53 tayangan

Diunggah oleh Rathish Arumugam

- Molecular Spectroscopy of Acetylene and Methane
- problem set 2
- Cary UVVis
- Calculation of Thermodynamic Properties
- Heat, Jun 2011
- CHE554 Lect9 Fluorescence
- Dupuis 1989
- 96
- Molecular Orbital Theory
- Oleg L. Polyansky et al- Water on the Sun: Line Assignments Based on Variational Calculations
- Molecular Geometry and Bonding Theory
- Group Theory and its Application to Chemistry
- IR-Spectras-http.pdf
- Solutions ch05.doc
- Section 1_Structure and Bonding in Hydrocarbons (1)
- Basic UV
- Energy Bands
- Understanding Cosmetic Laser Surgery
- File dich_2
- nanosc2nc

Anda di halaman 1dari 29

University of Cambridge

Electronic Spectroscopy

2

3

A diatomic molecule may undergo electronic, vibrational and rotational transitions.

The Born-Oppenheimer approximation (“Since the energies of the various motions are

very different, motions of a diatomic molecule may be considered as independent”)

allows us to express the total molecular energy as:

Etotal ≈ Eelec + Evib + Erot

or equivalently using term values:

T ≈ Te + G(v) + F(J)

where Te is the electronic energy which depends only on the electronic configuration

and nuclear repulsion. A change in the total energy of a molecule (in wavenumbers) is:

Δεtotal = Δεelec + Δεvib + Δεrot cm-1

where the approximate orders of magnitude of the three quantities are:

Δεelec ≈ Δεvib x 103 ≈ Δεrot x 106

Vibrational changes thus produce a “coarse structure”, and rotational changes a “fine

structure” on the electronic transitions. Unlike in vibrational and rotational

spectroscopies, all molecules give electronic spectra.

Ignoring rotational changes, we have

Δεtotal = Δεelec + Δεvib cm-1

or

εtotal = εelec + (v + 1/2)ϖe – xe(v + 1/2)2 ϖe cm-1 (v = 0, 1, 2,…)

where ϖe is the equilibrium vibrational frequency expressed in wavenumbers and xe is

the anharmonicity constant. The lower energy states are marked with a double prime,

and the higher states by a single prime. The figure below shows the vibrational coarse

structure in an electronic transition from the ground state (v’ = 0), to a higher state. By

convention, X is used to denote the electronic ground state, and A, B, C etc. the excited

states in order of increasing energy. The electronic energy is measured from the bottom

of the respective potential energy curves, while the lowest molecular energy level is

offset upwards by the zero point energy of that vibration. In general v” ≠ v’.

4

Vibrational transitions occur providing the electronic transition dipole moment and the

Franck-Condon factors are non-zero. In the infrared, the selection rules for v arise from

the symmetry of the different vibrational wavefunctions, and are strictly Δv = ±1 for the

simple harmonic oscillator. For an anharmonic oscillator, this strict rule begins to break

down and overtones are allowed, albeit with rapidly declining intensity. For vibrational

transitions between different electronic levels, this rule breaks down completely and

there is now no longer any restriction on Δv, so that every v’ ← v” transition has some

probability, giving rise to many spectral lines. However, absorption spectra from the

ground state are much simpler: virtually all the molecules are in their lowest vibrational

state (v” = 0), so that the only transitions we observe are (0, 1), (0, 2), (0, 3) etc.

Note that the upper state is given first within the brackets. Each set of transitions in a

band is called a v’ progression, since the value of v’ increases by unity for each line in

the set. The lines in a band are closer together at high frequencies because of the

5

anharmonicity of the upper state vibrations, which causes vibration energy levels to

converge. Note that, in general, the spacings of vibrational energy levels in the two

electronic states are different.

To quantify:

Δεtotal = Δεelec + Δεvib. = (ε’ – ε”) +

+ [(v’ + 1/2)ϖe’ – xe’(v’ + 1/2)2 ϖe’ – (v” + 1/2)ϖe” – xe”(v” + 1/2)2 ϖe”]

cm-1

If a sufficient number (at least five) lines can be resolved in the band, the values of xe’,

ϖe’, xe”, ϖe” and (ε’ – ε”) can be calculated. Information on the excited electronic states is

particularly valuable, since such states are extremely unstable, and therefore short-lived.

The Deslandres table is a convenient means of verifying vibrational assignments. The

differences between rows and columns should be constant, corresponding to the energy

difference between a particular pair of vibrational levels in either the upper state (rows)

or the lower state (columns):

below. Vibrational wavenumbers are shown in bold, with the differences in plain

characters.

