energy curve for nuclear motion of a diatomic molecule can be approximated by a harmonic oscillator near the minimum, i.e. with the potential energy E = V(r) = k(r-re)2 , (15.49)

with k the force constant. The resulting classical vibrational frequency is

(15.50)

where : is the reduced mass (not the dipole moment!). The quantum mechanical energy levels are thus given as E = h<(v + ), using energy units. A more realistic potential energy curve is the three-parameter (De, re and $) Morse oscillator of eq. (15.19), that gives the vibrational energy levels, G(v) = Te(v + ) - Texe(v + )2 now customarily in cm-1 units, with (15.52) (15.51)

(15.53)

(15.54) In this case there is a single anharmonicity correction term Texe (which is always written as a single symbol). The vibration-rotation energy levels of the Morse oscillator (15.19) can be written as E(v,J) = Te(v + ) - Texe(v + )2 + Be J(J + 1) - D[J(J + 1)]2 - "e (v+) J(J + 1) + . . .,

(15.53)

in which Be, D and "e are given by equations (15.14), (15.18) and (15.20), respectively. Note that while the vibrational energy expression (15.52) is exact for the Morse oscillator, the rotational terms

-15appearing in equation (15.53) are not [9]. In equations (15.53) and (15.54) all of the spectroscopic constants, including the Morse $ parameter, are in cm-1 and the fundamental constants are in SI units. A Morse oscillator also has the dissociation energy De = Te2/(4 Texe). In the above equations, the symbol De is customarily used for both the dissociation energy and the equilibrium centrifugal distortion constant, relying on the context to distinguish between the two. Here in equation (15.53), the subscript e has been deleted for clarity. While large number of potential energy functions have been proposed, the Dunham form , (15.56)

with

(15.57)

and

(15.58)

is the most widely used. The vibration-rotation energy levels of the Dunham potential are given by the double sum E(v, J) = EYjk (v + )j [J(J + 1)]k. (15.59)

The Dunham coefficients Yjk can be related back to the Dunham potential parameters ai [9] and to the customary spectroscopic constants as follows: Y10 = Te Y01 = Be Y02 = -De Y03 = He The customary vibrational energy level expression is G(v) = Te(v + ) - Texe(v + )2 + Teye(v + )3 + Teze(v + )4 + .... (15.60) The relationship between potential parameters and spectroscopic constants contains some correction terms, first derived by Dunham, and additional terms are needed to account for the breakdown of the Born-Oppenheimer approximation [15]. Notice that the use of Dunham Yik constants avoids the confusion created by constants with the same symbol such as the equilibrium centrifugal distortion Y20 = -Texe Y11 = -"e Y12 = -$e Y30 = Teye Y21 = (e Y40 = Teze

-16constant and the dissociation energy (both De), as well as the customary negative signs in front of Texe, "e and De. The best collection of spectroscopic constants for diatomics remains the book by Huber and Herzberg [16]. A harmonic oscillator has selection rules )v = 1, which leads to the fundamental vibrational band v = 1 : 0 plus various hot bands, coresponding to v = 2 :1, 3 : 2, .... By definition, a hot band occurs between two excited vibrational levels. Vibrational bands can appear in absorption v = 1 7 0 or emission v = 1 6 0; it is customary to put the excited state quantum number first. Real molecules are anharmonic oscillators because the potential energy function contains cubic and higher order terms (15.56), and because the dipole moment is not simply a linear function of the internuclear separation, but rather has the form

(15.61)

A real diatomic molecule is thus both mechanically and electrically anharmonic. This anharmonicity allows overtone transitions to appear with )v = 2, 3, ... Each increase in )v results in a decrease in intensity of an order of magnitude (or more). In terms of the vibrational constants, a fundamental band occurs at )G = <1-0 = Te - 2 Texe + ..., a hot band with )v = 1 occurs at )Gv+ = <v+17v = Te - 2 Texe(v + 1) + ..., and the first overtone occurs at <2 70 = 2 Te - 6 Texe + ..., with )Gv+ defined as )Gv+ = Gv + 1 - Gv. (15.65) (15.64) (15.63) (15.62)

A simple heteronuclear diatomic molecule such as HCl has a fundamental vibration-rotation transition that occurs in the infrared region near 2900 cm-1. The rotational selection rules are )J = 1. Transitions are labeled by their )J = JN - JO = -3, -2, -1, 0, 1, 2, 3 values as N, O, P, Q, R, S and T, respectively. For electric dipole-allowed transitions, only )J = 1, 0, -1, (P, Q, R) are possible. However, in the case of HCl there is no net spin or orbital angular momentum so that )J = 0 transitions are absent. Multiphoton transitions, Raman transitions, magnetic dipole transitions and electric quadrupole transitions have the possibility of occuring with |)J|>1.

