Mark J.

Moody Honors Quantum Mechanics 2-27-2013

On Schrdinger : An Undulatory Theory of the Mechanics of Atoms and Molecules

Quantum mechanics many apparent oddities and counterintuitive postulates have gained increasing public fascination ever since its development and reformulation during the early twentieth century. Quantum means discreet or countable, and is the name for the branch of physics devoted to dealing with and interpreting the intrinsic nature of elementary particles and atoms while describing the physical phenomena that we observe on these microscopic scales. One of the bases for quantum theory, the Schrdinger equation, provides a mathematical description of the wave-particle duality set forth by Albert Einstein in his 1905 Annus Mirabilis Papers. In 1900, Max Planck developed an equation relating the energy of light to its frequency, showing them to be directly proportional, offset only by a constant (Plancks action quantum). Einstein used Plancks work to understand the photoelectric effect and to describe light in terms of quantized energy packets, commonly referred to as light quanta or photons. Light was already well known to be a wave, its frequency determining various properties such as color in the visible spectrum. This wave-particle duality is the foundation off of which quantum mechanics launched. Physics was thought to be a nearly complete science as the nineteenth century drew to a close, with more accuracy attained simply through greater metric precision. However, based on our current understanding of the universe and our world, this view was not even tenuously correct, and the discovery and study of blackbody radiation began to alter this former static perception. As the kinetic energy of atoms within a solid substance increases (i.e., the objects temperature increases), those atoms emit radiation in the form of electromagnetic energy. Generally, there will be a particular wavelength and intensity of emitted energy relative to a particular temperature. For each temperature, there exists a radiation wavelength of higher energy density than the surrounding longer or shorter wavelengths. These maxima occur at

different frequencies for different temperatures. A blackbody is such a solid that it is idealized to absorb all incident radiation and also perfectly emit this radiation. Although the idealized blackbody is a hypothetical construct since a perfectly ideal system isnt achievable, a blackbody can be experimentally approximated by an enclosed cavity with a small hole in one side of the enclosure. A blackbody at room temperature would appear black because most of the emitted radiation would leave the body as infra red light invisible to the human eye. No explanation based on classical mechanics succeeded in describing or accounting for the maxima observed in blackbody radiation, until finally in 1900, Max Planck completed an empirical equation for the radiations function, F(x) as follows: ( ) Where k represents Boltzmanns constant and ( ) .

represents an unknown constant. Planck

proceeded to treat the blackbody experiment as a set of isotropic oscillators with the ability to interact with electromagnetic radiation. He proposed each of these oscillators to have its own vibrational frequency, represented by . Planck then proposed that each oscillators energy exists in discreet values such that where represents the oscillators energy, n is the oscillators frequency. This

represents integer values, h is a universal constant, and

formula asserts that the energy values for these oscillators are quantized; that is, they exist in discreet units of countable values and are not continuously and evenly distributed. Planck further postulated that both the absorption and emission of radiation energy are directly correlated to jumps in energy level corresponding to a gain or loss of a quantum of radiant energy, the magnitude being . As is required by the second law of thermodynamics,

differential entropy is equivalent to differential energy over temperature -- temperature remaining constant for blackbody radiation. In other words, or states that

temperature measures the increase in entropy when energy is added to a system. Using

Maxwell-Boltzmann statistics coupled with the average energy of an oscillator, Planck showed that the previously unknown constant . The constant, is just , yielding the function ) ( is ) ( ) ( )

must have the units of (

and is frequently referred , and although has been proven time

to as Plancks action quantum. The specific value of

Planck was incredulous of his own work, his calculation of the value of and again to be a fundamental constant of nature. [5]

In 1905, Albert Einstein suggested an extension of Plancks discoveries that provided an explanation for the details associated with the photoelectric effect. The photoelectric effect was displayed by way of a well documented experiment using an electropositive metal as a cathode biased negatively with regard to an anode, or opposing conductive plate. The cathode attracts positive charge and the anode attracts negative charge. As this cathode is illuminated with various frequencies of incoming light, a current is produced between the cathode and anode. In other words, negatively charged electrons are ejected from the surface of the cathode metal and attracted to the surface of the anode metal. For each type of metal used for the cathode, there is a frequency of incoming light below which the effect ceases. The more electropositive the metal, the lower the frequency -- the longer the wavelength -- one can use to produce the effect. This frequency wavelength relation is known as the characteristic wavelength of the material. Group 1A metals respond very well to the visible spectrum of incoming electromagnetic radiation, given that they have a prior disposition to lose an electron to form a complete valence band. One conundrum of the photoelectric effect had been that although the magnitude of current between plates is directly proportional to the amount or intensity of incoming light, the threshold value for producing a

current was entirely dependent upon the lights frequency/wavelength, and is completely independent of the lights intensity. Once again, classical mechanics provided no solution to this quandary. Einstein postulated that the radiant energy itself is quantized; that is, the light/electromagnetic radiation transmits energy in quantized units. If this is true, then light transmits energy in like manner to a particle collision, and therefore must be comprised of particles or something that transmits energy like particles. These particles, or light quanta, have become known as photons. Assuming that electrons are free to move between atoms in the conduction bands of a conductive metal, the incoming photons must be able to overcome the attraction of the electron to the rest of the metal in order to produce the observed current, the photons energy being (the energy units of blackbody emission and absorption). After the

photons energy is used to overcome the attractive force between the electron and the metal, any additional energy would be imparted to the ejected electron as kinetic energy. Einstein expressed this as follows: the electron, is the electrons velocity and where is as previously defined, is the mass of

is the work function of the metal (the minimum

work necessary to remove an electron from the metal). That is, the work function is the ionization energy of the metal. Einsteins model also implies that where is the threshold frequency. Since

uncontaminated metal surfaces were exceedingly difficult to obtain and maintain, Einsteins equations remained unverified until Robert Millikan began working with freshly exposed metal surfaces in vacuum atmospheres in 1916. According to Einstein, a photons rest mass, zero, but since it travels at , the speed of light, the requirements of his theory of special is

relativity attribute a nonzero rest mass written as

to the photon. Therefore, the energy of a photon can be , where is the linear momentum of the individual

quantized photon. Furthermore, this equivalence shows that the momentum of a photon, , can be obtained by or . This assertion is a foundation stone for quantum mechanics

because it shows that light has an experimentally verified wavelength, thus acting as a wave, and simultaneously has a linear, particle-like momentum duality of electromagnetic radiation. [1] Gaseous elements also emit radiation when excited. When the atoms comprising some gaseous element are excited, excess energy is emitted as electromagnetic radiation. When the radiation is separated via prism into individual frequencies of light, the separated frequencies consist of several well defined lines. This is called the spectrum of the element. Each line represents a unique wavelength, and in the visible spectrum, this wavelength determines a particular color as observed by the human eye. The line spectrum of the hydrogen atom is the simplest known spectrum and is obtained by sending a high voltage electrical discharge through fairly low pressure . This electrical discharge both excites the atoms energetically and , all of which comprises the particle-wave

atomizes the hydrogen. The emitted radiation from excited atoms forms the hydrogen spectrum. Classical mechanics failed to provide a correct explanation for the appearance of the discreet frequency values observed in various atomic spectra, but in 1885, J.J. Balmer fit the positions of spectral lines in the visible region of the spectrum to the following formula: where A is 364.56 nanometers and m is an integer ranging from three to six. Later, in 1896, Johannes Rydberg generalized the formula to accommodate newly discovered spectral lines in the ultraviolet region of light, and in 1908, Walter Ritz further generalized the formula to

accommodate infrared spectral lines. The Balmer-Rydberg-Ritz formula is ( ) under the condition that and both are integers where is the )

wavelength of emitted light, R is the Rydberg constant (which is equal to 4/A or 109,677.8 and is the reciprocal wavelength. When , and , this equation reduces to

the original Balmer formula. Using the reciprocal wavelength , and assigning a variable , the Balmer-Rydberg-Ritz formula can be restated as Later, and . [5]

were recognized as electron orbitals, or shells that describe the energy represents an electron inhabiting an electron

level of the electron. A greater integer value of

shell further from the nucleus of an atom. As electrons jump between shells, excess energy is released in the form of electromagnetic radiation as an electron falls to a lower energy state, or energy is required to excite the electron up to a higher orbital. Once an electron is in this excited state, it naturally tends toward regaining a region of lower potential energy and transitions to a lower orbital, releasing energy. Interestingly, this travel cannot be accurately described using classical mechanics due to a potential energy barrier that the electron could not surmount classically. The electron does not exist in most of the region between shells, rather the electron tunnels between integer values of , existing in one state or the other. Once again, the quantization of spectral lines leads to the necessity of integer values for quantization of energy. Around the year 1910, Ernest Rutherford, Hans Geiger, and Ernest Marsden performed their famous gold foil experiment. Rutherford had already concluded that an atom is primarily empty space, and essentially tasked his apprentice Geiger to bombard the gold foil to give Geiger something to work on and to free himself for material he perceived to be of greater importance. and , and the

Rutherford did not expect Geiger to observe any scattering, but to show Geiger that atoms are, in fact, mostly empty space. The experiment consisted of directing a beam of alpha particles (produced by the radioactive decay of radon) normally into an exceptionally thin sheet of gold foil held in an evacuated chamber. A zinc sulfide screen was attached to the base of a microscope in such a way that incident alpha particles could strike the zinc sulfide detector, and the emitted fluorescence could be observed through the microscope. The microscope could be repositioned at different angles with respect to the foil to observe deflection in different directions. Deflected alpha particles should have been deflected by at most a few degrees since J.J. Thompsons plum pudding model of the atom was prevalent and accepted at the time. In Thompsons model, the positive charge of an atom is distributed almost uniformly throughout the atom and electrons exist as smaller particles inside this pudding. Alpha particles are essentially helium nuclei (unknown at that time), consisting of two protons and two neutrons. What was known is that alpha particles are huge in comparison to electrons, and should not have been deflected much by their presence. One problem with the plum pudding model of the atom is that electrons were assumed to be motionless with regard to the atom, which would imply the impossibility for such a distribution to remain stable. Coulombs law predicts that the entire atom should collapse due to the force exertion between opposite charges accelerating their components masses. Yet, if electrons maintained orbital motion, stability could be achieved except for the fact that Maxwells electrodynamic equations predict that accelerating charges lose energy to radiation. So the electrons would lose energy and spiral into the nucleus.

However, the Rutherford experiment did produce deflections at completely unexpected angles, some at nearly 180 degree separation from the expected value, moving back toward the alpha source. As stated by Rutherford: It was quite the most incredible event that has ever happened to me in my life. It was almost as incredible as if you fired a 15-inch shell at a piece of tissue paper and it came back and hit you. On consideration, I realized that this scattering backward must be the result of a single collision, and when I made calculations I saw that it was impossible to get anything of that order of magnitude unless you took a system in which the greater part of the mass of the atom was concentrated in a minute nucleus. It was then that I had the idea of an atom with a minute massive centre, carrying a charge. Rutherfords experiment comprises the discovery of and support for the nuclear theory of the atom. Electrons do orbit a small, dense, positively charged mass or nucleus. [6] Then, in 1913, Neils Bohr proposed his solution to the stability dilemma, simultaneously providing a model for the Balmer-Rydberg-Ritz formula. Primarily, Bohr recognized that Maxwells electrodynamic laws were developed in response to observations on an ultra-atomic scale, and describe such Coulomb force interactions. If Maxwells equations do not apply on a subatomic scale, the issue of radiation is of no concern to an electron in terms of losing orbital kinetic energy when it remains in the same energy state. Considering the simplest case possible, the hydrogen atom, such that the only rotational variables are that of a single proton, the nucleus, and a single electron, both moving about their center of mass. The total energy of the atom is represented by where is total energy, is kinetic energy and is potential energy. , the reduced mass of the is the mass of the nucleus (in this case a

The rotational kinetic energy is given by system such that proton) and

where

is the mass of the electron and

is the electrons orbital velocity. The coulombic potential energy is given by

where

is the atomic number,

is the charge of an electron, and

is the radial

separation distance between proton and electron. with being the permittivity of free space. Thus,

is a standard electrodynamic constant becomes , and

total energy is given by

(neglecting rest mass).

Although this equation is correct, as stated, it isnt particularly useful since one is limited in ones measurements. One cannot accurately (at least directly) observe either of the values or . Utilizing the classical mechanics relationship that orbital potential energy, in this case the electrostatic force between the nucleus and electron, produces centripetal acceleration. Therefore, (centripetal force = electrostatic force). Although Bohr did not explicitly

use the quantum postulate, which states that the orbital angular momentum of such a system must be quantized such that , where is an integer 1 or greater. ( and is usually truncated where .

to the form .) Solving for unobservable variables, one gets

. Upon substituting these values into the energy equation, one obtains Each different value for n yields a different energy value, which means that the total energy for the hydrogen atom is quantized. is called the first Bohr radius and its value must be tailored

to fit the specific atom for whose energy one is solving. The lowest energy for an atom occurs at , and the negative of this energy represents the ionization energy for the hydrogen atom. In order to acquire the Balmer-Rydberg-Ritz formula, Bohr made the assumption that the absorption or emission of electromagnetic radiation by an atom is due to a transition from one quantum state of the atom to another. For such transitions whose quantum numbers are and

such that

is greater than

, the energy differences between quantum numbers is shown to ( ) ( )

satisfy a condition likened to that of blackbody emitters. In particular where

is the frequency of either absorbed or emitted radiation. This shows that as an

atoms electron transitions between states, a photon is either absorbed or emitted with an energy directly corresponding to the above stated Rydberg-Ritz formula in the following form: constant is shown to be . [4][5] . Using these parameters, we obtain the Balmer( ) where Rydbergs

The above described Bohr model very closely agrees with many observed features of single electron systems but fails to explain the spectral minutiae of multi electron systems or the fact that what appears to be a single spectral line even for a single electron system is actually a series of multiple tightly spaced lines when observed under high resolution. Even so, the general accuracy of the Bohr model for single electron systems provided the insight that the energies of all atoms are quantized and the observed spectral lines emitted from excited gaseous states arise from transitions governed by the above equation for the changes in energy state. Bohrs prominent result led to further development, but with the exception of the hydrogen model, the Bohr model fails to predict numerical values for the individual energies of the electron state concerned with the transitions. In 1924, Louis de Broglie shared an unexpected insight correlating the nature of photons to electrons. Before de Broglie drew this correlation, electrons were assumed to be corpuscular in nature, as this fit with well established experimental evidence, ingluding: the deflection of cathode rays by electromagnetic fields and ensuing charge to mass ratio for electrons; Robert Millikans oil drop experiment and determination of electric charge for an electron (and therefore

the mass also); the demonstration that electron velocity is dependent upon the medium through which it travels and not uniform for any given medium; and the observation of electron tracks in supersaturated vapor (a cloud chamber). The Bohr model also seemed to support a corpuscular nature for electrons. De Broglie speculated that the particle-like nature of the photon in a light wave could entail a reciprocal behavior in corpuscular matter. De Broglie observed that all natural phenomena involve only two entities: matter and radiation. The first described by both classical and relativistic mechanics, the second described by electromagnetic wave theory. Symmetry frequently plays a role in natural phenomena, and de Broglie speculated whether any such symmetry exists between particulate matter and electromagnetic radiation. He began developing his theory by drawing correlations between classical mechanics and geometric optics. For example, particle trajectory is comparable to the path of a light ray, particulate potential energy is similar to the optic refractive index, both of which are a function of position. Also, the mechanical principle of de Maupertuis is similar to the optical principle of Fermat. The principle of de Maupertuis from mechanics is a specific case of the more general principle of least action. In basic terms, this principle states that the integral over the

trajectory of a particle is a minimum, where E is total energy, V is potential energy (and hence EV is kinetic energy), and s is the path length. The principle of Fermat from optics is the principle of least time. This principle states that the integral ( ) over the path of a light ray is a minimum, where n is the refractive

index and s is again path length. De Broglie eventually concluded and showed that waves in general that follow the same trajectory as the particle they are associated with, such as the

specific case of a light wave associated with a photon, must satisfy Einsteins equation for the linear momentum of a photon: . This draws a generally unexpected bridge between the

fields of mechanics and optics, and remarkably accounts for some previously undefined quantum phenomena. As shown by de Broglie, Einsteins equation for the linear momentum of a photon accounts for the quantization of angular momentum for the Bohr model of the atom, thereby modifying the idea of a purely corpuscular electron, yet still being compatible with the corpuscular nature of light. De Broglie went on to point out that the electron in a stable Bohr orbit can be accurately regarded as a standing wave or else the wave would cancel itself due to phase shifts and destructive interference. Therefore, the standing wave necessitates an integer multiple of wavelengths and can be written as with being an integer 1 or greater. Upon ,

substitution for the wavelength, lambda, from Einsteins equation, we obtain simply the Bohr quantum condition.

The first experimental corroboration of de Broglies matter waves came in 1927 when Clinton Davisson and Lester Germer directed a beam of electrons onto the surface of a nickel crystal in Bell Laboratories of New York. They found that the electrons were diffracted in like manner to x-ray diffraction in a crystal lattice, and were able to use the Bragg equation along with the known spacing of a nickel crystal to calculate the wavelengths of the electrons. These wavelengths corresponded in excellent agreement with those set forth by de Broglies matterwave duality relationship. This experiment was the first evidence that electrons are, in fact, both particles and waves simultaneously. [3][5]

All of these prior theories and corroborating experimentation forms the basis of what Schrdinger used to formulate his quantum mechanical wave equation. The existence of matterwaves implies the necessary existence of some wave equation to describe them. No model to this point had accurately described the observed quantum features of atoms. But even though the Bohr model of the atom is unsuccessful in accounting for the quantum states of an atom with more than one electron, the features presented in Bohrs model must also be present in any more complete representation of quantum theory. Bohr extensively used his correspondence principle, which states that any complete theory of quantum mechanics and the laws governing subatomic scales must reduce to classical mechanical laws under such limiting conditions that classical laws are known and shown to be valid. Schrdinger began by presenting de Broglies matter-waves, or phase-waves and by using the previously defined correlations between Hamiltonian classical mechanics and the optical principal of Fermat. De Broglies matter-waves were thought to correspond to the motion of material points, especially with regard to electrons and protons. Schrdingers position is rather that material points actually consist of wave-systems and nothing but wavesystems. Under this proposal, all variance in matter is simply due to a variance in wave structure, since the matter is completely made up by the wave and nothing else. Schrdinger readily admitted that his extreme conception may prove to be incorrect since it had not offered any explanation for why such wave-systems are observed in the natural world as mass-points of definite mass and charge. Schrdinger also presented the case that the opposing viewpoint, neglecting wave-particle duality and treating purely material points, had led to severe complications and discrepancies with regard to atomic mechanics, making it highly desirable to develop a new method of conceiving such systems. Schrdingers proposition is a

systematic correlation between these two extremes in an attempt to describe a correlation between every feature of physical phenomena. Schrdinger presented the following advantages for his wave theory over the thenpresiding wave theory. Both the laws of motion governing a particle, and the quantum conditions are simultaneously satisfied and solved for by a single Hamiltonian principle. The inconsistency existing to that point in quantum theory between the frequencies of motion and emission vanishes since the frequency of emission coincides with the differences of the frequency of motion. A definitively localized electric charge in regard to position and time can be correlated to the proposed wave-system, and coupled with Maxwells equations for electrodynamics, which account for the frequencies, intensities and polarizations of emitted light, makes a great number of correspondence and selection principles unnecessary. It seemed to Schrdinger that it would be possible, using his wave-theory, to pursue in far greater detail the transitions between energy states that had remained inexplicable and could not be accurately described by the Bohr model. Lastly, on points where Schrdingers new theory disagreed with the previous theory with respect to particular values for energy or frequency, his new theory was (and is) better supported by experimental evidence. [7] After De Broglie developed his matter-waves conceptualization of particle-wave duality using a correlation between the mechanics principle of Maupertuis and the optics principle of Fermat, Schrdinger added significantly to the scope of this correlation. He developed a general formula for describing quantum phenomena that gives rise to quantum numbers naturally unlike Plancks or Bohrs equations by which one had to assume the numbers based on previously derived logic rather than receiving them experimentally. Schrdinger reasoned that the most

fundamental nature of waves is their interference behavior. Therefore, he reasoned that it should be possible to begin with the classical wave equation and mathematically formulate a bridge to interconnect wave optics to general wave mechanics capable of describing and predicting quantum phenomena. For Maxwells electromagnetic waves, we can derive the wave equation governing the waves motion through space as follows. We know from Maxwells equations that , , and where E is the electric field, B is the magnetic represents Faradays law, and yields

field and c is the speed of light in a vacuum.

