Molecular Orbital Theory

Club Alchemy Handout Molecular Orbital Theory

Name: _________________________ Prerequisites -

Class: _________

Date: __________

Able to appreciate the need for a model for atomic bonding Basic understanding of VSEPR and valence bond theory Understanding of the wave particle duality of electrons General understanding of the Schrdingers equation and the wavefunction

Introduction The failure of the VSEPR and valence bond theories prompted the formulation of a more advanced theory to explain bonding between atoms. The molecular orbital theory proposes that electrons of atoms are delocalized over the entire molecule. The VB theory instead proposes that electrons are confined to between the atoms in the bond. Superposition of Atomic Orbitals In MO theory, electrons in atomic orbitals are represented as wavefunctions. The wavefunction of the molecular orbital is then the sum of the atomic orbitals with a mixing coefficient ci, which can be determined numerically using the Schrdingers equation: = ci The same rules for AOs apply for MOs as well. Similar to electrons in AOs, electrons in MOs can be described using the Schrdingers equation, thus they too have a set of unique quantum numbers. AOs mix to form the same number of MOs, each containing a maximum of two electrons with opposite spins. Such orbitals are classified into bonding, anti-bonding and non-bonding orbitals. Question 1: Which rule states that no two electrons can have the same set of quantum numbers?

Bonding orbitals come from the superposition of two atomic wavefunctions which are in phase (see Fig. 1 below). The phase is represented by the + and - signs on the orbitals (and not the charge!). The constructive interference will result in a higher electron density between the atoms. This increase of electron density results in a greater shielding effect for the repulsion between the two nuclei. There is also electrostatic attraction between the electrons and the two positive nuclei. This makes the molecule more energetically stable than the individual atoms. As a result such orbitals will strengthen the bond. Anti-bonding orbitals come from the destructive interference of two atomic wavefunctions which are not in phase. Electrons in anti-bonding orbitals spend more
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time further from the nuclei than when they are in the separate atoms. This results in less shielding between the two positive nuclei and destabilizes the bond. Anti-bonding orbitals are typically marked with an *. Electrons in non-bonding orbitals spend most of their time around only one of the atoms and hence do not affect the bond strength (these orbitals can be seen in Fig 6 below). The bond order shows whether a bond can be formed between two atoms. It is calculated by Bond Order = (No. of Bonding Electrons No. of Anti-Bonding Electrons)/2 The bond order tells us about the stability of the bonding of 2 atoms. If the bond order is 0, there is no special preference for the bonded state over the unbonded state, thus atoms will just collide and bounce away from each other. Conversely if the bond order is greater than 1, the bonding of the 2 atoms will result in a lower energy state than not bonding. The bond order between diatomic elements also tells us the type of bonds between them. For example, N2 atoms have a bond order of 3, thus it means that a triple bond is formed between each N atom.

Question 2: What is the energy absorbed upon the breaking of one particular bond in a specific molecule?

Regions of electron density

Enhanced electron density

Node

Fig 1: Constructive and Destructive Interference for the Formation of MOs

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Molecular Orbital Theory

MO Diagrams

Fig 2: MO diagram for H2 MOs can be represented in a diagram like the one above. MO diagrams allow us to better understand the bonding between the atoms, and also allow us to predict special characteristics about the molecule, as we will see later. So how to draw a MO diagram? First, the AOs of each atom are drawn at the sides. An equal number of MOs Question 3: of different energy levels are then drawn in the middle. Which principle states that The positions of the various orbitals are important, electrons will occupy higher orbitals are at a higher energy level. The orbitals of lower energies electrons will occupy the orbital that is of a lower first? energy first and each MO can only have 2 electrons of different spins. Check that the total number of MOs is the same as the sum of the number of AOs of both atoms and the total number of electrons in the MOs is the same as the total number of electrons in both atoms. However, there are variations to how MO diagrams can be drawn, as we will see from those below. H2 In the H2 molecule, two s orbitals overlap head-on to form a sigma bonding orbital and a sigma anti-bonding orbital. Normally, the two electrons in hydrogen occupy the bonding molecular orbital, with antiparallel spins. If molecular hydrogen is irradiated by ultra-violet light of certain intensity, the molecule may absorb the energy, and one electron is promoted to its antibonding orbital, and the atoms will separate. Practice Show with a MO diagram why He2 does not exist.

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Molecular Orbital Theory

Li2

Fig 3: MO diagram for Li2 For the MOs formed from the 1s AOs, the overall bond order is 0. Hence, the effects of these two orbitals cancel out each other and they do not contribute to the bonding. However, the two 2s AOs overlap to form a filled 2 and an empty 2* MO. The bond order of 1 is reflected as the single bond in Li2.

Find out what the subscripts u and g represent for the MOs.

N2

Fig 4: MO diagram for N2 In N2, the bond orders for the MOs from the 1s and the 2s atomic orbitals are 0. The bond order for the MOs from the 2p orbitals is 3, with a sigma bond and two pi bonds. This is reflected in the triple bond between the nitrogen atoms.