-17It is customary to label the upper energy level with a single prime and the lower with a double prime, and to write the upper level first. The fundamental 1-0 vibrational band of HCl thus has energy levels E(vN = 1, JN) = <1-0 + BN JN(JN + 1) E(vO = 0, JO) = BO JO(JO + 1) with <1-0 = Te - 2 Texe + .... called the vibrational band origin. The R branch lines ()J = +1) occur at <R(J + 17J) = <1-0 + 2BN + (3BN - BO)J + (BN - BO)J2, and the P branch lines ()J = -1) occur at <P(J - 17J) = <1-0 - (BN + BO)J + (BN-BO)J2, (15.69) (15.68) (15.66) (15.67)

when the effects of centrifugal distortion are ignored. If the quantity m = J + 1 for the R branch and m = -J for the P branch is defined then the two equations (15.68) and (15.69) can be combined as <P and R = <1-0 + (BN + BO)m + (BN - BO)m2. (15.70)

Indeed, all infrared bands can be represented by a higher order polynomial in m when centrifugal distortion is included. If BN . BO then the R and P branch lines are spaced by about 2B with a band gap of 4B near the origin because of the missing m = 0 line (Figure 15.2). 15.3.2 LINEAR MOLECULES The vibrational motion of linear molecules (like other polyatomics) is approximated by a set of independent normal modes. Each normal mode is represented by a simple harmonic oscillator so that the vibrational energy is given by a sum over the 3N-5 normal modes as

(15.71)

where each normal mode i has a frequency Li and a vibrational quantum number vi. Due to the degeneracy, the number of different vibrational frequencies can be less than 3N-5 and hence the sum is usually written in the form

-18, (15.72)

where di is the degeneracy of the ith mode and the sum is over the distinct vibrational frequencies. For example, CO2 has 4 normal modes but the bending modes are doubly degenerate so that there are only 3 fundamental frequencies corresponding to the symmetric stretch <1(Fg) at 1388 cm-1, the bending mode <2(Bu) at 667 cm-1 and the antisymmetric stretch <3(Fu) at 2349 cm-1. The infrared spectrum of CO2, however, contains strong <2 and <3 bands because <1 has no oscillating dipole moment and is thus forbidden. Degenerate vibrational modes have an additional complication because they have vibrational angular momentum angular momentum, in addition to the rotational angular momentum, now called . Thus the total , is the vector sum of rotational and vibrational contributions,i.e. . (15.73)

The vibrational angular momentum quantum number R can have values R= v, v-2, ... 1 or 0 for a degenerate bending mode with v quanta. Thus v = 0 has R = 0, v = 1 has R = 1, v = 2 has R = 2 and 0, v = 3 has R = 3 and 1, etc. Notice that all levels with R > 0 have a 2-fold degeneracy (associated with R), even though only *R* is used as a label. The complete energy level expression for the vibrational energy levels of a real anharmonic molecule is

(15.74)

where dr and ds are the degeneracies of the rth and sth mode, and t applies to degenerate modes with vibrational angular momentum. For CO2 this expression becomes

-19-

(15.75)

in which the six xijs and the g2 term account for the anharmonic behavior, and vibrational resonances are ignored. Indeed most molecules display interactions between vibrational modes that shift some of the energy levels away from the values predicted by eq. (15.75). These vibrational perturbations have been classified into various types such as Fermi resonance and Coriolis resonance interactions [12]. There is no convenient collection of vibrational frequencies of stable molecules other than the older work of Shimanouchi [17]. Jacox has compiled vibrational constants for transient polyatomics [18]. Linear molecules have two basic types of vibrational motion: parallel to the linear axis (z-axis) and perpendicular to the linear axis (in the xy-plane). Those parallel to the axis involve bonding stretching motions while those perpendicular involve bending motions. Stretching modes are thus called parallel bands and bending modes are called perpendicular bands because of the direction of the oscillating dipole moment. Parallel bands like the <3 mode of CO2 have rotational selection rules )J = 1 and have spectra identical to those of a diatomic like HCl. Perpendicular modes have rotational selection rules )J = 0, 1 and thus have P, Q and R branches. Ignoring the effect of the R-type doubling term, equation (15.32), results in equations (15.68) and (15.69) for P and R branches and <Q = <1-0 + (BN-BO)J(J+1) (15.76)

for the Q branch. The selection rule for vibrational angular momentum is )R = 1 and the R-doubling of the excited state rotational levels does not appear directly in the spectrum because the two nearly degenerate levels have opposite total parity. Each J level of the ground state thus connects to only one of the two R-doublets. A perpendicular band like <2 of CO2 thus has a strong Q branch piled up near the band origin in addition to the P and R branches. The additional possible complications of fine and hyperfine structure have been ignored. Polyatomic molecules, however, have one additional common feature that needs to be discussed: combination bands. For a collection of harmonic oscillators, the selection rule on vi is )vi = 1 and )vj=0 for all ji. Thus only fundamental bands can appear in a cold spectrum. For a real anharmonic molecule, overtones similar to those in the diatomic case can appear. Combination modes are similar to overtones in that two or more vibrational quanta can be exchanged but they can belong to different