6

v” = 0 v” = 1 – 0 1 v” = 2 – 1 2 v” = 3 – 2 3

v’ = 0 64748 2143 62605 2117 60488 2090 58398

v’ = 1 – 0 1480 1480 1480 1480

1 66228 2143 64085 2117 61968 2090 59878

v’ = 2 – 1 1440 1440 1440 1440

2 67668 2143 65525 2116 63409 2090 61319

v’ = 3 – 2 1402 1402 1402 1402

3 69070 2143 66927 2117 64810 2090 62720

The vibrational lines in a progression are not of the same intensity. Intensities of the

vibrational bands are determined by three factors:

˜ coefficient).

(1) The intrinsic strength of the transition (the B

(2) The populations of the levels involved.

(3) The overlap of the vibrational wavefunctions (the Franck-Condon factor).

€ “Since electronic transitions occur very rapidly

The Franck-Condon principle states:

(≈ 10-15 s), vibration and rotation of the molecule do not change the internuclear distance

appreciably during the transition”. The intensity of a transition is greatest for the

largest of the vibrational wavefunctions. The figure shows the probability distribution

for a diatomic molecule. The nuclei are most likely to be found at distances apart given

by the maxima of the curve for each vibrational level.

potential energy diagram. Consider three distinct situations.

7

(1) If the internuclear distances in the upper and lower states are equal (re” ≈ r e’), the

most probable transition is (0, 0), as indicated by the vertical line in the figure below.

However, there is a non-zero probability of (1, 0), (2, 0), (3, 0) etc. transitions. The

successive lines will therefore have rapidly diminishing intensities.

(2) If the excited electronic state has a slightly larger nuclear separation than the ground

state (re” > re’), the most probable (and thus most intense) transition is (2, 0). The

intensities of the neighbouring transitions are lower.

(3) When the excited electronic state has a considerably larger nuclear separation than

the ground state (re” >> re’), the vibrational state to which the transition takes place

has a high v’ value. Further, transitions can occur to levels where the molecule has

energy in excess of its dissociation energy. From such states the molecule will

dissociate without any vibrations and, since the fragments which are formed may

take up any value of kinetic energy, the transitions are not quantized and a

continuum results.

8

The Franck-Condon factor can be derived quantum mechanically from the fact that the

intensity of any transition is proportional to the square of the transition dipole moment:

Mfi = ∫ Ψ*f µ Ψi dτN

where µ is the dipole moment operator and both Ψf and Ψi are functions of the electronic

and vibrational states of the upper and lower levels, Ψ e’v’ and Ψ e”v” respectively. The

rotational component of the total wavefunction is ignored at this stage.

Separating the dipole moment operator into electronic and a nuclear components:

µ = µe + µ N

and writing Ψe’v’ as Ψ e’Ψv’ (the Born Oppenheimer approximation), the transition dipole

moment becomes:

Mfi = ∫ ∫ Ψ*e’Ψ*v’(µe + µN)Ψe”Ψv” dτedτN

= ∫ Ψ*e’ µeΨe”dτe ∫ Ψ*v’Ψv” dτN

+ ∫ Ψ*e’Ψe”dτe ∫ Ψ*v’ µN Ψv” dτN

Note that, neglecting anharmonicity, vibrational wavefunctions within one electronic

state are orthogonal, but between different electronic states they are not. Since Ψ*e’ and

Ψe” are distinct electronic states (which are orthogonal), the second term is zero, and the

transition dipole moment can be written as:

Mfi = Relec v' v"

and

€

v' v" = ∫ Ψ*v’ Ψv” dτN

The intensity of the transition is proportional to Mfi2, and thus to v' v" 2, which is

the Franck-Condon factor, consistent with the classical approach.

€

Dissociation energy €

The figure below shows two ways in which electronic excitation can lead to dissociation.

The figure on the left describes the case for re” >> r e’. The dashed lines of the Morse

curve represent the dissociation of the normal and excited molecule, the dissociation

energies being Do’ and Do”. The total energy of the dissociation products from the upper

state is greater by an amount Eex than that of the products of dissociation in the lower

state. This is the excitation energy of the products of dissociation. The lower

wavenumber limit of the spectral continuum must represent just sufficient energy to

9

cause no more than dissociation. The dissociation products separate with zero kinetic

energy, and we have:

v˜ continuum limit = Do” + Eex cm-1

€ lead to an approximate value of D ”, and hence, since D ” + E is accurately

often o o ex

than one spectroscopic dissociation limit is found (corresponding to dissociation into

two or more different states of products), the separation between the excitation energies

often corresponds with the separations between only one set of excited states of the

atoms observed spectroscopically. This gives the nature and the energies of the excited

products.

When the internuclear distances in both states are such that transitions near to the

dissociation limit are of negligible probability, no continua appear in the spectra.