the generation of an electromotive force (voltage) as induced by fluctuations in a nearby magnetic field. represents Amperes law and is essentially the reverse of

Faradays law. It shows that a moving charged particle (and changing electric field) generates a resulting magnetic field. and are essentially Gauss law as applied to ( ( [ ]) ) , where [ ] in which [ ] can

electricity and magnetism. From these laws, it is shown that the familiar vector identity can apply as such: be any vector. Therefore ( [ ])

, which is the electromagnetic wave equation. [8]

Restricting the dimensional construct to a uni dimensional system and replacing our vector E with ( , the one dimensional classical wave equation is where

) represents the amplitude in the classical sense with respect to position and time, and c is and solving the =
( )

the speed of light in a vacuum. Reforming this equation to differential equation yields an solution of the form ( )

where

(spatial frequency) , by (

(temporal frequency), C is some constant and is wavelength,

is the phase, given

) in which x is position,

is frequency and t is time.

Replacing variables used in the classical model and using the same differential equation to solve, Schrdinger could incorporate the two primary quantum relationships known at that time, waveparticle duality and quantized radiation using de Broglies wavelength relationship and the Planck-Bohr relationship for frequency, yielding the phase as , and ( where ,

. Upon taking the first derivative of psi with respect to time one gets ) , which is easily reshaped to the form . Upon taking the

first derivative of psi with respect to position instead of with respect to time one gets ( ) which can also easily be reshaped to the form . The previous form

of the equation can be understood as the x component of a linear momentum operator. That is, the linear momentum of psi can be represented by , a differential operator acting on the

wave function with respect to position. For a classical system of mass m in a conservative force field, the total energy (in the x direction) is given by ( ) ( ) where ( )

, all else previously defined. Substituting the ( )=

momentum operator into this total energy equation yields

( ) in which the exact form for V(x) depends upon the system in question. Substituting this energy operator back into yields * ( )+ . [2][5][8]

This form, *

( )+

, is the one dimensional Schrdinger wave with the ) . This

equation. To generalize the equation to three dimensions, we can simply replace laplacian operator , V(x) with V(x,y,z) and ( ) with (

equation and its foundations have revolutionized the conceptualization of physics at one the most foundational levels of human understanding. This equation leads to the ability to solve for the wave system of any particle, by which one can describe every physical property of the such a system. Although Schrdinger attempted to interpret his wave functions as electric charge densities to no avail, Max Born developed the probabilistic interpretation of Schrdingers equation by which all quantum solutions are described by probability densities rather than charge densities. Nevertheless, Schrdingers insight and development of this equation has shown no discrepancies with any conducted experiment, and has continuously been validated by experimental evidence. This feat forms the foundation of quantum mechanics.

Works Cited
[1] A. Einstein, Uber einen die Erzeugung und Verwandlung des Lichtes betreffenden heuristischen Gesichtspunkt / On a heuristic viewpoint concerning the production and transformation of light, Annalen der Physik 322 (4th series 17), (6), 132-148 (1905). [2] D.J. Griffiths, Introduction to Quantum Mechanics, (Prentice Hall, New Jersey, 2005), 2nd ed. [3] L. de Broglie, Recherches sur la theorie des quanta / On the theory of quanta, Annales de Physique 3, 22 (1925). [4] N. Bohr, On the constitution of atoms and molecules, Philosophical Magazine 26, (6), 1-25 (1913). [5] Pilar, Frank. Elementary Quantum Chemistry. second edition. New York: McGraw-Hill, 1990. 124. Print. [6] Rutherford, Ernest. "The Scattering of alpha and beta Particles by Matter and the Structure of the Atom."London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 21.125 (1911) [7] Schrodinger, Erwin. "An Undulatory Theory of the Mechanics of Atoms and Molecules." Physical Review. 28.6 (1926): 1049-1070. Print. [8] Ward, David. "How to Derive the Schrodinger Equation."arvix.org/abs/physics. Massachusetts Institute of Technology, 2 Feb 2008. Web. 25 Feb 2013. <http://arxiv.org/pdf/physics/0610121.pdf>.