-20modes. For example, anharmonicity allows the <1 + <3 and the <1 + <2 modes of CO2 to appear in the spectrum at 3716 cm-1 and 2076 cm-1, respectively. Note that in the CO2 case, the first overtone modes are all forbidden by symmetry although they can be located using Raman spectroscopy [7]. 15.3.3 SYMMETRIC TOPS The vibrational energy levels of a symmetric top are given, in general, by expressions (15.72) and (15.73) for linear polyatomics, although the number of modes is 3N-6 rather than 3N-5. Modes in symmetric top molecules can also be doubly degenerate and can have associated vibrational angular momentum. In many ways, linear polyatomic molecules are special cases of symmetric top molecules. There are two types of vibrational mode in a symmetric top, parallel and perpendicular, depending on the orientation of the oscillating dipole moment relative to the top axis. The case of parallel bands is relatively simple and will be discussed first. A typical prolate symmetric top molecule is CH3F. CH3F has six vibrational frequencies: <1(a1) at 2965 cm-1, the symmetric C-H stretch; <2(a1) at 1475 cm-1, the symmetric CH3 umbrella bend; <3(a1) at 1048 cm-1, the C-F stretch; <4(e) at 2982 cm-1, the antisymmetric C-H stretch; <5(e) at 1471 cm-1, the antisymmetric bend; and <6(e) at 1196 cm-1, the CH3 rock. The <1, <2 and <3 modes are parallel modes while <4, <5 and <6 are doubly-degenerate perpendicular modes. For the parallel modes the selection rules are )K=0, )J=0, 1 (except for K=0 when )J=1). Because these parallel symmetric top selection rules are very similar to those for a perpendicular transition of a linear molecule, the bands will be similar. The bands thus have simple P, Q, R branches although for the symmetric top each rotational line will show K-structure at high resolution. As in the pure rotational case, each rotational line will split into J+1 K-components because K=0, 1, ... J. The perpendicular case is much more complicated and is difficult to summarize. The doubly degenerate excited vibrational states are strongly split by a large first-order Coriolis interaction [12]. The rotational energy levels are given either as E=BJ(J + 1) + (A-B)Ka2 K 2A.Ka (prolate top) (15.77) or E=BJ(J + 1) + (C - B)Kc2 K 2C.K (oblate top) (15.78)

where . is a Coriolis coupling constant. The vibrational angular momentum is now . units along the top axis and . need not be an integer (unlike the linear molecule case where the projection is R, with R integral). This large Coriolis splitting strongly shifts the K-structure associated with the perpendicular selection rules )J = 0, 1 and )K = 1. This results in widely shifted sub-bands, with each sub-band associated with a particular KN 7 KO transition and having a P, Q and R branch. The sub-band origins [7] are located at <sub = <1-0 + [AN(1-2.)-BN] 2 [AN(1-.)-BN]K + [(AN - BN) - (AO - BO)]K2 (15.79)

-21for K + 1 7K (+ sign) and K - 1 7 K (- sign) for the prolate top. The K sub-bands are thus approximately spaced by 2[A(1-.)-B]. The usual expressions (15.68), (15.69) and (15.76) for P, Q and R branch lines hold approximately for each sub-band. Depending on the magnitudes of A, B and . these perpendicular bands can have well-separated sub-bands or a massively congested appearance with strongly overlapping sub-bands. The absorption line intensities are given by the general expression eq. (15.22) but the transition moment factor needs to be evaluated for the symmetric top. In particular, , (15.80)

where SJK is a rotational line strength factor called a Hnl-London factor and :10 is to be interpreted as a vibrational transition dipole moment, rather than the permanent dipole moment as in the pure rotational case. A collection of infrared band strengths of molecules can be found in the book edited by Rao and Weber [19]. The Hnl-London factors SJK are provided in Table 15.2 for the 9 different JN KN 7 JO KO cases. The absorption coefficient " for the E1 7E0 transition is then given by

(15.81)

where the degeneracy factors in the upper (d1) and lower (d0) states need to be included together with the line shape function g(<-<10). If the upper state is unpopulated then N1 . 0. For a symmetric top the degeneracy factors are 2J + 1 for K = 0 and 2(2J + 1) for K > 0. Note also that the effects of nuclear spin are not included in equation (15.81). For emission the expression for the Einstein A coefficient for emission from level 1 is . (15.82)

These Hnl-London factors and the intensity expressions are very useful in that they can be used for diatomics, linear molecules and symmetric tops for pure rotational, vibrational and electronic transitions. The quantum number K can be interpreted as the projection of any angular momentum along the symmetry axis. For example, for pure rotational transitions of diatomic and linear molecules in 1E+ electronic states OKO = 0, O)KO = 0 and )J = +1 so that S = J + 1, in agreement with equation (15.27). Similarly, pure rotational transitions of symmetric tops have )K = 0, )J = +1. For infrared transition of diatomic molecules in 1E+ electronic states OKO = 0, O)KO = 0, and )J = 1 so that SJ = J+1 in the R branch and SJ = J in the P branch. For linear polyatomics the intensity expressions for parallel transitions are the same as for diatomics. For fundamental perpendicular transitions, however, R = 1 = OKO in the excited state and R = 0 = OKO in the ground state. Thus the first column with )K = +1 applies and SJ = (J+2)/4, (2J + 1)/4 and (J-1)/4 for the P, Q and R branches, respectively. Notice that in this case the Q branch lines are about twice as intense as the P and R