However, it is still possible to determine the dissociation energy by noting how the

vibrational lines converge. The separation between the neighbouring vibrational levels:

Δε = εv+1 – εv = ϖe[1 – 2xe(v + 1)] cm-1

This separation decreases with increasing v, and the dissociation limit is reached when

Δε tends to zero. The maximum value of v is vmax, where

ϖe[1 – 2xe(vmax + 1)] = 0

so that

vmax = (1/2xe) – 1

Since xe is of the order of 10-2, vmax is about 50.

10

The expression for the separation of vibrational levels given above does not apply

exactly at high values of v because higher order anharmonicity terms are then

significant. However, it is still possible to obtain the dissociation energy by using the

Birge-Sponer extrapolation, involving plotting Δε versus the vibrational quantum

number v. The plot is not a straight line, but by extrapolating it to Δε = 0 we obtain vmax,

while the area under the plot gives the dissociation energy directly.

To summarize, provided that transitions are assigned correctly, the two methods

available for the determination of the dissociation energies Do” and Do’ are:

(1) The Birge-Sponer extrapolation

(2) If the Morse potential is assumed to be correct, the equilibrium vibration

frequencies νe’ and ν e” and the anharmonicity constants v˜ exe’ and v˜ exe” can be

determined for the two levels using:

v˜ (v” = 1 ← v” = 0) = v˜ e” – 2 v˜ exe”

€ €

v˜ (v” = 2 ← v” = 1) = v˜ e” – 4 v˜ exe”

v˜e2 €

€ De = €

4 v˜e x e €

€ €

A minimum of five entries in the Deslandres table (the bordered region) is required for

the determination of the dissociation energies of both electronic states.

€

Rotational fine structure of electronic-vibrational transitions

If we ignore centrifugal distortion and use the Born-Oppenheimer approximation, the

total energy of a diatomic molecule is:

˜ J(J + 1)

εtotal = εelec + εvib + B cm-1

while changes in the total energy are

€

11

Δεtotal = Δ(εelec + εvib) + Δ[ B

and the wavenumber of a spectroscopic line corresponding to such a change is:

˜ J(J + 1)]

v˜ spect. = v˜ v’,v” + Δ[ B cm-1

€

where v˜ v’,v” represents the wavenumber of electronic-vibrational transitions.

The selection rule for J depends on the type of electronic transition which the molecule

€ €

undergoes. If both€ the lower and upper electronic states are 1Σ states (with no

€

electronic angular momentum about the internuclear axis, S = 0), the selection rule is:

ΔJ = ±1 only for 1Σ ↔ 1Σ transitions

whereas for all other transitions (provided that at least one of the states has S ≠ 0) the

rule is:

ΔJ = 0 or ±1

In the latter case there is an added restriction that a state with J = 0 cannot undergo a

transition to another J = 0 state: J = 0 ↔ J = 0 is not allowed. Once more conservation of

angular momentum can be used to explain these selection rules. However, for

electronic transitions bond orders are expected to change and thus bond lengths are

likely to be markedly different between different electronic states (e.g. CO). The

spreading out or bunching up of transitions which occurs in vibrational-rotational

spectra may thus be more marked for electronic transitions, and “band heads” now

become evident at low J. Frequently these are more visible in spectra than the band

origin, resembling Q branches in IR spectra.

Thus for transitions between 1Σ states, only P and R branches will appear, while for

other transitions Q branches will appear in addition. We have for the difference of the

two electronic states:

giving the P, R and Q branches as follows:

(1) P branch: ΔJ = –1, J” = J’ + 1

€ € ν˜ = v€

˜ – ( ˜

B ’ +

€

˜ ”)(J’ + 1) + ( B

B ˜’– B

˜ ”) (J’ + 1)2 cm-1

P v',v"

where J’ = 0, 1, 2,…

(2) R branch: ΔJ = +1, J’ = J” + 1

€ € € € € €

ν˜ R = v˜v',v" + ( B˜ ’ + B˜ ”)(J” + 1) + ( B˜ ’ – B˜ ”) (J’ + 1)2 cm-1

where J” = 0, 1, 2,…

These two equations can be combined into:

€ € € € €

€ ν˜ P,R = v˜v',v" + ( B˜ ’ + B˜ ”) m + ( B˜ ’ – B˜ ”) m2 cm-1

where m = ±1, ±2,… with positive m values for the R branch (ΔJ = +1) and negative

values for the P branch (ΔJ = –1). Note that m cannot be zero (as this would correspond

€ € € € € €

12

to J’ = –1 for the P branch), so that no line from the P and R branches appears at the

band origin, v˜v',v" . The figure shows the resulting spectra for ˜’< B

B ˜ ” and a 10%

˜ ’ and

difference in the magnitude of B ˜ ”.

