Molecular Orbital Theory Quiz

PDF page 442: Experiments show that each O2 molecule has two unpaired electrons. The Lewis-structure model does not predict the presence of these two unpaired electrons. Unlike oxygen, the apparent weight of most molecules decreases slightly in the presence of an inhomogeneous magnetic field. Materials in which all of the electrons are paired are diamagnetic and weakly repel a magnetic field. Paramagnetic and diamagnetic materials do not act as permanent magnets. Only in the presence of an applied magnetic field do they demonstrate attraction or repulsion.

PDF page 443: Molecular orbital theory (MO theory) provides an explanation of chemical bonding that accounts for the paramagnetism of the oxygen molecule. It also explains the bonding in a number of other molecules, such as violations of the octet rule and more molecules with more complicated bonding (beyond the scope of this text) that are difficult to describe with Lewis structures. Additionally, it provides a model for describing the energies of electrons in a molecule and the probable location of these electrons. Unlike valence bond theory, which uses hybrid orbitals that are assigned to one specific atom, MO theory uses the combination of atomic orbitals to yield molecular orbitals that are delocalized over the entire molecule rather than being localized on its constituent atoms. MO theory also helps us understand why some substances are electrical conductors, others are semiconductors, and still others are insulators.

PDF page 442: This electronic structure adheres to all the rules governing Lewis theory. There is an O=O double bond, and each oxygen atom has eight electrons around it. However, this picture is at odds with the magnetic behavior of oxygen. By itself, O2 is not magnetic, but it is attracted to magnetic fields. Thus, when we pour liquid oxygen past a strong magnet, it collects between the poles of the magnet and defies gravity, as in Figure 8.1. Such attraction to a magnetic field is called paramagnetism, and it arises in molecules that have unpaired electrons. And yet, the Lewis structure of O2 indicates that all electrons are paired. How do we account for this discrepancy? Magnetic susceptibility measures the force experienced by a substance in a magnetic field. When we compare the weight of a sample to the weight measured in a magnetic field (Figure 8.27), paramagnetic samples that are attracted to the magnet will appear heavier because of the force exerted by the magnetic field. We can calculate the number of unpaired electrons based on the increase in weight.

PDF page 458: paramagnetism phenomenon in which a material is not magnetic itself but is attracted to a magnetic field; it occurs when there are unpaired electrons present

PDF page 442: Experiments show that each O2 molecule has two unpaired electrons. The Lewis-structure model does not predict the presence of these two unpaired electrons. Unlike oxygen, the apparent weight of most molecules decreases slightly in the presence of an inhomogeneous magnetic field. Materials in which all of the electrons are paired are diamagnetic and weakly repel a magnetic field. Paramagnetic and diamagnetic materials do not act as permanent magnets. Only in the presence of an applied magnetic field do they demonstrate attraction or repulsion.

PDF page 458: diamagnetism phenomenon in which a material is not magnetic itself but is repelled by a magnetic field; it occurs when there are only paired electrons present

PDF page 442: Experiments show that each O2 molecule has two unpaired electrons. The Lewis-structure model does not predict the presence of these two unpaired electrons. Unlike oxygen, the apparent weight of most molecules decreases slightly in the presence of an inhomogeneous magnetic field. Materials in which all of the electrons are paired are diamagnetic and weakly repel a magnetic field. Paramagnetic and diamagnetic materials do not act as permanent magnets. Only in the presence of an applied magnetic field do they demonstrate attraction or repulsion.

PDF page 454: ⎛ ⎞ The O2 molecule has enough electrons to half fill the π* , π* level. We expect the two electrons that occupy ⎝ 2py 2pz⎠ these two degenerate orbitals to be unpaired, and this molecular electronic configuration for O2 is in accord with the fact that the oxygen molecule has two unpaired electrons (Figure 8.40). The presence of two unpaired electrons has proved to be difficult to explain using Lewis structures, but the molecular orbital theory explains it quite well. In fact, the unpaired electrons of the oxygen molecule provide a strong piece of support for the molecular orbital theory.

PDF page 443: Molecular orbital theory (MO theory) provides an explanation of chemical bonding that accounts for the paramagnetism of the oxygen molecule. It also explains the bonding in a number of other molecules, such as violations of the octet rule and more molecules with more complicated bonding (beyond the scope of this text) that are difficult to describe with Lewis structures. Additionally, it provides a model for describing the energies of electrons in a molecule and the probable location of these electrons. Unlike valence bond theory, which uses hybrid orbitals that are assigned to one specific atom, MO theory uses the combination of atomic orbitals to yield molecular orbitals that are delocalized over the entire molecule rather than being localized on its constituent atoms. MO theory also helps us understand why some substances are electrical conductors, others are semiconductors, and still others are insulators.

PDF page 458: molecular orbital theory model that describes the behavior of electrons delocalized throughout a molecule in terms of the combination of atomic wave functions

PDF page 443: Molecular orbital theory describes the distribution of electrons in molecules in much the same way that the distribution of electrons in atoms is described using atomic orbitals. Using quantum mechanics, the behavior of an electron in a molecule is still described by a wave function, Ψ, analogous to the behavior in an atom. Just like electrons around isolated atoms, electrons around atoms in molecules are limited to discrete (quantized) energies. The region

PDF page 458: linear combination of atomic orbitals technique for combining atomic orbitals to create molecular orbitals

PDF page 443: of space in which a valence electron in a molecule is likely to be found is called a molecular orbital (Ψ ). Like an atomic orbital, a molecular orbital is full when it contains two electrons with opposite spin. We will consider the molecular orbitals in molecules composed of two identical atoms (H2 or Cl2, for example). Such molecules are called homonuclear diatomic molecules. In these diatomic molecules, several types of molecular orbitals occur. The mathematical process of combining atomic orbitals to generate molecular orbitals is called the linear combination of atomic orbitals (LCAO). The wave function describes the wavelike properties of an electron. Molecular orbitals are combinations of atomic orbital wave functions. Combining waves can lead to constructive interference, in which peaks line up with peaks, or destructive interference, in which peaks line up with troughs (Figure 8.28). In orbitals, the waves are three dimensional, and they combine with in-phase waves producing regions

PDF page 458: molecular orbital region of space in which an electron has a high probability of being found in a molecule

PDF page 458: bonding orbital molecular orbital located between two nuclei; electrons in a bonding orbital stabilize a molecule

PDF page 444: There are two types of molecular orbitals that can form from the overlap of two atomic s orbitals on adjacent atoms. The two types are illustrated in Figure 8.29. The in-phase combination produces a lower energy σs molecular orbital (read as "sigma-s") in which most of the electron density is directly between the nuclei. The out-of-phase addition (which can also be thought of as subtracting the wave functions) produces a higher energy molecular orbital (read as "sigma-s-star") molecular orbital in which there is a node between the nuclei. The asterisk signifies that the orbital is an antibonding orbital. Electrons in a σs orbital are attracted by both nuclei at the same time and are more stable (of lower energy) than they would be in the isolated atoms. Adding electrons to these orbitals creates a force that holds the two nuclei together, so we call these orbitals bonding orbitals. Electrons in the σ*s orbitals are located well away from the region between the two nuclei. The attractive force between the nuclei and these electrons pulls the two nuclei apart. Hence, these orbitals are called antibonding orbitals. Electrons fill the lower-energy bonding orbital before the higher-energy antibonding orbital, just as they fill lower-energy atomic orbitals before they fill higher-energy atomic orbitals.

PDF page 458: antibonding orbital molecular orbital located outside of the region between two nuclei; electrons in an antibonding orbital destabilize the molecule

PDF page 444: There are two types of molecular orbitals that can form from the overlap of two atomic s orbitals on adjacent atoms. The two types are illustrated in Figure 8.29. The in-phase combination produces a lower energy σs molecular orbital (read as "sigma-s") in which most of the electron density is directly between the nuclei. The out-of-phase addition (which can also be thought of as subtracting the wave functions) produces a higher energy molecular orbital (read as "sigma-s-star") molecular orbital in which there is a node between the nuclei. The asterisk signifies that the orbital is an antibonding orbital. Electrons in a σs orbital are attracted by both nuclei at the same time and are more stable (of lower energy) than they would be in the isolated atoms. Adding electrons to these orbitals creates a force that holds the two nuclei together, so we call these orbitals bonding orbitals. Electrons in the σ*s orbitals are located well away from the region between the two nuclei. The attractive force between the nuclei and these electrons pulls the two nuclei apart. Hence, these orbitals are called antibonding orbitals. Electrons fill the lower-energy bonding orbital before the higher-energy antibonding orbital, just as they fill lower-energy atomic orbitals before they fill higher-energy atomic orbitals.

PDF page 444: There are two types of molecular orbitals that can form from the overlap of two atomic s orbitals on adjacent atoms. The two types are illustrated in Figure 8.29. The in-phase combination produces a lower energy σs molecular orbital (read as "sigma-s") in which most of the electron density is directly between the nuclei. The out-of-phase addition (which can also be thought of as subtracting the wave functions) produces a higher energy molecular orbital (read as "sigma-s-star") molecular orbital in which there is a node between the nuclei. The asterisk signifies that the orbital is an antibonding orbital. Electrons in a σs orbital are attracted by both nuclei at the same time and are more stable (of lower energy) than they would be in the isolated atoms. Adding electrons to these orbitals creates a force that holds the two nuclei together, so we call these orbitals bonding orbitals. Electrons in the σ*s orbitals are located well away from the region between the two nuclei. The attractive force between the nuclei and these electrons pulls the two nuclei apart. Hence, these orbitals are called antibonding orbitals. Electrons fill the lower-energy bonding orbital before the higher-energy antibonding orbital, just as they fill lower-energy atomic orbitals before they fill higher-energy atomic orbitals.

PDF page 444: There are two types of molecular orbitals that can form from the overlap of two atomic s orbitals on adjacent atoms. The two types are illustrated in Figure 8.29. The in-phase combination produces a lower energy σs molecular orbital (read as "sigma-s") in which most of the electron density is directly between the nuclei. The out-of-phase addition (which can also be thought of as subtracting the wave functions) produces a higher energy molecular orbital (read as "sigma-s-star") molecular orbital in which there is a node between the nuclei. The asterisk signifies that the orbital is an antibonding orbital. Electrons in a σs orbital are attracted by both nuclei at the same time and are more stable (of lower energy) than they would be in the isolated atoms. Adding electrons to these orbitals creates a force that holds the two nuclei together, so we call these orbitals bonding orbitals. Electrons in the σ*s orbitals are located well away from the region between the two nuclei. The attractive force between the nuclei and these electrons pulls the two nuclei apart. Hence, these orbitals are called antibonding orbitals. Electrons fill the lower-energy bonding orbital before the higher-energy antibonding orbital, just as they fill lower-energy atomic orbitals before they fill higher-energy atomic orbitals.

PDF page 445: The side-by-side overlap of two p orbitals gives rise to a pi (π) bonding molecular orbital and a π* antibonding molecular orbital, as shown in Figure 8.31. In valence bond theory, we describe π bonds as containing a nodal plane containing the internuclear axis and perpendicular to the lobes of the p orbitals, with electron density on either side of the node. In molecular orbital theory, we describe the π orbital by this same shape, and a π bond exists when this orbital contains electrons. Electrons in this orbital interact with both nuclei and help hold the two atoms together, making it a bonding orbital. For the out-of-phase combination, there are two nodal planes created, one along the internuclear axis and a perpendicular one between the nuclei.

PDF page 458: pi bond (π bond) covalent bond formed by side-by-side overlap of atomic orbitals; the electron density is found on opposite sides of the internuclear axis