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Physics Today
Bohr’s molecular model and the melding of classical and quantum mechanics M. Ya. Amusia
Published Aug 1, 2014 • 1 citation
Abstract With considerable interest I read the article “Bohr’s molecular model, a century later” by Anatoly Svidzinsky, Marlan Scully, and Dudley Herschbach (Physics Today, January 2014, page 33). It is always interesting to see how our current understanding sheds new light on the revolutionary scientific ideas of the past. I agree with the authors that although quantum mechanics is the real basis for atomic- and molecular-physics computations, the old Bohr model that treats electrons in atoms like tiny planets moving around the sun-nucleus is intuitively clear and very attractive.As I see it, the aim of the article is to show how to use Bohr’s approach to treat not only simple atoms but molecules. An important point in that approach is reconciliation of quantum mechanics with Bohr’s ideas. The authors claim that in infinite dimensions, quantum mechanics “morphs into classical mechanics.”I cannot say, however, that the infinite-dimension system is a clarifying model to describe physical or chemical objects. I do not see that the reference to chromodynamics (and to Edward Witten’s article in Physics Today, July 1980, page 38) is a clarifying one. Far from convincing are statements like “Hence the large-D limit, where 1/D → 0, is closer to the real world (1/D = 1/3) than is the oft-used D = 1 regime. Indeed, results obtained at large D usually resemble those for D = 3.” I confess it sounds too lacking in rigor to be convincing.But the large-D limit per se is not what bothers me. Of great concern is the assumption that the radial part of the D-dimensional Schrödinger equation in Hartree units looks like this:(1)where Z is the nuclear charge and l is the angular momentum.Equation (1) has no sense for D = 1. Indeed, in one dimension, a finite angular momentum requires infinite speed of a rotating particle. Therefore, for D = 1, the correct equation is(2)which does not follow from equation (1) at D = 1.But most important is that equation (1) implies that the Coulomb potential does not depend on D. That could have been considered correct before it became clear that the Coulomb law follows from Maxwell’s equations when one considers a field generated by a point-like electric charge. So to obtain the Coulomb law for a two-dimensional space, one has to consider Maxwell equations in a two-dimensional world. For a point-like charge, those equations lead to a 1/(ln r) instead of 1/r dependence. If one takes into account the D-dependence of the Coulomb potential, derivations performed in the Physics Today article become meaningless. Indeed, when using an unrealistic equation (1), how can one believe that it illuminates Bohr’s quite realistic and physical postulates?© 2014 American Institute of Physics.
DOI 10.1063/pt.3.2459 Related papers Bohr’s molecular model and the melding of classical and quantum mechanics
Leonard D. Mlodinow
Permit me to add some information to the article entitled, “Bohr’s molecular model, a century later.” The authors discuss the idea of “dimensional scaling,” approximating the spectra of atoms and molecules by employing perturbation theory to expand around the infinite-dimension/classical limit. That technique of approximating the Schrödinger equation, originally called the 1/N expansion, was developed and applied to numerous problems in the 1980s, including simple atoms, quarkonium, and the hydrogen molecule.11. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0,22. C. M. Bender, L. D. Mlodinow, N. Papanicolaou, Phys. Rev. A 25, 1305 (1982). https://doi.org/10.1103/PhysRevA.25.1305,33. T. Imbo, U. Sukhatme, Phys. Rev. D 31, 2655 (1985); https://doi.org/10.1103/PhysRevD.31.2655M. Kumar, A. Srivastava, J. K. Bhattacharjee, K. Banerjee, Phys. Lett. A 117, 226 (1986). https://doi.org/10.1016/0375-9601(86)90081-2 It grew out of attempts in the 1970s to formulate quantum chromodynamics in the limit of a large number of colors. The use of the 1/N expansion in atomic physics was discussed by Edward Witten (Physics Today, July 1980, page 38), who pointed out that his discussion was based on work that applied the method to hydrogen and helium atoms.11. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0The work in reference 11. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0 made use of algebraic methods for the analysis, but the coordinate space method was also developed and was initially used to treat the strong-field Zeeman effect.22. C. M. Bender, L. D. Mlodinow, N. Papanicolaou, Phys. Rev. A 25, 1305 (1982). https://doi.org/10.1103/PhysRevA.25.1305 A nice description of the status of the field at the time was given by Laurence Yaffe (Physics Today, August 1983, page 50). Many additional applications of that method in the physics literature may be found in reference 44. A. Chatterjee, Phys. Rep. 186, 249 (1990). https://doi.org/10.1016/0370-1573(90)90048-7.REFERENCESSection:ChooseTop of pageREFERENCES <<1. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 , Google ScholarCrossref, ISIL. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0, , Google ScholarCrossref, ISI2. C. M. Bender, L. D. Mlodinow, N. Papanicolaou, Phys. Rev. A 25, 1305 (1982). https://doi.org/10.1103/PhysRevA.25.1305, Google ScholarCrossref, ISI3. T. Imbo, U. Sukhatme, Phys. Rev. D 31, 2655 (1985); https://doi.org/10.1103/PhysRevD.31.2655, Google ScholarCrossref, ISIM. Kumar, A. Srivastava, J. K. Bhattacharjee, K. Banerjee, Phys. Lett. A 117, 226 (1986). https://doi.org/10.1016/0375-9601(86)90081-2, , Google ScholarCrossref, ISI4. A. Chatterjee, Phys. Rep. 186, 249 (1990). https://doi.org/10.1016/0370-1573(90)90048-7, Google ScholarCrossref, ISI© 2014 American Institute of Physics.
Physics Today • Aug 1, 2014• 1 citation
Bohr’s molecular model and the melding of classical and quantum mechanics
Petar Grujić
Anatoly Svidzinsky, Marlan Scully, and Dudley Herschbach have illustrated well how the molecular theory might have looked had quantum mechanics not been invented. It’s worth noting that Niels Bohr was not alone in his attempts to extend semiclassical mechanics to systems more complex than the hydrogen atom. From 1913 to 1925, many semiclassical models of two-electron systems were proposed.As we see from the authors’ figure 3a, Bohr assumed that electrons in hydrogen molecules move around the molecular axis out of phase. It is a remarkable fact that Werner Heisenberg put forward in 1922 a two-electron atomic model that had electrons moving similarly out of phase and that ascribed a fractional quantum number (½) to the bending mode of the configuration.11. G. Tanner, K. Richter, J.-M. Rost, Rev. Mod. Phys. 72, 497 (2000). https://doi.org/10.1103/RevModPhys.72.497 Although Heisenberg’s model predicted the ground-state helium level, which was in excellent agreement with the spectroscopic data, Bohr opposed the model, since a noninteger quantum number was considered sacrilege. For the same reason, Bohr never published his own results. However, the asynchronous two-electron atomic model turned out to be the fertile one, though the corresponding classical configurations can have very complex structure.22. P. Grujic, N. Simonovic, J. Phys. B 28, 1159 (1995). https://doi.org/10.1088/0953-4075/28/7/011REFERENCESSection:ChooseTop of pageREFERENCES <<1. G. Tanner, K. Richter, J.-M. Rost, Rev. Mod. Phys. 72, 497 (2000). https://doi.org/10.1103/RevModPhys.72.497, Google ScholarCrossref, ISI2. P. Grujic, N. Simonovic, J. Phys. B 28, 1159 (1995). https://doi.org/10.1088/0953-4075/28/7/011, Google ScholarCrossref, ISI© 2014 American Institute of Physics.
Physics Today • Aug 1, 2014• 1 citation
Bohr’s molecular model and the melding of classical and quantum mechanics
Anatoly A. Svidzinsky, Marlan O. Scully, Dudley R. Herschbach
Svidzinsky, Scully, and Herschbach reply: We agree with M. Y. Amusia that a statement we made about the infinite dimension limit is “lacking in rigor.” It was intended simply to provide heuristic insight into why, for a wide variety of problems, the large-D limit has proven to be a useful starting approximation to obtain results for D = 3.Amusia’s other concerns are answered in a 1975 paper on a D-scaling treatment of helium by David Herrick and Frank Stillinger.11. D. R. Herrick, F. H. Stillinger, Phys. Rev. A 11, 42 (1975). https://doi.org/10.1103/PhysRevA.11.42 They gave a rigorous derivation of the D-dimensional hydrogen atom Hamiltonian, shown as equation 1 in Amusia’s letter. That solution applies for D ≥ 2, as implied in the figure included in box 1 of our article. Herrick and Stillinger also showed that for the correct D → 1 limit, the Z/r term becomes a δ-function. In D-scaling, contrary to Amusia’s assumption, the D = 3 form of Coulomb’s law can be used for dimensional continuation to the large-D limit. The D-dependent similarity transformation affects the Laplacian, not the potential energy. Both theory and application are amply presented in references given in our article (particularly references 8–11). D-scaling, using just elementary algebra, has attained correlation energies for multielectron atoms with accuracy comparable to or better than conventional electronic calculations.22. See, for example, S. Kais, R. Bleil, J. Chem. Phys. 102, 7472 (1995); https://doi.org/10.1063/1.469059D. K. Watson, D. Z. Goodson, Phys. Rev. A 51, R5 (1995), and references therein. https://doi.org/10.1103/PhysRevA.51.R5The papers of Leonard Mlodinow33. See D. R. Herschbach, J. Chem. Phys. 84, 838 (1986), for analysis of the papers cited in reference 1 of Mlodinow’s letter. https://doi.org/10.1063/1.450584 and several other authors, especially the earlier paper by Herrick and Stillinger,11. D. R. Herrick, F. H. Stillinger, Phys. Rev. A 11, 42 (1975). https://doi.org/10.1103/PhysRevA.11.42 fostered the development of D-scaling for electronic structure. Since the kinship of Bohr’s model to dimensional scaling was not recognized until 2005, we did not dwell on that history, other than citing the tutorial article by Edward Witten. The treatment of H2 that Mlodinow cites in the second part of his reference 3 is a deliberately drastic approximation and gives less than 40% of the bond dissociation energy.As emphasized by Petar Grujic, the bold, perplexing enterprise by Niels Bohr motivated much further work melding classical and quantum mechanics. We note that D-scaling has a distinctive character. It might aptly be termed “semiquantum” rather than semiclassical. Although in the large-D limit the equations become classical, quantum mechanics is hidden in the D-dependent units adopted for distance and energy. At that limit, electrons take fixed positions in the D-scaled space and the first-order correction in (1/D) has them execute harmonic vibrations about those positions. In the prequantum era, such behavior was postulated by Gilbert Lewis and Irving Langmuir,44. P. Coffey, Cathedrals of Science: The Personalities and Rivalries That Made Modern Chemistry, Oxford U. Press, New York (2008), chap. 5, esp. p. 139. motivated by chemical arguments but disdained by physicists and considered incompatible with the Bohr model.REFERENCESSection:ChooseTop of pageREFERENCES <<CITING ARTICLES1. D. R. Herrick, F. H. Stillinger, Phys. Rev. A 11, 42 (1975). https://doi.org/10.1103/PhysRevA.11.42, Google ScholarCrossref, ISI2. See, for example, S. Kais, R. Bleil, J. Chem. Phys. 102, 7472 (1995); https://doi.org/10.1063/1.469059, Google ScholarCrossref, ISID. K. Watson, D. Z. Goodson, Phys. Rev. A 51, R5 (1995), and references therein. https://doi.org/10.1103/PhysRevA.51.R5, , Google ScholarCrossref, ISI3. See D. R. Herschbach, J. Chem. Phys. 84, 838 (1986), for analysis of the papers cited in reference 1 of Mlodinow’s letter. https://doi.org/10.1063/1.450584, Google ScholarCrossref, ISI4. P. Coffey, Cathedrals of Science: The Personalities and Rivalries That Made Modern Chemistry, Oxford U. Press, New York (2008), chap. 5, esp. p. 139. Google Scholar© 2014 American Institute of Physics.