-22branch lines. 15.3.4 ASYMMETRIC TOPS The vibrational energy levels of asymmetric tops are given by the general energy level expression (15.74). The symmetry of asymmetric tops is sufficiently low that degenerate vibrational levels and a resulting vibrational angular momentum does not occur. The energy level expression then simplifies to

(15.83)

There are thus 3N-6 distinct vibrational frequencies for asymmetric rotor molecules. These modes are allowed if they have an oscillating dipole moment. The rotational energy levels and line strengths of the asymmetric rotor are not given by analytical formulae. Energy levels and intensities are thus computed numerically by diagonalizing the asymmetric rotor Hamiltonian using symmetric top basis functions. Line intensities are computed numerically, based on the known Hnl-London factors that describe transition moment matrix elements between the symmetric top basis functions. The bands of an asymmetric top are classified by whether they have oscillating dipole moments in the a, b or c directions. Bands are a-type, b-type or c-type if they have transition dipole moments :a, :b or :c. These transition dipole moments are proportional to dipole moment derivatives in the a, b and c directions for the particular motion described by the normal mode in question. For example, in H2O the symmetry axis is the b-axis so the symmetric stretching motion and the bending motion are both b-type bands. The antisymmetric stretching motion, in contrast, gives an oscillating dipole moment along the a-axis which lies in the plane of the molecule and is perpendicular to the symmetry axis. The rotational selection rules for a -, b - and c-type transitions have already been given. In general, a molecule with sufficiently low symmetry can have a mode that has an oscillating dipole moment with components in a, b and c directions and thus all three types of transitions will be found in this band. In general, asymmetric rotor bands have a very complex appearance. However, if the molecule is close to a symmetric rotor (i.e., *6*.1) then the bands will look like parallel or perpendicular (with .=0) bands of the corresponding symmetric top. 15.3.5 SPHERICAL TOPS Because of their high symmetry, spherical tops always have some degenerate vibrational modes and the full vibrational energy level expression (15.74) applies. Only triply degenerate fundamental vibrational modes are infrared active. For example, CH4 has 4 vibrational frequencies: <1 (a1) at 2914 cm-1, the symmetric C-H stretch; <2 (e) at 1526 cm-1, the doubly degenerate bend, <3 (t2) at 3020 cm-1, the antisymmetric C-H stretch and; <4 (t2) at 1306 cm-1, the triply degenerate bend.

-23Only <3 and <4 appear strongly in the spectrum. The triple vibrational degeneracy of the allowed modes causes complications in the excited state energy levels [12]. There is a strong first order Coriolis effect that splits them into three components. The excited vibration-rotation energy levels are found at E+ = <1-0 + BJ(J + 1) + 2B.J E0 = <1-0 + BJ (J + 1) - 2B. EG = <1-0 + BJ (J + 1) - 2B. (J + 1) (15.84) (15.85) (15.86)

where <1-0 is the band origin and there are . units of vibrational angular momentum present. The rotational selection rule is )J = 0, 1 but no obvious tripling is present in the spectrum. This is because only the E+ levels are used for the P branch, E0 for the Q branch and EG for the Rbranch. The Coriolis effect is thus similar to that discussed for perpendicular bands of symmetric tops. At low resolution, spherical top bands have a P Q R structure similar to a perpendicular band of a linear molecule or a parallel band of a symmetric top. At higher resolution, however, cluster splittings appear in the lines and they require a surprisingly sophisticated theory [20] to account for their magnitude. 15.3.6 RAMAN SPECTROSCOPY So far no mention has been made of the Raman effect and other light scattering phenomena. When the non-resonant interaction of radiation with a molecule occurs, the scattered photon usually has the same energy as the incident photon (Rayleigh scattering). However, the scattering event can be inelastic and the molecule will therefore be left in a different vibrational, rotational or electronic state. This phenomenon is the Raman effect [7, 21, 22] and it has a typical scattering efficiency of 10-5. Although the Raman effect is very weak, the availability of high-power lasers has made observations routine. A Raman spectrum is obtained by measuring the energy lost (or gained) by the scattered photon. The Raman effect is particularly useful for measuring the vibrational frequencies of large molecules in condensed phases. Modern Raman spectroscopy is limited usually by the presence of trace amounts of fluorescent impurities in the sample. The selection rules for the Raman effect are different those that govern the normal dipolar interaction of radiation and matter. The transition operator, c.f. equation (15.5), involves matrix elements of the molecular polarizability tensor rather than the dipole pole moment (vector) operator [22]. This difference makes the selection rules for the Raman effect similar to those for two photon spectroscopy [23]. For example, the rotational selection rules for the vibration-rotation Raman spectrum of HCl are )J = 0, 2 rather than the )J = 1 dipole selection rules. For molecules like CO2 that have a center of inversion symmetry, the infrared active modes are Raman inactive and vice versa. Raman spectroscopy thus has complementary selection rules to ordinary infrared spectroscopy

-24and different intensities for the vibrational modes. The vibrational frequencies of molecules are mainly deduced from infrared and Raman spectra as well as from vibronic transitions (section 15.4). Vibrational frequencies vary from molecule to molecule, but certain regularities are obvious. In particular, certain types of chemical bonds and functional groups have characteristic stretching and bending frequencies. These characteristic group frequencies (Table 15.3[2,13]) are widely used for qualitative analysis in organic [24] and inorganic [25] chemical spectroscopy. The analysis of materials is the main practical application of vibrational spectroscopy. 15.4 ELECTRONIC SPECTRA