B P branch lines appear at the low

wavenumber side of the band origin, and the spacing between the lines increases with

€ €

m. €

The R branch appears on the high wavenumber side, and the line spacing decreases

€ at which

rapidly with m. The point € the R branch separation decreases to zero is known

as the band head.

ν˜ Q = v˜v',v" + ( B˜ ’ – B˜ ”)J” + ( B˜ ’ – B˜ ”) J”2 cm-1

The Q branch lines lie on the low wavenumber side of the origin.

The

€ Fortrat € €

€ diagram € €

Rewrite the expressions for the P, R and Q lines with continuously variable parameters p

and q:

ν˜ P,R = v˜v',v" + ( B˜ ’ + B˜ ”) p + ( B˜ ’ – B˜ ”) p2

ν˜ Q = v˜v',v" + ( B˜ ’ – B˜ ”) q + ( B˜ ’ – B˜ ”) q2

Each equation represents a Fortrat parabola, where p takes both positive and negative

€ € € € € €

values, while q is always positive. The band head is clearly at the vertex of the P, R

parabola. € € the position

€ € We calculate € € of the vertex by differentiation:

˜’+ B

d ν˜ P,R /dp = B ˜ ” + (B

˜’– B

˜ ”) p = 0

13

or

˜’+ B

p = – (B ˜ ”)/2( B

˜’– B

˜ ”) for band head

˜’< B

If B ˜ ”, the band head occurs at positive p values (i.e. in the R branch). Conversely,

˜’> B

if B ˜ ”, the band head is found at negative p values (i.e. in the P branch). A 10%

€ € € €

˜ ’ and B

difference between B ˜ ” gives p = 11.

€ €

€ €

€ €

Predissociation

A phenomenon called predissociation arises when the Morse curves of a molecule in

two different excited states intersect, with one of the states being stable (with a

minimum on the energy curve), and the other continuous. Suppose a transition takes

place from some lower state into the vibrational levels shown bracketed on the left.

Now if a transition takes place into the levels labelled a, b or c, a normal vibrational-

electronic spectrum occurs, complete with rotational fine structure. Two such bands

14

appear on the left of the spectrum below. However, for a transition into the levels

labelled d, e or f, the molecule may “cross over” onto the continuous curve and

dissociate. Such transition (known as “radiationless transfer”) is faster than the time

taken by the molecule to rotate (ca. 10-10 s), but usually slower than the vibrational time

(ca. 10-13 s). Thus predissociation will occur before the molecule rotates (destroying the

rotational fine structure), while the vibrational structure is preserved. If the cross-over

is faster than the vibrational time, a complete continuum will be observed.

An atomic orbital is the space within which an electron belonging to the orbital spends

95% of its time. The orbital ψ is described by three quantum numbers: n, l and m (or lz).

The energy of the orbital also depends on electron spin. In molecular orbital theory

orbitals embrace two or more nuclei. The same rules: (1) lowest energy first; (2)

maximum of two paired electrons per orbital; (3) parallel spins in degenerate orbitals,

apply to the filling of molecular orbitals. In the LCAO theory, the approximate shape of

molecular orbitals is made up by taking sums and differences of the atomic orbitals. For

the hydrogen molecule we have the sum:

ψ H 2 = ψ1s + ψ1s

This bonding orbital (called 1sσ, as it is produced from two s atomic orbitals) is a simple

symmetrical ellipsoid. It does not change sign upon inversion about the centre of

€

symmetry, which is marked by the subscript g (German gerade = even). The orbital is

thus known as 1sσg.

The difference:

ψ H 2 = ψ1s − ψ1s

In this antibonding orbital (called 1sσ∗) the charge is concentrated outside the nuclei,

which repel one another. This orbital does change sign upon inversion, which is

€

marked by the subscript u (German ungerade = odd). It is thus known as 1sσu*.

15

The energies of the two s orbitals depend on the internuclear distance as shown below.

Using the same procedure we obtain the two 2pσ orbitals by combining atomic 2p z

orbitals:

16

When two 2py orbitals combine, the result is as follows:

The figure below shows the various orbitals in order of increasing energy. For light

diatomic molecules, such as Li2, there is considerable overlap and interaction between

2pπu, 2pσg, and 2sσu* orbitals. For H2 this overlap does not occur, so that the two cases

are considered separately.

17

Hydrogen, H2. In the ground state there are two 1s electrons occupying the molecular

1sσg orbital with opposing spins. Their energy is lower than in two separate atoms, so

that the molecule is stable.

Helium, He2. There is a total of four electrons. Only two can go to 1sσ g, the others

would have to go to 1sσ u*. However, since more energy would be absorbed by the

former than evolved by the latter, the molecule is unstable.

Nitrogen, N2. Given a total of 14 electrons, omitting the asterisks, the configuration is:

1sσg21sσu22sσg22sσu22pσg22pπu4

1sσg2 and 1sσu2 as well as 2sσg2 and 2sσu2 contributions cancel each other, and we are left

with six electrons, in bonding 2pσg and 2pπu orbitals. This results in a triple bond.

Oxygen, O2. There are two more electrons than in the nitrogen molecule. The lowest

available orbital is the antibonding 2pπg*. Two electrons in this orbital cancel the

contribution from two electrons in 2pπu, and we are left with four electrons, i.e. a double

bond. Further, since the antibonding 2pπg* orbitals are degenerate, the electrons occupy

one each to satisfy electron repulsion. However, according to Hund’s rule, their spins

must be parallel. The unpaired electrons make the oxygen molecule paramagnetic.

The total energy of an electron depends mainly on its distance from the nucleus

(represented by the quantum number n) and the orbital and spin angular momenta

(quantum numbers l and s), and on the way these are coupled together (quantum

number j).

The same applies to electrons in molecules. However, in order to discuss the

components of the vector l we need to specify some reference direction called the z

direction. The angular momentum of a diatomic molecule is referenced to the

internuclear axis. Thus, l can be thought of as precessing about the internuclear axis,

but with a well defined component (in units of h) along it. The direction of the angular

momentum along the internuclear axis does not affect the overall energy, so that for

ml > 0 there is a degeneracy of two.

When referring to molecules, the equivalent Greek symbols are used, lower case for

individual electrons, upper case for the sum over the molecule. Thus, the angular

momentum of electron i along the internuclear axis is λi (i.e. σ electrons have λ = 0, π

electrons λ = 1 etc.), and the total molecular orbital angular momentum is:

i i

€ €

18

The same argument applies to spin angular momentum, with the projection of spin

angular momentum along the inter-nuclear axis denoted Σ (equivalent to S in an atom).

This Σ is not to be confused with a Σ state, for which Λ = 0. Thus for a diatomic

molecule, the total angular momentum J (neglecting nuclear spin) is now the vector sum

of the orbital (Λ), spin (Σ) and rotational (R) angular momentum:

Note that the rotational angular momentum is perpendicular to the inter-nuclear axis

(since Iz = 0). The total angular momentum thus has a projection Ω (in units of h) along

the inter-nuclear axis. There are always 2S+1 spin components, where 2S+1 is the spin

multiplicity.

Each electronic state can thus be described by a term symbol of the form:

(spin multiplicity)

[Component of L](net angular momentum component)

2S+1

or ΛΩ

NO, which in its ground state has an electronic configuration …(2pσ)2(2pπ)4(2pπ∗), has a

single unpaired electron. Its spin multiplicity is thus 2 (a doublet state), and it has total

orbital angular momentum of 1 (an unpaired π electron). Its term symbol is thus 2Π, or

more completely 2Π1/2 or 2Π3/2, depending on whether the spin and orbital angular

momentum components are parallel or anti-parallel. Clearly NO may also possess

19

rotational angular momentum, but this does not affect the term symbol which refers to

the electrons alone.

Two additional subscripts and superscripts are used in term symbols. The parity

indicates whether a wavefunction has the same sign (g) or the opposite sign (u) under

the process of inversion. Heteronuclear molecules do not have centres of inversion and

thus g and u are not applicable. The second parameter indicates the symmetry of the

electronic wavefunction with respect to reflection in a plane containing the nuclei, and

is applied only to Σ wavefunctions. If an electronic orbital wavefunction is symmetric

with respect to reflection (Σ+) it must, by the Pauli principle, be associated with an anti-

symmetric electron spin wavefunction, and vice-versa.

For example, the ground state electronic configuration of O2 is …(2pσ g)2(2pπu)4(2pπ∗g)2.

Hund’s rules indicate that the lowest energy state is the triplet (which is symmetric in

−

spin), and the term symbol is thus 3 Σ g .

€ orbital momentum spin total

momentum momentum

atoms

single electron l (symbol s, p, d for l = 0, 1, 2,…) s j

single electron

(z-component) lz sz jz

several electrons L (symbol S, P, D for L = 0, 1, 2,…) S J

several electrons

(z-component) Lz Sz Jz

molecules

single electron l s ja

single electron λ (symbol σ, π, δ for λ = 0, 1, 2,…) σ ω

(axial component)

several electrons L S Ja

several electrons Λ (symbol Σ, Π, Δ for Λ = 0, 1, 2,…) Σ Ω

(axial component)

20

There are two electrons. We thus expect to find singlet and triplet states, depending on

whether the electron spins are paired or parallel. In the ground state both electrons are

in the same 1sσg orbital, and must form a singlet state. We have λ1 = λ 2 = 0 and Λ = 0:

the state is thus 1Σ. We also specify the orbital geometry: since both electrons are in the

same orbital, we write 1Σg. Finally, since the wavefunction of the electron is unchanged

upon reflection in the plane of symmetry, the full term symbol for the ground state of H2

is (1sσg)2 1Σg+.

We consider the three possible excited states: (1sσg2sσg), (1sσg2pσg) and (1sσg2pπu).

singlet states, S = 0. Both constituting orbitals are even and symmetrical, so we have

(1sσg2sσg) 1Σg+.

(1sσg2pσg). We have again a 1Σ state, since both electrons are σ, but the overall state is

now odd (a combination of an electron arising from an even 1s state with an electron

from an odd p state gives and overall odd state). Thus (1sσg2pσg) 1Σu+.

(1sσg2pπu). Now Λ = λ1 + λ2 = 1, since one electron is in a π state and one originates from

a 2p orbital, the overall state is (1sσg2pπu) 1Πu.

The energies of the three states are 1Σu+ < 1Πu < 1Σg+.

Similar states are obtained by excitation to 3s and 3p states, 4s and 4p states, etc. In

addition, for n = 3, 4,… electrons can also be excited to the nd orbital. In this case we

have for the energies: (1sσndδ) 1Σg+ < (1sσndπ) 1Πg < (1sσndδ) 1Δg.

21

Transitions between the various energy levels follow the selection rules:

1. ΔΛ = 0, ±1

This is rationalised in terms of conservation of angular momentum of molecule plus

photon which has a spin angular momentum of h. For ΔΛ = 0, rotational angular

momentum changes by one (ΔJ = ± 1). Thus transitions Σ ↔ Σ, Σ ↔ Π and Π ↔ Π,

etc. are allowed, but Σ ↔ Δ, for example, is not allowed.

2. ΔS = 0.

Transitions which change the multiplicity are weak for molecules formed of light atoms,

where spin-orbit coupling is small. For heavier atoms, spin-orbit coupling effects are

larger, and transitions for which ΔS ≠ 0 can be seen.

3. ΔΩ = 0, ±1.

Σ+ states can go only to into other Σ+ states (or to Π states), while Σ– can go only to Σ– (or

Π). Thus Σ+ ↔ Σ+ and Σ– ↔ Σ–

g ↔ u (where applicable).

Consider now some triplet states of molecular hydrogen (S = 1). Both electrons occupy

the same orbital, so that the state of the lowest energy will be either (1sσ g2sσg),

(1sσg2pσg) or (1sσ g2pπu). The first two are 3Σ states, and the third is 3Π. Following the

above selection rules, the order of the energies will be:

22

Note that, because of the ΔS = 0 selection rule, transitions between singlet and triplet

states are not allowed.

For CO, the allowed electronic electric dipole transitions are:

The O2 molecule

23

The only allowed electronic electric dipole transition from the ground state is B ← X.

As O2 is homonuclear, no vibration-rotation spectrum would be expected within the X

state. Thus O2 would not be expected to absorb at wavelengths longer than ~ 200 nm.

Given the shapes of the two potential energy curves, this absorption would be expected

to be very temperature dependent (stronger at higher temperatures).

Hückel molecular orbital theory has been used to obtain a semi-quantitative picture of

the π-electronic structure of a number of organic molecules. Radiative transitions may

occur between these different electronic states.

The non-bonding state, n, corresponds to the lone pairs of electrons on the oxygen atom.

In its electronic ground state the HOMO (the X state) is the n-state. Promotion of

electrons leads to A and a states etc. The lowest energy electron promotion is to the π*

state, leading to a π* ← n transition, which occurs at ~290 nm. The other transitions

shown occur at shorter wavelengths (higher energies), e.g. the σ* ← n occurs at 190 nm.

Consider a hydride H2A, where A is a polyvalent atom and the H–A bonds are at 90o to

one another. Two of the p orbitals of A are involved, leaving the third (“non-bonding”)

orbital unaffected. We label the bonding orbitals as a1 and a2. In the linear molecule we

encounter “orbital hybridization”, whereby atom A mixes its s orbital with one of its p

orbitals, forming two strong-bonding sp hybrid orbitals. In this configuration there are

24

now two non-bonding p orbitals, N 1 and N 2, and two bonding orbitals formed by

overlap between sp hybrids and hydrogen 1s, called b1 and b2. Given that the energy of

a non-bonding orbital is higher than that of a bonding orbital and that the sp orbital is

lower in energy than a p bonding orbital, we plot the energy changes for a smooth

transition from 90o to 180o bonding.