Physics Today • Aug 1, 2014• 2 citations
Classical Quantum Mechanics
Randell L Mills
Despite its successes, quantum mechanics (QM) has remained mysterious to all who have encountered it. Starting with Bohr and progressing into the present, the departure from intuitive, physical reality has widened. The connection between QM and reality is more than just a “philosophical” issue. It reveals that QM is not a correct or complete theory of the physical world and that inescapable internal inconsistencies and incongruities arise when attempts are made to treat it as physical as opposed to a purely mathematical “tool.” Some of these issues are discussed in a review by F. Laloe [Am. J. Phys. 69, 655 (2001)]. In an attempt to provide some physical insight into atomic problems and starting with the same essential physics as Bohr of e moving in the Coulombic field of the proton and the wave equation as modified by Schrodinger, a classical approach is explored that yields a remarkably accurate model and provides insight into physics on the atomic level. The proverbial view, deeply seated in the wave-particle duality notion, that there is no large-scale physical counterpart to the nature of the electron may not be correct. Physical laws and intuition may be restored when dealing with the wave equation and quantummechanical problems. Specifically, a theory of classical quantum mechanics (CQM) is derived from first principles that successfully applies physical laws on all scales. Rather than using the postulated Schrodinger boundary condition “Ψ → 0 as r → ∞,” which leads to a purely mathematical model of the electron, the constraint is based on experimental observation. Using Maxwell’s equations, the classical wave equation is solved with the constraint that the bound (n = 1)state electron cannot radiate energy. By further application of Maxwell’s equations to electromagnetic and gravitational fields at particle production, the Schwarzschild metric is derived from the classical wave equation, which modifies general relativity to include conservation of spacetime in addition to momentum and matter/energy. The result gives a natural relationship among Maxwell’s equations, special relativity, and general relativity. CQM holds over a scale of spacetime of 85 orders of magnitude — it correctly predicts the nature of the universe from the scale of the quarks to that of the cosmos. A review is given by G. Landvogt [Internat. J. Hydrogen Energy 28, 1155 (2003)].
Physics Essays • Dec 1, 2003• 26 citations
Z. Ficek
This chapter illustrates Niels Bohr's ideas in some detail. In the formulation of his model, Bohr assumed that the electron in the hydrogen atom moves under the influence of the Coulomb attraction between it and the positively charged nucleus, as assumed in classical mechanics. The Bohr model was very successful in explaining the discrete atomic spectra of one-electron atoms. The Bohr model is, of course, a theoretical model of an atom. Using Bohr's quantization postulate, find the linear velocity of the electron's sphere. To find the radius of the orbit, Bohr postulated that the angular momentum of the electron is quantized, i.e., it can only take values that are integer multiples of ħ. The chapter begins with considering the classical equation of motion for the electron in a circular orbit, which is based on Newton's laws of motion and Coulomb's law of electric force.
• Mar 3, 2017• 0 citations
With considerable interest I read the article “Bohr’s molecular model, a century later” by Anatoly Svidzinsky, Marlan Scully, and Dudley Herschbach (Physics Today, January 2014, page 33). It is always interesting to see how our current understanding sheds new light on the revolutionary scientific ideas of the past. I agree with the authors that although quantum mechanics is the real basis for atomic- and molecular-physics computations, the old Bohr model that treats electrons in atoms like tiny planets moving around the sun-nucleus is intuitively clear and very attractive.As I see it, the aim of the article is to show how to use Bohr’s approach to treat not only simple atoms but molecules. An important point in that approach is reconciliation of quantum mechanics with Bohr’s ideas. The authors claim that in infinite dimensions, quantum mechanics “morphs into classical mechanics.”I cannot say, however, that the infinite-dimension system is a clarifying model to describe physical or chemical objects. I do not see that the reference to chromodynamics (and to Edward Witten’s article in Physics Today, July 1980, page 38) is a clarifying one. Far from convincing are statements like “Hence the large-D limit, where 1/D → 0, is closer to the real world (1/D = 1/3) than is the oft-used D = 1 regime. Indeed, results obtained at large D usually resemble those for D = 3.” I confess it sounds too lacking in rigor to be convincing.But the large-D limit per se is not what bothers me. Of great concern is the assumption that the radial part of the D-dimensional Schrödinger equation in Hartree units looks like this:(1)where Z is the nuclear charge and l is the angular momentum.Equation (1) has no sense for D = 1. Indeed, in one dimension, a finite angular momentum requires infinite speed of a rotating particle. Therefore, for D = 1, the correct equation is(2)which does not follow from equation (1) at D = 1.But most important is that equation (1) implies that the Coulomb potential does not depend on D. That could have been considered correct before it became clear that the Coulomb law follows from Maxwell’s equations when one considers a field generated by a point-like electric charge. So to obtain the Coulomb law for a two-dimensional space, one has to consider Maxwell equations in a two-dimensional world. For a point-like charge, those equations lead to a 1/(ln r) instead of 1/r dependence. If one takes into account the D-dependence of the Coulomb potential, derivations performed in the Physics Today article become meaningless. Indeed, when using an unrealistic equation (1), how can one believe that it illuminates Bohr’s quite realistic and physical postulates?© 2014 American Institute of Physics.
