Abstract
Quantum chemical calculations rely on a few fortunate circumstances, like usually small relativistic and negligible electrodynamic (QED) corrections, and large nuclei-to-electrons mass ratio. Unprecedented progress in computer technology has revolutionized quantum chemistry, making it a valuable tool for experimenters. It is important for computational chemistry to elaborate methods that look at molecules in a multiscale way, provide its global and synthetic description, and compare this description with those for other molecules. Only such a picture can free researchers from seeing molecules as a series of case-by-case studies. Chemistry is a science of analogies and similarities, and computational chemistry should provide the tools for seeing this.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Notes
- 1.
Computational chemistry contributed significantly to applied mathematics, because new methods had to be invented in order to treat the algebraic problems of a previously unknown scale (like for M of the order of billions), see, e.g., Roos (1972).
- 2.
That is, derived from the first principles of (non-relativistic) quantum mechanics.
- 3.
It is difficult to define what computational chemistry is. Obviously, whatever involves calculations in chemistry might be treated as part of it. This, however, sounds like a pure banality. The same is true with the idea that computational chemistry means chemistry that uses computers. It is questionable whether this problem needs any solution at all. If yes, the author sticks to the opinion that computational chemistry means quantitative description of chemical phenomena at the molecular level.
- 4.
Perhaps the best known is GAUSSIAN, elaborated by a large team headed by John Pople.
- 5.
The speed as well as the capacity of computer, memory increased about 100 billion times over a period of 40 years. This means that what now takes an hour of computations, would require in 1960 about 10,000 years of computing.
- 6.
In addition, we assume the computer is so clever, that it automatically rejects those solutions, which are not square-integrable or do not satisfy the requirements of symmetry for fermions and bosons. Thus, all non-physical solutions are rejected.
- 7.
Bond patterns are almost the same for different conformers.
- 8.
For a dipeptide one has something like ten energy minima, counting only the backbone conformations (and not counting the side chain conformations for simplicity). For a very small protein of, say, a hundred amino acids, the number of conformations is therefore of the order of 10100, a very large number exceeding the estimated number of atoms in the Universe.
- 9.
The low-frequency vibrations may be used as indicators to look at possible instabilities of the molecule, such as dissociation channels, formation of new bonds, etc. Moving all atoms, first according to a low-frequency normal mode vibration and continuing the atomic displacements according to the maximum gradient decrease, we may find the saddle point, and then, sliding down, detect the products of a reaction channel.
- 10.
The integration of \(\vert \Psi {\vert }^{2}\) is over the coordinates (space and spin ones) of all the electrons except one (in our case the electron 1 with the coordinates \(\mathbf{r},{\sigma }_{1}\)) and in addition the summation over its spin coordinate \(({\sigma }_{1})\). As a result one obtains a function of the position of the electron 1 in space: \(\rho (\mathbf{r})\). The wave function \(\Psi \) is antisymmetric with respect to exchange of the coordinates of any two electrons, and, therefore, \(\vert \Psi {\vert }^{2}\) is symmetric with respect to such an exchange. Hence, the definition of \(\rho \) is independent of the label of the electron we do not integrate over. According to this definition, \(\rho \) represents nothing else but the density of the electron cloud carrying N electrons, and is proportional to the probability density of finding an electron at position r.
- 11.
Strictly speaking the nuclear attractors do not represent critical points, because of the cusp condition (Kato 1957).
- 12.
We may also analyze \(\rho \) using a “magnifying glass” represented by − Δρ.
- 13.
One has to be aware of a related mathematical trap. Applying even the smallest uniform electric field immediately transforms the problem into one with metastable energy (the global minimum corresponding to dissociation of the system, with the energy equal to \(-\infty \)), see, e.g., Piela (2007), p. 642.
References
Bader, R. F. W. (1994). Atoms in molecules. A quantum theory. Oxford: Clarendon Press.
Bloch, F. (1928). PhD Thesis. University of Leipzig.
Born, M., & Oppenheimer, J. R. (1927). Zur Quantentheorie der Molekeln. AnnalenPhysik,389,457.
Boys, S. F., Cook, G. B., Reeves, C. M., & Shavitt, I. (1956). Automatic fundamental calculations of molecular structure. Nature, 178, 1207.
Brown, G. E., & Ravenhall, D. G. (1951). On the interaction of two electrons. Proceedings of the Royal Society A, 208, 552.
Cotton, F. A. (1990). