Third quantum number

It follows that the only possible values for la + Ip are S A and the computation of vibronic levels can be carried out for each K block separately. Matrix elements of the electronic operator diagonal with respect to the electronic basis [first of Eqs. (60)], and the matrix elements of T are diagonal with respect to the quantum number I = la + Ip. The off-diagonal elements of [second and third of Eqs. (60)] connect the basis functions with I — la + Ip and I — l + l — l 2A. 

The third quantum number m is called the magnetic quantum number for it is only in an applied magnetic field that it is possible to define a direction within the atom with respect to which the orbital can be directed. In general, the magnetic quantum number can take up 2/ + 1 values (i.e. 0, 1,. .., /) thus an s electron (which is spherically symmetrical and has zero orbital angular momentum) can have only one orientation, but a p electron can have three (frequently chosen to be the jc, y, and z directions in Cartesian coordinates). Likewise there are five possibilities for d orbitals and seven for f orbitals. 

Soon after Bohr developed his initial configuration Arnold Sommerfeld in Munich realized the need to characterize the stationary states of the electron in the hydrogen atom by. means of a second quantum number—the so-called angular-momentum quantum number, Bohr immediately applied this discovery to many-electron atoms and in 1922 produced a set of more detailed electronic configurations. In turn, Sommerfeld went on to discover the third or inner, quantum number, thus enabling the British physicist Edmund Stoner to come up with an even more refined set of electronic configurations in 1924. 

When tlte first quantum number takes the value one, the second quantum number can only be zero and likewise toe third quantum number. Now according to Pauli s exclusion principle it is forbidden for more than one electron in a. shell, therefore having the same n value, to have the same values for the remaining three quantum numbers. This gives the prediction that a maximum of two electrons occupy the first shell and that these share the same first three quantum numbers but differ in the value of the fourth, adopting one of two values. For the n 2 shell the situation is more complicated, since there are two possible values for the second quantum number, namely one and zero (as shown in Figure 6). When the second quan-... 

Figure 6. Wolfgang Pauli s discovery of the exclusion principle led to his development of a fourth quantum number to describe the electron. At the time, it was known that each successive electron shell in an atom could contain % 8, 18. .. 2nz electrons (where n is the shell number), and Pauli s fourth number made it possible to explain this. When an electron s first quantum number is one, the second and third must be zero, leaving two possibilities for the fourth number Thus the first shell can contain only two electrons. At = 2, there are four possible combinations of the second and third numbers, each of which has two possible fourth numbers. Thus the second shell closes when it contains eight electrons.

But does the fact that the third shell can contain 18 electrons, for example, which emerges from the relationships among the quantum numbers, also explain why some of the periods in the periodic system contain eighteen places Actually not exactly. If electron shells were filled in a strictly sequential manner there would be no problem and the explanation would in fact be complete. But as everyone is aware, the electron shells do not fill in the expected sequential manner. The configuration of element number 18, or argon is,... 

But I want to return to my claim that quantum mechanics does not really explain the fact that the third row contains 18 elements to take one example. The development of the first of the period from potassium to krypton is not due to the successive filling of 3s, 3p and 3d electrons but due to the filling of 4s, 3d and 4p. It just so happens that both of these sets of orbitals are filled by a total of 18 electrons. This coincidence is what gives the common explanation its apparent credence in this and later periods of the periodic table. As a consequence the explanation for the form of the periodic system in terms of how the quantum numbers are related is semi-empirical, since the order of orbital filling is obtained form experimental data. This is really the essence of Lowdin s quoted remark about the (n + , n) rule. 

For example, if the first quantum number is 3 the second quantum number can take values of 2, 1, or 0. Each of these values of will generate a number of possible values of mt and each of these values will be multiplied by a factor of two since the fourth quantum number can adopt values of 1/2 or -1/2. As a result there will be a total of 2n2 or 18 electrons in the third shell. This scheme thus explains why there will be a maximum total of 2, 8, 18, 32, etc., electrons in successive shells as one moves further away from the nucleus. 

The problem is this the third row of the periodic table contains 8, not 18, electrons. It turns out that while quantum numbers provide a satisfying deductive explanation of tbe total number of electrons that any shell can hold, the correspondence of tliese values with the number of elements that occur in any particular period is something of a coincidence. The familiar sequence In which the s, p, d, and f orbitals are filled (see diagram, left) has essentially been determined by empirical means. Indeed. Bohr s failure to derive the order for the filling of the orbitals has been described by some as one of the outstanding problems of quantum mechanics. 

The third quantum number required to specify an orbital is mh the magnetic quantum number, which distinguishes the individual orbitals within a subshell. This quantum number can take the values... 

The symbols in the second column represent the electronic state in particular the first number is the total quantum number of the excited electron. We shall see later that in one case at least the symbol is probably incorrect. The third column gives the wave-number of the lowest oscillational-rotational level, the fourth the effective quantum number, the fifth and sixth the oscillational wave-number and the average intemuclear distance for the lowest oscillational-rotational level. The data for H2+ were obtained by extrapolation, except rQ, which is Burrau s theoretical value (Section Via). 