Permit me to add some information to the article entitled, “Bohr’s molecular model, a century later.” The authors discuss the idea of “dimensional scaling,” approximating the spectra of atoms and molecules by employing perturbation theory to expand around the infinite-dimension/classical limit. That technique of approximating the Schrödinger equation, originally called the 1/N expansion, was developed and applied to numerous problems in the 1980s, including simple atoms, quarkonium, and the hydrogen molecule.11. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0,22. C. M. Bender, L. D. Mlodinow, N. Papanicolaou, Phys. Rev. A 25, 1305 (1982). https://doi.org/10.1103/PhysRevA.25.1305,33. T. Imbo, U. Sukhatme, Phys. Rev. D 31, 2655 (1985); https://doi.org/10.1103/PhysRevD.31.2655M. Kumar, A. Srivastava, J. K. Bhattacharjee, K. Banerjee, Phys. Lett. A 117, 226 (1986). https://doi.org/10.1016/0375-9601(86)90081-2 It grew out of attempts in the 1970s to formulate quantum chromodynamics in the limit of a large number of colors. The use of the 1/N expansion in atomic physics was discussed by Edward Witten (Physics Today, July 1980, page 38), who pointed out that his discussion was based on work that applied the method to hydrogen and helium atoms.11. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0The work in reference 11. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0 made use of algebraic methods for the analysis, but the coordinate space method was also developed and was initially used to treat the strong-field Zeeman effect.22. C. M. Bender, L. D. Mlodinow, N. Papanicolaou, Phys. Rev. A 25, 1305 (1982). https://doi.org/10.1103/PhysRevA.25.1305 A nice description of the status of the field at the time was given by Laurence Yaffe (Physics Today, August 1983, page 50). Many additional applications of that method in the physics literature may be found in reference 44. A. Chatterjee, Phys. Rep. 186, 249 (1990). https://doi.org/10.1016/0370-1573(90)90048-7.REFERENCESSection:ChooseTop of pageREFERENCES <<1. L. D. Mlodinow, N. Papanicolaou, Ann. Phys. 128, 314 (1980); https://doi.org/10.1016/0003-4916(80)90323-1 , Google ScholarCrossref, ISIL. D. Mlodinow, N. Papanicolaou, Ann. Phys. 131, 1 (1981). https://doi.org/10.1016/0003-4916(81)90181-0, , Google ScholarCrossref, ISI2. C. M. Bender, L. D. Mlodinow, N. Papanicolaou, Phys. Rev. A 25, 1305 (1982). https://doi.org/10.1103/PhysRevA.25.1305, Google ScholarCrossref, ISI3. T. Imbo, U. Sukhatme, Phys. Rev. D 31, 2655 (1985); https://doi.org/10.1103/PhysRevD.31.2655, Google ScholarCrossref, ISIM. Kumar, A. Srivastava, J. K. Bhattacharjee, K. Banerjee, Phys. Lett. A 117, 226 (1986). https://doi.org/10.1016/0375-9601(86)90081-2, , Google ScholarCrossref, ISI4. A. Chatterjee, Phys. Rep. 186, 249 (1990). https://doi.org/10.1016/0370-1573(90)90048-7, Google ScholarCrossref, ISI© 2014 American Institute of Physics.
Anatoly Svidzinsky, Marlan Scully, and Dudley Herschbach have illustrated well how the molecular theory might have looked had quantum mechanics not been invented. It’s worth noting that Niels Bohr was not alone in his attempts to extend semiclassical mechanics to systems more complex than the hydrogen atom. From 1913 to 1925, many semiclassical models of two-electron systems were proposed.As we see from the authors’ figure 3a, Bohr assumed that electrons in hydrogen molecules move around the molecular axis out of phase. It is a remarkable fact that Werner Heisenberg put forward in 1922 a two-electron atomic model that had electrons moving similarly out of phase and that ascribed a fractional quantum number (½) to the bending mode of the configuration.11. G. Tanner, K. Richter, J.-M. Rost, Rev. Mod. Phys. 72, 497 (2000). https://doi.org/10.1103/RevModPhys.72.497 Although Heisenberg’s model predicted the ground-state helium level, which was in excellent agreement with the spectroscopic data, Bohr opposed the model, since a noninteger quantum number was considered sacrilege. For the same reason, Bohr never published his own results. However, the asynchronous two-electron atomic model turned out to be the fertile one, though the corresponding classical configurations can have very complex structure.22. P. Grujic, N. Simonovic, J. Phys. B 28, 1159 (1995). https://doi.org/10.1088/0953-4075/28/7/011REFERENCESSection:ChooseTop of pageREFERENCES <<1. G. Tanner, K. Richter, J.-M. Rost, Rev. Mod. Phys. 72, 497 (2000). https://doi.org/10.1103/RevModPhys.72.497, Google ScholarCrossref, ISI2. P. Grujic, N. Simonovic, J. Phys. B 28, 1159 (1995). https://doi.org/10.1088/0953-4075/28/7/011, Google ScholarCrossref, ISI© 2014 American Institute of Physics.