We see that (1) the energy of N1 remains constant; (2) the energy of the bonding orbital

a1 decreases as it passes over into the stronger b1 orbital; (3) bonding orbital a2 becomes

non-bonding N2, thus increasing in energy; (4) bonding orbitals b1 and b2 are formed by

absorption of the non-bonding s into a1; (5) 90o to 180o represent maxima and minima on

the energy curves.

Consider BeH2. Be has the electronic ground state configuration 1s22s2, with two outer

bonding electrons. Each hydrogen atom contributes a further electron, so that BeH2 has

four electrons to place into molecular orbitals. The most stable state will be for two

electrons to go into b1 and two into b 2, thus producing a linear molecule. However,

when the molecule is electronically excited, the next available orbitals for the excited

electron are N 2 or N1. With a configuration b12b21N21 the most stable state will be at a

bond angle α. Thus the excited state is bent.

Linear molecules such as CO2 and HC ≡ CH become bent on excitation.

25

Electronic spectra of polyatomic molecules are very complex and difficult to interpret.

However, the vibrational frequencies of a particular atomic grouping within a molecule,

such as CH3, C=O or C=C, are fairly insensitive to the nature of the rest of the molecule,

as are the bond length and dissociation energy. We may therefore, as an approximation,

discuss the spectrum of each bond in isolation. Such bonds are said to be “localized”. If

we recognize the lines from such a bond in the spectrum, we may assume that its

vibrational frequency gives a good estimate of the dissociation energy of the molecule.

We note that molecules can be investigated spectroscopically in their very short-lived

excited states.

Conjugated molecules are those in which there is an alternation of single and double

bonds along a chain of carbon atoms. The π molecular orbital energy level diagrams of

conjugated molecules can be constructed using a set of approximations suggested by

Hückel in 1931. In this approach, the π orbitals are treated separately from the σ

orbitals, and the latter form a rigid framework which determines the general shape of

the molecule. All the carbon atoms are treated identically.

The effect of bond conjugation is to shift the π* ← n absorption to lower energies. When

two isolated double bonds are brought into conjugation, both levels are shifted to give

bonding and anti-bonding orbitals:

The effect is that the LUMO π* orbital is shifted downwards, and the π* ← n absorption

shifts to lower energy. Repeated conjugation increases this effect. When sufficient

conjugation is present, the energy of the LUMO π* orbital is lowered to the point where

ν2 corresponds to the visible region of the spectrum (~500 nm rather than 290 nm), a

feature which is exploited in tuneable dye lasers.

26

The chromophore activity is due to an π* ← π transition, corresponding to absorption at

180 nm. When the double bond is part of a conjugated chain, the energies of the

molecular orbitals lie closer together, and the π* ← π transition moves to longer

wavelengths. It may even lie in the visible region if the conjugated system is long

enough.

An important example is the photochemical mechanism of vision. The retina of the eye

contains “visual purple”, a combination of a protein with 11-cis-retinal, which acts as a

chromophore and is a receptor of photons entering the eye. 11-cis-retinal itself absorbs

at 380 nm, but in combination with the protein the absorption maximum shifts to ca. 500

nm and tails into the blue. The conjugated double bonds are responsible for the ability

of the molecule to absorb over the entire visible region. They play another important

role: in its electronically excited state the conjugated chain can isomerize by twisting

about an excited C=C bond, forming 11-trans-retinal. The primary step in vision is

photon absorption followed by isomerization, which triggers a nerve impulse to the

brain.

27

Following the absorption of a photon, the processes which may occur are:

Re-emission. This is simply a reverse of absorption.

Fluorescence. The spontaneously emitted fluorescent radiation ceases immediately

after the exciting radiation is switched off. The initial radiation takes the molecule into

an excited electronic state. The excited molecule gives up its energy non-radiatively via

collisions with the surrounding molecules, thus going down the vibrational levels to the

lowest vibrational level of the electronically excited state. At that point, the

surrounding molecules may be unable to accept the larger energy difference needed to

lower the molecule to the ground electronic state. They may survive long enough to

28

during the collisions). The fluorescence spectrum has a vibrational structure

characteristic of the lower electronic state.

Phosphorescence. The initial radiation takes the molecule into an excited electronic

state. Because the energy curves of the singlet and triplet state cross one another, the

molecule may undergo intersystem crossing and become a triplet state. This happens

when the molecule contains a heavier atom, such as S, because the spin-orbit coupling is

then large. The molecule deposits its energy via collisions with the surrounding

molecules, but becomes trapped at the lowest vibrational energy level of the triplet. It

cannot radiate its energy, because return to the ground state is spin-forbidden.

However, the radiative transition is not totally spin-forbidden because of the spin-orbit

coupling, so that the molecule is able to radiate weakly.