Which a — 2 orbital does the third electron in a lithium atom occupy Screening causes the orbitals with the same principal quantum number to decrease in stability as / increases. Consequently, the 2 S orbital, being more stable than the 2 orbital, fills first. Similarly, 3 S fills before 3 p, which fills before 3 d, and so on. 

A complete specification of how an atom s electrons are distributed in its orbitals is called an electron configuration. There are three common ways to represent electron configurations. One is a complete specification of quantum numbers. The second is a shorthand notation from which the quantum numbers can be inferred. The third is a diagrammatic representation of orbital energy levels and their occupancy. 

The third solution to Schrodinger s equation produces the magnetic quantum number, usually designated as m. Allowable values of this quantum number range from -f to +f. A summary of... 

The next element is lithium, with three electrons. But the third electron does not go in the Is orbit. The reason it does not arises from one the most important rules in quantum mechanics. It was devised by Wolfgang Pauli (and would result in a Nobel Prize for the Austrian physicist). The rule Pauli came up with is called the Pauli exclusion principle it is what makes quantum numbers so crucial to our understanding of atoms. 

The exclusion principle states that no two electrons in an atom can have the same set of quantum numbers. The Is orbital has the following set of allowable numbers n= 1, f = 0, m = 0, mg = +1/2 or -1/2. All of these numbers can have only one value except for spin, which has two possible states. Thus, the exclusion principle restricts the Is orbital to two electrons with opposite spins. A third electron in the Is orbital would have to have a set of quantum numbers identical to those of one of the electrons already there. Thus, the third electron needed for lithium must go into the next higher energy shell, which is a 2s orbital. 

Depending on the permitted values of the magnetic quantum number m, each subshell is further broken down into units called orbitals. The number of orbitals per subshell depends on the type of subshell but not on the value of n. Each orbital can hold a maximum of two electrons hence, the maximum number of electrons that can occupy a given subshell is determined by the number of orbitals available. These relationships are presented in Table 17-5. The maximum number of electrons in any given energy level is thus determined by the subshells it contains. The first shell can contain 2 electrons the second, 8 electrons the third, 18 electrons the fourth, 32 electrons and so on. 

From the mathematical restrictions on the solution of the equations comes a set of constraints known as quantum numbers. The first of these is n, the principal quantum number, which is restricted to integer values (1, 2, 3,. ..). The second quantum number is 1, the orbital angular momentum quantum number, and it must also be an integer such that it can be at most (n — 1). The third quantum number is m, the magnetic quantum number, which gives the projection of the 1 vector on the z axis as shown in Figure 2.2. 

As noted above, not all possible transitions between energy levels are theoretically allowed. Each energy level is uniquely characterized by a set of quantum numbers. The integer used to define the energy level in the above discussion (1,2, 3, etc.) is called the principal quantum number, n. The sub-levels described by the letters (s, p, d, /, etc.) are associated with the second quantum number, given the symbol /, with l = 1 synonymous with s, 2 =p, etc. The multiplicity of levels associated with each sub-level (i.e., the number of horizontal lines for each orbital in Figure Al.l) is defined by a third quantum number mh which has values 0, 1... 1. Thus, -orbitals only have one sub-level, p-orbitals have three (with m/ values 0 and d= 1), d-orbitals have five, etc. The selection rules can... 

The exceptions begin with the fourth energy level. The fourth energy level begins to fill before all the sublevels in the third shell are complete. More complications in the sequence appear as the value of the principle quantum number increases. The sequence of orbital filling, with complications, is Is, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, and so on. 

The third quantum number is the magnetic quantum number ( /). It describes the orientation of the orbital around the nucleus. The possible values of m1 depend on the value of the angular momentum quantum number, /. The allowed values for m/ are —/ through zero to +/. For example, for /= 2 the possible values of mi would be —2, —1, 0, +1, +2. This is why, for example, if / = 1 (a p orbital), then there are three p orbitals corresponding to m/ values of—1, 0, +1. This is also shown in Figure 10.3. 

QUANTUM NUMBER FIRST ELECTRON SECOND ELECTRON THIRD ELECTRON FOURTH ELECTRON FIFTH ELECTRON SIXTH ELECTRON... 

As for the third and fourth quantum numbers, in agreement with what is generally mentioned in textbooks on chemistry, such as, for instance, Greenwood and Earnshaw (1997) we may say that ... 

With Na, the electron configuration of which may also be described as [Ne s1, the third period begins. A similar situation is found for each of the other periods in the Table the number of the period is the principal quantum number of the least tightly bound electron of the first element (an alkali metal) of the period. A few more details of these questions and the characteristics of special points in the Periodic Table are discussed in following paragraphs. The electron configurations of all the elements are given in Chapter 5. 

Orbitals have a variety of different possible shapes. Therefore, scientists use three quantum numbers to describe an atomic orbital. One quantum number, n, describes an orbital s energy level and size. A second quantum number, I, describes an orbital s shape. A third quantum number, mi, describes an orbital s orientation in space. These three quantum numbers are described further below. The Concept Organizer that follows afterward summarizes this information. (In section 3.3, you will learn about a fourth quantum number, mg, which is used to describe the electron inside an orbital.)... 

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