Svidzinsky, Scully, and Herschbach reply: We agree with M. Y. Amusia that a statement we made about the infinite dimension limit is “lacking in rigor.” It was intended simply to provide heuristic insight into why, for a wide variety of problems, the large-D limit has proven to be a useful starting approximation to obtain results for D = 3.Amusia’s other concerns are answered in a 1975 paper on a D-scaling treatment of helium by David Herrick and Frank Stillinger.11. D. R. Herrick, F. H. Stillinger, Phys. Rev. A 11, 42 (1975). https://doi.org/10.1103/PhysRevA.11.42 They gave a rigorous derivation of the D-dimensional hydrogen atom Hamiltonian, shown as equation 1 in Amusia’s letter. That solution applies for D ≥ 2, as implied in the figure included in box 1 of our article. Herrick and Stillinger also showed that for the correct D → 1 limit, the Z/r term becomes a δ-function. In D-scaling, contrary to Amusia’s assumption, the D = 3 form of Coulomb’s law can be used for dimensional continuation to the large-D limit. The D-dependent similarity transformation affects the Laplacian, not the potential energy. Both theory and application are amply presented in references given in our article (particularly references 8–11). D-scaling, using just elementary algebra, has attained correlation energies for multielectron atoms with accuracy comparable to or better than conventional electronic calculations.22. See, for example, S. Kais, R. Bleil, J. Chem. Phys. 102, 7472 (1995); https://doi.org/10.1063/1.469059D. K. Watson, D. Z. Goodson, Phys. Rev. A 51, R5 (1995), and references therein. https://doi.org/10.1103/PhysRevA.51.R5The papers of Leonard Mlodinow33. See D. R. Herschbach, J. Chem. Phys. 84, 838 (1986), for analysis of the papers cited in reference 1 of Mlodinow’s letter. https://doi.org/10.1063/1.450584 and several other authors, especially the earlier paper by Herrick and Stillinger,11. D. R. Herrick, F. H. Stillinger, Phys. Rev. A 11, 42 (1975). https://doi.org/10.1103/PhysRevA.11.42 fostered the development of D-scaling for electronic structure. Since the kinship of Bohr’s model to dimensional scaling was not recognized until 2005, we did not dwell on that history, other than citing the tutorial article by Edward Witten. The treatment of H2 that Mlodinow cites in the second part of his reference 3 is a deliberately drastic approximation and gives less than 40% of the bond dissociation energy.As emphasized by Petar Grujic, the bold, perplexing enterprise by Niels Bohr motivated much further work melding classical and quantum mechanics. We note that D-scaling has a distinctive character. It might aptly be termed “semiquantum” rather than semiclassical. Although in the large-D limit the equations become classical, quantum mechanics is hidden in the D-dependent units adopted for distance and energy. At that limit, electrons take fixed positions in the D-scaled space and the first-order correction in (1/D) has them execute harmonic vibrations about those positions. In the prequantum era, such behavior was postulated by Gilbert Lewis and Irving Langmuir,44. P. Coffey, Cathedrals of Science: The Personalities and Rivalries That Made Modern Chemistry, Oxford U. Press, New York (2008), chap. 5, esp. p. 139. motivated by chemical arguments but disdained by physicists and considered incompatible with the Bohr model.REFERENCESSection:ChooseTop of pageREFERENCES <<CITING ARTICLES1. D. R. Herrick, F. H. Stillinger, Phys. Rev. A 11, 42 (1975). https://doi.org/10.1103/PhysRevA.11.42, Google ScholarCrossref, ISI2. See, for example, S. Kais, R. Bleil, J. Chem. Phys. 102, 7472 (1995); https://doi.org/10.1063/1.469059, Google ScholarCrossref, ISID. K. Watson, D. Z. Goodson, Phys. Rev. A 51, R5 (1995), and references therein. https://doi.org/10.1103/PhysRevA.51.R5, , Google ScholarCrossref, ISI3. See D. R. Herschbach, J. Chem. Phys. 84, 838 (1986), for analysis of the papers cited in reference 1 of Mlodinow’s letter. https://doi.org/10.1063/1.450584, Google ScholarCrossref, ISI4. P. Coffey, Cathedrals of Science: The Personalities and Rivalries That Made Modern Chemistry, Oxford U. Press, New York (2008), chap. 5, esp. p. 139. Google Scholar© 2014 American Institute of Physics.
