Multielectron atoms, quantum numbers

For reasons we will discuss later, a fourth quantum number is required to completely describe a specific electron in a multielectron atom. The fourth quantum number is given the symbol ms. Each electron in an atom has a set of four quantum numbers n, l, mi, and ms. We will now discuss the quantum numbers of electrons as they are used in atoms beyond hydrogen. 

Now the parity of a multielectron, ionic, or atomic wave function is given by TT ( — l)/fc, where lk (the angular-momentum quantum number)... 

The Pauli Exclusion Principle states that no two electrons of any single atom may simultaneously occupy a slate described by only a single set of quantum numbers. Five such numbers arc needed to describe fully the quantum-mechanical conditions of an electron. For j-j coupling this set is generally ti. I., v. j. iij. and for l.-S it is /t. /. j. u(. nr,. From die coupling of the angular momentum associated with the latter sets a full description of the multielectron stale, described by it, L. S, J. Mis determined. 

The three quantum numbers n, l, and wi/ discussed in Section 5.7 define the energy, shape, and spatial orientation of orbitals, but they don t quite tell the whole story. When the line spectra of many multielectron atoms are studied in detail, it turns out that some lines actually occur as very closely spaced pairs. (You can see this pairing if you look closely at the visible spectrum of sodium in Figure 5.6.) Thus, there are more energy levels than simple quantum mechanics predicts, and a fourth quantum number is required. Denoted ms, this fourth quantum number is related to a property called electron spin. 

The importance of the spin quantum number comes when electrons occupy specific orbitals in multielectron atoms. According to the Pauli exclusion principle,... 

Which two of the four quantum numbers determine the energy level of an orbital in a multielectron atom ... 

In a hydrogen atom, the orbital energy is determined exclusively by the principal quantum number n—all the different values of / and mi are degenerate. In a multielectron atom, however, this degeneracy is partially broken the energy increases as / increases for the same value of n. 

In this volume, principal consideration is given to the lighter elements, so that the Russell-Saunders (549) vector model of the atom is used. In this model a multielectron atom is assumed to have the quantum numbers n, L = lif Ml, 8 = siy (or n, L, J = L + S, Mj). This implies stronger and Si-Sj coupling than U-Si coupling. It follows from Pauli s principle that for a closed shell =... 

Values of the magnetic quantum number, mp, depend on the value off. When = 0, mp can only take one value (0) when = 1, mp has three possible values (+1, 0, or -1). There are five possible values of mp when - 2 and seven when C = 3. In more familiar terms, there is only one sort of s orbital there are three sorts of p orbitals, five sorts of d orbitals, and seven sorts of f orbitals. All three p orbitals are degenerate as arc all five d orbitals and all seven f orbitals (for both single-electron and multielectron atoms). We shall see how to represent these orbitals later. 

A multielectron atom can exist in several electronic states, called microstates, which are characterized by the way the electrons are distributed among the atomic orbitals. The number of microstates for a free atom with a valence shell consisting of a set of degenerate orbitals with orbital angular momentum quantum number I housing n electrons is given by ... 

In a free multielectron atom or ion, the spin and orbital angular moments of the electrons couple to give a total angular momentum represented in the Russell-Saunders scheme by the quantum number J. Since J arises from vectorial addition of L (the total orbital quantum number) and 5 (total spin quantum number), it may take integral (or half-integral... 

The quantum numbers that describe states of multielectron atoms are defined as follows ... 

To this point in the discussion of multielectron atoms, the spin and orbital angular momenta have been treated separately. In addition, the spin and orbital angular momenta couple with each other, a phenomenon known as spin-orbit coupling. In multielectron atoms, the S and L quantum numbers combine into the total angular momentum quantum number J. The quantum number J may have the following values ... 

In atoms with more than one electron, wave functions should include the coordinates of each particle, and a new term representing the electrostatic interactions between electrons. Even for the case of only two electrons, such a wave equation is so complex that it has never been solved exactly. To analyse multielectron atoms some approximations have to be made. The most practical one is to assume that the electron considered moves in an electrical potential that is a combination of all other electrons and the nucleus, and that this potential has spherical symmetry. This approximation has proven very useful, as it allows a description of energy states in a similar manner to that employed for the H atom by using a comparable set of four quantum numbers. An important, additional condition appears no two electrons can have the same set of quantum numbers in other words, no more than one electron can occupy the same energy state. This is Pauli s exclusion principle. 

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