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Molecular Orbital Theory

O2

Fig 5: MO diagram for O2 molecule As can be seen from the MO diagram, the bond order of O2 is 2, with two electrons in the MO, four in the MOs and two in the * MOs. Despite its bond order of 2, oxygen is highly reactive due to the two unpaired electrons in the * orbital (diradical). These two unpaired electrons also contribute to a special property of the oxygen molecule, as we will explore later. LiF

Question 4: Which rule results in the two unpaired electrons in the * orbital?

Fig 6: the molecular orbital diagram of LiF

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Molecular Orbital Theory

Above is a diagram of the MO diagram of LiF. Notice that the energy level of the Li electron is higher than the energy level of the F electrons. This is due to the fact that F is highly electronegative, thus the electrons are more stable. Since Li only has one occupied valence orbital, only one bonding and one antibonding orbital are possible. The electrons in orbitals on F that cannot bond with Li are left on F as lone pairs and are called non-bonding electrons. Paramagnetism The ability to explain and predict paramagnetism is one of the main successes of the MO theory over the other two theories. Paramagnetism is a form of magnetism which occurs only in the presence of an externally applied magnetic field. Constituent molecules of paramagnetic materials have permanent magnetic moments. However, in the absence of an applied field, these dipoles do not interact with one another and are randomly oriented due to thermal agitation, resulting in zero net magnetic moment. When a magnetic field is applied, the dipoles will tend to align with the applied field, resulting in a net magnetic moment in the direction of the applied field. This property is due to the presence of unpaired electrons. This can be easily deduced from the MO diagram of the molecule. An example of a paramagnetic molecule is oxygen (it has two unpaired * electrons). If the molecule does not have any unpaired electrons, it is said to be diamagnetic. Hckels Rule A compound has to satisfy several characteristics to be considered aromatic. It has to have a conjugated system (alternating single and double bonds) on a coplanar structure, with atoms arranged in a ring. The final condition is given by Hckels rule, which states that the number of electrons in the system has to fulfil the equation 4n+2, where n is a positive integer or 0. Another success of the MO theory is its ability to explain the reason behind this rule. As can be seen from Figures 6 and 7, all bonding MOs in aromatic compounds are filled while all antibonding MOs are empty. Thus in aromatic compounds bonding is the strongest possible. Hckels rule is thus a formula for the various total numbers of electrons that are needed to achieve this form of stability. Question 5: What form of magnetism do magnetic materials like iron exhibit?

Fig 7: MOs of Benzene (C6H6)

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Molecular Orbital Theory

E Antibonding

Bonding Cyclopendienyl anion Benzene Cycloheptatrienyl cation

Fig 8: MO diagrams of 3 aromatic compounds (n=2) Antiaromatic compounds are a highly unstable and reactive category of compounds that instead have 4n electrons in their system. Again, we can explain this phenomenon using MO theory. As shown in Figure 8, there is one electron each in each of the nonbonding degenerate molecular orbitals. This causes a decrease in the overall bond order. The presence of the unpaired electrons also increases the reactivity of the specie. Due to their instability, antiaromatic compounds are often twisted in a way to form non-planar molecules, achieving the more stable non-aromatic state.

Cycloheptatrienyl anion

Figure 8: MO diagram of the antiaromatic cycloheptatrienyl anion

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Molecular Orbital Theory

Conclusion In many aspects the molecular orbital theory is much more powerful and superior than the VSEPR and VB theories. Other than its ability to explain paramagnetism and Hckels rule, MO theory has also found applications in explaining various reactions in Chemistry, such as the electrocyclic additions, cycloaddition reactions and nucleophilic reactions in organic chemistry. According to the theory, Lewis acids and bases can also be classified into soft and hard, with soft-soft and hard-hard reactions being preferred. Despite its superiority over the other two theories, the complexities of MO theory make it difficult to be applied to less simple molecules. Furthermore, it is not always necessary to use a more powerful but complex theory to explain phenomena which can be explained more simply by less powerful theories. VSEPR is still commonly used to explain the shapes of molecules, and hybridization theory in VB theory is still used to explain many reactions and shapes of organic compounds. References: http://www.meta-synthesis.com/webbook/39_diatomics/diatomics.html http://www.usm.maine.edu/~newton/Chy251_253/Lectures/Aromaticity/AromaticityFS.h tml http://physics.kenyon.edu/coolphys/FranklinMiller/protected/Paramag.html http://en.wikipedia.org/wiki/Molecular_orbital_theory RJC Chemistry Olympiad Training Notes

Prepared by Ang Yi Hui, Liu Wing Chung, Daniel Lo

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Molecular Orbital Theory

Answer to questions: Question 1 Which rule states that no two electrons can have the same set of quantum numbers? Answer: Paulis Exclusion Principle. Question 2 What is the energy absorbed upon the breaking of one particular bond in a specific molecule? Answer: Bond dissociation energy. A similar concept, the bond energy, represents the average energy absorbed upon the breaking of a particular bond in different molecules. Question 3 Which principle states that electrons will occupy orbitals of lower energies first? Answer: Aufbau Principle. Question 4 Which rule results in the two unpaired electrons in the * orbital? Answer: Hunds rule. Thus we can see that the same rules and principles apply to both the AOs and the MOs. Question 5 What form of magnetism do magnetic materials like iron exhibit? Answer: Ferromagnetism. There are many magnetic states which various magnetic materials exhibit. Do find out more about the other states.

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