incident wa —e _— fe \ a | : th Introduction and Background to Quantum Mechanics Understanding molecular behavior through the use of quantum mechanical ideas requires a fundamental understanding of quantum mechanics itself. In this chap- ter, we discuss some of the aims of theoretical chemistry, mention key concepts from classical physics, including both particle and wave behavier, and briefly summarize some of the carly history of quantum mechanics. Ideas such as wave-particle duality, the uncertainty principle, and wave mechanics underlie the work in the remainder of the book 1.1 AIM OF THEORETICAL CHEMISTRY Prior to the development of quantum mechanics, molecular chemistry was es- sentially an empirical science. Elements and compounds were categorized into groups (e.g., the periodic table, alkanes, alkenes, alkynes, etc.), and there were empirical rules concerning the interrelationships of different chemical proper ties (structural, thermodynamic, reactivity, etc). The underlying physical basis far these rules was largely unknown, and this ignorance hindered attempts to generalize the rules to different kinds of molecules. ‘Quantum mechanics changed molecular chemistry to a more exact science in which most molecular behavior can be understood on the basis of one uni- fied concept: the Schrodinger equation, In this picture, the empirical rules can. be derived by studying the behavior of solutions af the Schriidinger equation, and this, in principle, enables the rules ta be generalized. The following table 12 Introduction and Background to Quantum Mechanics Chapter 1 Empirical uke ‘Quantwin property Pauling’s rule (relates bond energy Occupation numbers of bonding andl ‘and length) ‘untibaruling molecular extyitals approximately detersune both bond enersy and band length Arrhenius formula {chemical reactions are ——‘Morriers wi potentinl-energy surfaces. activated) determine activation ene egy LLingar froc-oncrey relations Inductive electron density changes in aromatic {Hammett rule) systems determine substituent effects gives some empirical rules and their underlying rationalization, based on quan- tum mechanics. Ithas been suggested (by Dirac) that quantum mechanics changes the prac- lice of chemistry to an exercise in applied mathematics, wherein it is only solu- tions to the Schridinger equation that need be determined to understand any chemical problem, This statement is true more in principle than in practice for most problems, however, as the computational complexity associated with solv- ing the Schrodinger equation is often quite formidable. But it also means that the development of accurate and efficient methods for solving the Schréidinger equation for molecular systems is an important research topic in chemistry and that understanding quantum mechanies is an essential part of one’s chemical ed- ucation. One significant consequence of this research and education in the chem- ical applications of quantum mechanics has been the emergence of several software companies whosc survival depends on the ability of quantum methods to solve chemical problems that are important to industry. ‘The detailed history of the discovery of quantum mechanics is now largely decoupled fram its modern practice, but there are key concepts that are best un- derstood ina historical context, This chapter describes these concepts, as well as background material from classical physics that is relevant to understanding mo- Jecular quantum mechanies. In addition, the chapter serves as an introduction to the basic concepts of quantum mechanics that are defined more rigorously in Chapter 2. Our intention in this development is to keep the evel of mathemat- ics as low as possible—ideally requiring nothing beyond what is covered in un- dergradvate calculus courses. However, a few topics go beyond this level, so in Appendix A we give a short primer on those subjects: complex variables; differ- ential equations; and matrices, determinants, and cigenvalues. 1.2 KEY CONCEPTS FROM CLASSICAL PHYSICS To understand quantum mechanics, it is necessary first to understand classical mechanics and classical wave theory. Here we give just the essentials of each, plus some simple examples that also show up in quantum mechanicsSection 1.3 Classical Mechanics 3 1.3 CLASSICAL MECHANICS 1.3.1 Potential-Energy Functions The motions we are interested in involve particles moving under the influence of forces that may be derived from a poiential-cnergy function that we denote by V. This situation could involve two particles interacting with each other subject to a coulomb potential _ ats vin = ee. a.) where r is the distance between the particles, q, and q, are the charges on each particle, and &, is the permittivity of free space. [Note: Throughout this text, we use SI units The corresponding CGS formula would omit the factor 1/(4:«,).) A gravitational potential would have the same form, except that it is always at= tractive and the charges are replaced by the masses of the particles. For either coulomb or gravitational potentials, the potential appropriate for many particles is just the sum of all the two-particle potentials, Another example would be a harmonic oscillator, which can be thought of asa single particle moving in a parabolic potential. For motion in one dimension, the potential is Vix) = hae’ (1.2) where x is the displacement of the particle from equilibrium and & is a parame- ter known as the force constant. This potential is appropriate for describing the motion of a mass oscillating at the end of a spring or for describing the motion of atoms vibrating in a molecule or crystal EXERCISE 1.1. For the CO molecule, the force constant is (40188 N/m. If the mole- cule is displaced by 1.0 pm (0.01 A) from its equilibrium position, how much vibrational potential energy is present in the molecule? = }(00185 N/m)(i.0 10 my’ = 93 x 107 J = 0.00557 J/mol 1.3.2 Newton's Second Law Newton's second law consists of an equation that determines the evolution of the coordinate and velocity of a particle (or particles) with time, given initial val- ues for the coordinate and velocity. The usual expression for Newton's law (or Newton's equation) for a single particle moving in one dimension is ma= F, (13)