Despite its successes, quantum mechanics (QM) has remained mysterious to all who have encountered it. Starting with Bohr and progressing into the present, the departure from intuitive, physical reality has widened. The connection between QM and reality is more than just a “philosophical” issue. It reveals that QM is not a correct or complete theory of the physical world and that inescapable internal inconsistencies and incongruities arise when attempts are made to treat it as physical as opposed to a purely mathematical “tool.” Some of these issues are discussed in a review by F. Laloe [Am. J. Phys. 69, 655 (2001)]. In an attempt to provide some physical insight into atomic problems and starting with the same essential physics as Bohr of e moving in the Coulombic field of the proton and the wave equation as modified by Schrodinger, a classical approach is explored that yields a remarkably accurate model and provides insight into physics on the atomic level. The proverbial view, deeply seated in the wave-particle duality notion, that there is no large-scale physical counterpart to the nature of the electron may not be correct. Physical laws and intuition may be restored when dealing with the wave equation and quantummechanical problems. Specifically, a theory of classical quantum mechanics (CQM) is derived from first principles that successfully applies physical laws on all scales. Rather than using the postulated Schrodinger boundary condition “Ψ → 0 as r → ∞,” which leads to a purely mathematical model of the electron, the constraint is based on experimental observation. Using Maxwell’s equations, the classical wave equation is solved with the constraint that the bound (n = 1)state electron cannot radiate energy. By further application of Maxwell’s equations to electromagnetic and gravitational fields at particle production, the Schwarzschild metric is derived from the classical wave equation, which modifies general relativity to include conservation of spacetime in addition to momentum and matter/energy. The result gives a natural relationship among Maxwell’s equations, special relativity, and general relativity. CQM holds over a scale of spacetime of 85 orders of magnitude — it correctly predicts the nature of the universe from the scale of the quarks to that of the cosmos. A review is given by G. Landvogt [Internat. J. Hydrogen Energy 28, 1155 (2003)].
This chapter illustrates Niels Bohr's ideas in some detail. In the formulation of his model, Bohr assumed that the electron in the hydrogen atom moves under the influence of the Coulomb attraction between it and the positively charged nucleus, as assumed in classical mechanics. The Bohr model was very successful in explaining the discrete atomic spectra of one-electron atoms. The Bohr model is, of course, a theoretical model of an atom. Using Bohr's quantization postulate, find the linear velocity of the electron's sphere. To find the radius of the orbit, Bohr postulated that the angular momentum of the electron is quantized, i.e., it can only take values that are integer multiples of ħ. The chapter begins with considering the classical equation of motion for the electron in a circular orbit, which is based on Newton's laws of motion and Coulomb's law of electric force.
The mere existence of stable atoms, and their arrangement into many-atom nanoscale structures, can only be explained by the laws of quantum mechanics. Indeed, the accumulated evidence regarding the internal structure of atoms motivated the formulation of quantum mechanics at the early twentieth century. Here we focus on single-electron (hydrogen-like) atoms. The dominance of the Coulomb central potential between the electron and nucleus, translates into a simple Schrödinger equation for their relative position distribution. Solving rigorously this equation reveals quantized energy levels, which explains the emission spectra of hydrogen-like atoms (Rydberg formula). The corresponding stationary probability density distributions for the electron around the nucleus are reminiscent of the Bohr model, where classical trajectories (orbits) are replaced by single-electron wave functions (orbitals). The degeneracies of different orbitals, associated with three quantum numbers, will later turn out to be critical for understanding many-electron atoms and the periodic table of the elements.