The electronic transitions of molecules show the greatest variety of all of the different types of spectra. This is largely because the spin and orbital angular momenta often change and the ground and excited states can have different geometries. In fact, transitions that change the symmetry of a molecule, such as linear to bent, are not uncommon. Changes in geometry, in addition to the necessity for considering effects such as spin-orbit and spin-rotation coupling, make the study of electronic spectra particularly complicated. Electronic transitions have associated vibrational and rotational structure. A particular rovibronic transition occurs at a line position < with < = Te + GN(vN) + FN(JN) - GO (vO) - FO(JO) (15.87)

where G(v) and F(J) are the vibrational and rotational energy level expressions already discussed, and Te is the equilibrium transition energy between the states. This expression assumes, of course, that the electronic, vibrational and rotational energies can be separated and that the states involved are not subject to some sort of fast dynamical process. If one or both of the states is, for example, predissociated or preionized then the rotational or even the vibrational structure may be intrinsically unresolvable. If a state participates in a fast dynamical process (time scale ~)t) then the linewidth ()E or )<) derived from Heisenbergs uncertainty principle, )E )t $ or )< )t $ may be larger than the rotational or vibrational structure. 15.4.1 DIATOMICS The various angular momenta in a diatomic molecule are illustrated in Figure 15.3 [2,26]. The total angular momentum (exclusive of nuclear spin) is always labeled as , and is the vector sum of (15.89) (15.88)

-25nuclear rotational , electron orbital and electron spin . momenta, viz. (15.90)

The components of along the A-B axis are called 7, E and S, respectively. Each state 2S+1 is identified by the term symbol 7. The degeneracy of the 2S+17 term is (2S + 1)2 because of the 2S + 1 different possible values of E = S, S-1, ..... - S and the two fold *7* orbital degeneracy. For states with 7 = 0, i.e. 2S+1E+ or 2S+1EG states, the degeneracy is 2S + 1. The superscripts + or - are added in this case to distinguish between electronic states that are symmetric (+) or antisymmetric (-) with respect to reflection in the symmetry plane containing the nuclei. For homonuclear molecules an additional right subscript is added to the term symbol, 2S+17g or 2S+17u. If the electronic wavefunction is symmetric with respect to inversion of the electrons through the center of symmetry then g is used, while u identifies the antisymmetric case. Notice that the g or u symmetry of an electronic state applies only to homonuclear molecules and is not to be confused with the total parity of a rovibronic state. Total parity is the symmetry associated with the inversion of all particles (electrons and nuclei) through the origin in the laboratory coordinate system. This is a symmetry operation for all molecules because the energy levels depend only on the relative positions of the particles, which are unchanged by this operation [2]. Spin-orbit coupling is accounted for by considering the phenomenological spin-orbit Hamiltonian, SO = A that causes an energy level splitting of ESO = A 7 E. (15.92) , (15.91)

The effect of spin-orbit coupling is thus to lift the (2S + 1)-fold spin degeneracy for 7>0. Each spincomponent of a 2S+17 term is then labeled with S which is written as a subscript, 2S+17S . A two-fold degeneracy remains to account for the *S* possibilities. Note that, by custom, 7 and S are usually not signed but that G is signed to differentiate the 2S+1 spin components. The selection rules for allowed one-photon electric dipole-allowed transitions are: 1. 2. 3. 4. 5. )7 = 0, 1 )S = 0 (light molecules only) )S = 0, 1 Only E+ - E+, EG - EG but A - E+ and A - EG are both allowed. Only g : u for homonuclear molecules.

Each electronic transition has associated vibrational and rotational structure. In the simplest

-26approximation the transition vN, JN 7 vO, JO occurs at . (15.93)

The line absorption or emission intensities are given by the usual formulae, (15.22) and (15.23). In the case of singlet - singlet electronic transitions (i.e., 17N - 17O) the transition dipole moment is given by , (15.94)

in which is the square of the electronic transition dipole moment, SJ is the Hnl-London factor (Table 15.2) and q is the Franck-Condon factor defined by (15.95) The Franck-Condon factor is the square of the overlap of the vibrational wavefunctions between the two electronic states. The Hnl-London factors are taken from Table 15.2, with 7 used for K. Thus, a 1E+ - 1E+ electronic transition has the same rotational line strength factors as an infrared transition of a diatomic and a 1A-1E+ electronic transition has the same Hnl-London factors as a perpendicular vibrational transition of a linear polyatomic molecule. Notice that the electronic and rotational degeneracy is also required in the expression for the absorption coefficient or for the Einstein A factor. The Franck-Condon factor q is a measure of how the electronic transition dipole moment is divided up amongst the different vibrational bands. If the two electronic potential energy curves are very similar in shape then only the diagonal ()v=0) vibrational bands are allowed because of the orthogonality of the vibrational wavefunctions, i.e. because * < vN * vO > *2 = *ij . (15.96)