29

- Molecular Spectroscopy of Acetylene and MethaneDiunggah olehlolcakes123
- problem set 2Diunggah olehapi-182809945
- Cary UVVisDiunggah olehMuhammad Rizki Ardiansyah
- Calculation of Thermodynamic PropertiesDiunggah olehdkchae0
- Heat, Jun 2011Diunggah olehemediage
- CHE554 Lect9 FluorescenceDiunggah olehprakush_prakush
- Dupuis 1989Diunggah olehSammy17
- 96Diunggah olehLucius Bomfim Filho
- Molecular Orbital TheoryDiunggah olehMuhammad Danish
- Oleg L. Polyansky et al- Water on the Sun: Line Assignments Based on Variational CalculationsDiunggah olehTreaxmeA
- Molecular Geometry and Bonding TheoryDiunggah olehAlmira Soliman
- Group Theory and its Application to ChemistryDiunggah olehDennis Michael
- IR-Spectras-http.pdfDiunggah olehalfian
- Solutions ch05.docDiunggah oleh신재호
- Section 1_Structure and Bonding in Hydrocarbons (1)Diunggah olehrachel
- Basic UVDiunggah olehHemant Gite
- Energy BandsDiunggah olehUr Love
- Understanding Cosmetic Laser SurgeryDiunggah olehAnishGorkhali
- File dich_2Diunggah olehTrần Hoa
- nanosc2ncDiunggah olehArshad Shaikh
- CRB, Electrical Enginering MaterialsDiunggah olehIrfan
- 3_25428_65Diunggah olehAhmed Zaghary
- Have Fundamental Constants Chan - Jonathan SarfatiDiunggah olehJeff Stutz
- The Photoelectric Effect (Notes)Diunggah olehChathumi Lelwala
- PhD.F09B 1ohei6dDiunggah olehrizal123

- Cool-roof-Historical-approach.pdfDiunggah olehRathish Arumugam
- 10.1.1.98.1782Diunggah olehRathish Arumugam
- Book1Diunggah olehRathish Arumugam
- Speed o MeterDiunggah olehRathish Arumugam
- AnnouncementDiunggah olehRathish Arumugam
- Abstract Sustain a BuildDiunggah olehRathish Arumugam
- sazgDiunggah olehRathish Arumugam
- Final Students SmallDiunggah olehRathish Arumugam
- PAS2050 Guide Cómo evaluar la huella de carbono bienes y serviciosDiunggah olehALBERTO GUAJARDO MENESES
- Baseline Study for Grid Emission Factor by PTM-DANIDADiunggah olehyogaanandh
- 06esim_02Diunggah olehRathish Arumugam

- Chapter 4 Gen Bio.pdfDiunggah olehmoni ohh
- Comparison of Properties of Ionic and Covalent CompoundsDiunggah olehDharline
- Reaction IntermediateDiunggah olehSiddarth Singh
- 2-ME-B@H-NEET-IP-QP-22-12-16Diunggah olehYASH
- Probelm set 1Diunggah olehapi-19824406
- 4-Copy of Chemical BondDiunggah olehTiwi Harjanti
- Brick_065_-_Bonding_-_Allotropes.pdfDiunggah olehWilliamPotash
- IGCSE Chemistry - Student GuideDiunggah olehn0tsew
- 1411FINALSAMPLE+KEYDiunggah olehKinal Patel
- BONDING (POGIL).pptxDiunggah olehKeeva Conor
- Intermolecular Forces EdexcelDiunggah olehKevin The Chemistry Tutor
- Lecture 1 & 2 Chemical BiologyDiunggah olehParth Mehra
- 1 grade 11 review answersDiunggah olehapi-363234558
- Chemistry 102Diunggah olehAvantiBadrinathan
- jmunitplanDiunggah olehapi-302258576
- ch21Diunggah olehGurumurthy Kalyanasundaram
- Chapter 8 PowerPointsDiunggah olehViren Patel
- SOL Review Part 5 Phases of MatterDiunggah olehUgur ASİT
- Chemistry Matters Ch07 Textbk ANSDiunggah olehZeneon
- Chemistry Module Form 4 Complete SetDiunggah olehDawana Nasuha
- chemical bondingDiunggah olehsatya176
- Chemistry : Notes Form 4Diunggah olehAzreena Rahim
- jipmer 2013 paperDiunggah olehKg Kg
- Chemistry Revision Pack - 2012Diunggah olehbogobon
- Timeline of Atomic StructureDiunggah olehprabhaentrance
- BPOCchapter2Diunggah olehJosiah Johnson
- Chapter 3-Chemical BondsDiunggah olehMarie Spencer Dunn
- standard 6 - bonding -- student notesDiunggah olehapi-236389111
- sdfasdfDiunggah olehMarman Fabro Anga-Angan
- O Level Chemistry Notes.pdfDiunggah olehDarren Khu Kuang Yau