This is generally not the case, however, and off-diagonal vibrational bands with )v 0 are usually found. If the equilibrium bond length changes substantially then the rotational structure of each vibrational band in an electronic transition will appear very different from a typical infrared vibrational band. For most vibration-rotation transitions BN .BO but for electronic transitions BN is often very different from BO. This leads to the formation of band heads, where the rotational lines in a branch pile up and turn around [2,6]. The expressions for line positions in P, Q and R branches (ignoring centrifugal distortion) are

-27<P,R = <0 + (BN + BO) m + (BN - BO) m2 and <Q = <0 + (BN - BO) m(m + 1) (15.98) (15.97)

with m = J for the Q branch, m = JO + 1 for the R branch and m = -JO for the P branch. These secondorder polynomials in m are called Fortrat parabolas [6]. The band head forms at

(15.99) and the head (<H) origin (<0) interval is given by . (15.100)

The appearance of non-singlet bands is substantially more complicated and will not be discussed in detail [2,26]. Basically, all of the rotational lines split into 2S + 1 components but this splitting can be small (Hunds case (b)) or large (Hunds case (a)) depending on the size of the spinorbit coupling parameter, A [2, 26]. In addition, the 2-fold 7 (or S) degeneracy is lifted as the molecule begins to rotate and the effects of 7-doubling (or S doubling) must also be considered [26]. 15.5.2 POLYATOMICS The electronic spectroscopy of polyatomic molecules can be very complex. In contrast to diatomic molecules, each electronic state has 3N-6 (or 3N-5) vibrational modes to be considered. The vibrational band structure of an electronic transition is then given by . (15.101)

A vibrational band is specified by providing the two sets of vibrational quantum numbers or more compactly . The vibrational selection rule for allowed electronic transitions is )vi = 0, 1, ... for totally symmetric vibrations and )vi = 0, 2, 4... for non-symmetric vibrations. The intensities of each of these vibrational bands is approximately determined by the product of a set of Franck-Condon factors, one for each mode, so that (15.102) where is the magnitude squared of the electronic transition dipole moment. Simple formulae

-28such as eq. (15.102) are often not useful in a quantitative sense because of effects such as vibronic coupling, which prevent the separation of electronic and vibrational motion. Each vibrational band has associated rotational structure with energy levels described in simple cases by the formulae already discussed. The spectra of linear and symmetric tops can generally be classified as parallel and perpendicular depending upon the direction of the electronic transition dipole moments. For asymmetric tops the rotational selection rules can be classified as atype, b-type and c-type depending upon the orientation of the electronic transition dipole moment. The electronic transition dipole moment can be evaluated using the electronic wavefunctions as (15.103) where the integration is over the electronic coordinates. The possibility of geometry changes coupled with the large number of special effects such as vibronic coupling, Jahn-Teller effect and RennerTeller effect, to say nothing of fine structure and hyperfine structure, make electronic spectroscopy of polatomics a fascinating and challenging area of study [8]. 15.6 STRUCTURE DETERMINATION

There is a direct relationship between the three moments of inertia and the molecular geometry, which may be expressed by the relations (15.104) (15.105) (15.106) where the ith atom of mass mi is located at (ai, bi, ci) in the principal axis system. High resolution spectroscopy is thus one of the most reliable methods for determining molecular geometry [27]. The main problem is that molecules have at most three moments of inertia, which is usually inadequate to determine the large number of bond angles and bond lengths. The solution is to record the spectra of isotopically substituted molecules and to assume that the geometry is invariant. In general, each isotopomer provides an additional three moments of inertia so that spectra of a sufficient number of isotopomers must be recorded in order to determine uniquely the unknown geometrical parameters. In this procedure, the center-of-mass equations Emi with =0 (15.107)

= (ai, bi, ci) for each isotopomer are required as constraints.

-29Over the years, a number of techniques have been devised to determine molecular structure from moments of inertia [11,27]. Each method provides a slightly different set of bond lengths and bond angles. The three most important types of structures are designated as r0-, re- and rs-structures. The best structure is considered to be the equilibrium or re-structure. Within the BornOppenheimer approximation it is only the re-structure that does not change with isotopic substitution. For a diatomic molecule, it is easy to obtain an re-structure because, eq. (15.14) only two Bv values are required in order to extrapolate to a Be value, from which the re value can then be calculated. For a polyatomic molecule, it is more difficult to determine Ae, Be and Ce because, in general, 3N-6 "e values are required for each rotational constant, see eqs. (15.44), (15.45) and (15.46). For larger molecules this is a very difficult task because a rotational analysis is required for each infrared fundamental (or equivalent information from a rotational or an electronic spectrum must be available). If IAe, IBe and ICe values are not available then structures may be calculated using the vibrationally- averaged moments of inertia derived from A0, B0 and C0 via eqs. (15.36), (15.37) and (15.38). This is unfortunate because rigid-body relationships such as IC = IA + IB (15.108)

for a planar molecular are most nearly true for equilibrium moments of inertia. In fact, eq. (15.108) never holds exactly; it is used to define a moment of inertia defect via ) = IC - IA - IB (15.109)

for planar molecules. Empirically, planar molecules should all have small positive ) values. Any deviations from the value of ) expected empirically is taken as evidence for non-planarity or for fluxional behavior. Most structures of polyatomic molecules are r0-structures. Even for diatomic molecules, r0 values are reported if only a single B0 value is available. For a bond between two heavy atoms, r0 and re distances differ only slightly. For a hydrogen bond length, however, r0 and re values differ substantially. Deuterium bond lengths are also shorter than corresponding H bond lengths because of the significantly smaller zero point energy (by approximately bonded to a heavy atom. ) for a deuterium atom

These problems with r0-structures have led over the years to numerous schemes (some of them empirical) to estimate re-structures. The most important of these methods is based on isotopic substitution and results in rs-structures (s for substitution). The basic ideas are due to Kraitchman and Costain [11]. By using the moments of inertia of a parent molecule and of the molecule with a single isotopic substitution in Kraitchmans equations, the distance to the substituted atom from the center of mass can be calculated. Thus, by repeated single isotopic substitution for each atom, a full substitution (rs) structure is derived. The rs-structure is a better approximation to the re-structure and

-30normally the bond lengths obey the inequality r0 $ rs $ re. It is rare that a full substitution structure is determined because of the work involved in making and recording spectra of all possible singlysubstituted isotopomers. In addition, some elements have only a single stable isotope. Generally, a partial rs-structure is determined using Kraitchmans equations for some of the atoms and then the remaining geometrical parameters are derived using the moments-of-inertia equations, (15.104), (15.105) and (15.106), or the center-of-mass equation (15.107). There are some convenient collections of molecular structures including the Handbook of Chemistry and Physics [13], the paper of Harmony et al. [28] and the Landolt-Bornstein series [29]. More recently the MOGADOC database [30] has become available with structural data based mainly on electron diffraction and microwave spectroscopy. Additional spectroscopic data are available from various specialized databases including HITRAN [31], GEISA [32] and the JPL catalog [33]. Although bond lengths (and angles) like vibrational frequencies vary from molecule to molecule, some regularities can be discerned. For example, the bond length between a carbon and a hydrogen atom is about 1.09 D in all molecules. Bond lengths are also inversely correlated with bond order, which is defined (approximately) as the number of electron pairs in the chemical bond holding two atoms together in a molecule. The concept of an average bond length is therefore useful and a table of typical values [13, 34] is provided (Table 15.4). Actual molecules may have bond lengths that differ somewhat from the values reported in Table 15.4.

-3115.6 1. REFERENCES L. Cohen-Tannoudji, B. Diu and F. Lalo, Quantum Mechanics, vol. 1 and 2, (John-Wiley, N.Y., 1977). P.F. Bernath, Spectra of Atoms and Molecules, (Oxford UP, N.Y., 1995). R.S. Mulliken, J. Chem. Phys. 23, 1997 (1955). P.R. Bunker and P. Jensen, Molecular Symmetry and Spectroscopy, 2nd edition (NRC Press, Ottawa, 1998). I. Mills, T. Cvitas, K. Homann, N. Kallay and K. Kuchitsu, Quantities, Units and Symbols in Physical Chemistry, 2nd edition, (Blackwell, Oxford, 1993). G. Herzberg, Spectra of Diatomic Molecules, 2nd edition (Van Nostrand Reinhold, N.Y., 1950). G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules, (Van Nostrand Reinhold, N.Y., 1945). G. Herzberg, Electronic Spectra and Electronic Structure of Polyatomic Molecules, (Van Nostrand Reinhold, N.Y., 1967). C.H. Townes and A.L. Schawlow, Microwave Spectroscopy, (Dover, N.Y., 1975). H.W. Kroto, Molecular Rotation Spectra (Dover, N.Y., 1992). W. Gordy and R. Cook. Microwave Molecular Spectra, 3rd edition, (Wiley, N.Y., 1984). D. Papousek and M.R. Aliev, Molecular Vibrational-Rotational Spectra, (Elsevier, Amsterdam, 1982). D.R. Lide, editor, Handbook of Chemistry and Physics, 79th ed. (CRC Press, Boca Raton, FL, 1998). D.M. Bishop, Group Theory and Chemistry, (Dover, N.Y., 1993). J.F. Ogilvie, The Vibrational and Rotational Spectrometry of Diatomic Molecules, (Academic Press, San Diego, 1998). K.P. Huber and G. Herzberg, Constants of Diatomic Molecules, (Van Nostrand Reinhold, N.Y., 1979).

2. 3. 4.

5.

6.

7.

8.

9. 10. 11. 12.

13.

14. 15.

16.

-3217. 18. T. Shimanouchi, J. Phys. Chem. Ref. Data, 9, 1149 (1980) and references therein. M. Jacox, Vibrational and Electronic Energy Levels of Polyatomic Transient Molecules, J. Phys. Chem. Ref. Data, Monograph No. 3, 1994; VEEL Database (NIST, Gaithersburg, MD). M.A.H. Smith, C.P. Rinsland, V. Malathy Devi, L.S. Rothman and K.N. Rao, in Spectroscopy of the Earths Atmosphere and the Interstellar Medium, K.N. Rao and A. Weber, eds. (Academic Press, San Diego, 1992). J.P. Champion, M. Lote and G. Pierre in Spectroscopy of the Earths Atmosphere and the Interstellar Medium, K.N. Rao and A. Weber, eds. (Academic Press, San Diego, 1992). N.B. Colthup, L.H. Daly and S.E. Wilberley, Introduction to Infrared and Raman Spectroscopy, 3rd edition, (Academic Press, San Diego, 1990). D.A. Long, Raman Spectroscopy, (McGraw-Hill, London, 1977). W. Demtrder, Laser Spectroscopy, 2nd edition, (Springer, Berlin, 1996). L.J. Bellamy, The Infrared Spectra of Complex Molecules, (Chapman and Hall, London, 1975). K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th edition, (Wiley, N.Y., 1986).

19.

20.

21.

22. 23. 24.

25.

26.

H. Lefebvre-Brion and R.W. Field, Perturbations in the Spectra of Diatomic Molecules, (Academic Press, Orlando, FL, 1986). A. Domenicano and I. Hargittai, Accurate Molecular Structures, (Oxford UP, N.Y., 1992). M.D. Harmony, V.W. Laurie, R.L. Kuczkowski, R.H. Schwendeman, D.A. Ramsay, F.J. Lovas, W.J. Lafferty and A.G. Maki, J. Phys. Chem. Ref. Data, 8, 619 (1979). Landolt-Bornstein Numerical Data and Functional Relationships in Science and Technology, New Series, Group II (Springer, Berlin). J. Vgt, MOGADOC Database, Sekt. Spektren and Strukturdokumentation, University of Ulm, D-89069, Ulm, Germany. L.S. Rothman et al., J. Quant. Spectrosc. Radiat. Transfer, 60, 665 (1998). N. Jacquinet-Husson et al., J. Quant. Spectrosc. Radiat. Transfer, 59, 511 (1998).

27. 28.

29.

30.

31. 32.

-3333. H.M. Pickett, R.I. Poynter, E.A. Cohen, M.L. Delitsky, J.C. Pearson and H.S.P. Mller, J. Quant. Spectrosc. Radiat. Transfer, 60, 891 (1998). S.R. Radel and M.H. Navidi, Chemistry, (West, St. Paul, MN, 1990).

34.

-34Table 15.1. Rigid Asymmetric Rotor Energy Levels for J = 0, 1, 2, 3 JJ 000 110 111 101 220 221 211 212 202 330 331 321 322 312 313 303 00 11 10 1-1 22 21 20 2-1 2-2 33 32 31 30 3-1 3-2 3-3 0 A+B A+C B+C 2A + 2B + 2C + 2[(B - C)2 + (A - C)(A - B)] 4A+ B +C A + 4B + C A + B + 4C 2A + 2B + 2C - 2[(B - C)2 + (A - C)(A - B)] 5A + 5B + 2C + 2[4(A - B)2 + (A - C)(B - C)] 5A + 2B + 5C + 2[4(A - C)2 - (A - B)(B - C)] 2A + 5B + 5C + 2[4(B - C)2 + (A - B)(A - C)] 4A + 4B + 4C 5A + 5B + 2C - 2[4(A -B)2 + (A - C)(B - C)] 5A + 2B + 5C - 2[4(A - C)2 - (A - B)(B - C)] 2A + 5B + 5C - 2[4(B - C)2 + (A - B)(A - C)] F(JJ)

-35Table 15.2. Hnl-London Rotational Line Strength Factors SJK )J = 1 )K = + 1 )K = 0 )K = -1

)J = 0

)J = -1

-36Table 15.3 Infrared Group Wavenumbers Group /CH H =C CH C/C C=C CC SH N=N C=O C/N CF CCl CBr CI 3020 2960 2050 1650 900 2500 H 1600 1700 2100 1100 650 560 500 C/CC 300 H C H 1450 H CH H 1000 =C H 1100 S=O /CH 1310 700 NH P=O 3350 1295 </cm-1 3300 Group OH </cm-1 3600

-37Table 15.4 Bond Lengths in Single Bonds H H C N O S F Cl Br I Multiple bonds Bond CCa C=C C/C CNa C=N C/N COa C=O C/O N/N
a

C 1.09 1.54

N 1.01 1.47 1.45

O 0.96 1.43 1.40 1.48

S 1.34 1.82 2.05

F 0.92 1.35 1.36 1.42 1.56 1.42

Cl 1.27 1.77 1.75 1.70 2.07 1.63 1.99

Br 1.41 1.94 1.79 1.72 2.27 1.76 2.14 2.28

I 1.61 2.14 1.97 1.87 1.91 2.32 2.47 2.67

0.74

Length/ 1.54 1.34 1.20 1.47 1.28 1.16 1.43 1.20 1.13 1.10

O=O 1.21 Single bonds, repeated for comparison purposes.

-38FIGURE CAPTIONS Figure 15.1 The correlation diagram and labeling of the rotational energy levels of an asymmetric top molecule. Figure 15.2 The vibration-rotation spectrum of a diatomic molecule such as HCl. Figure 15.3 Angular momenta in a diatomic molecule.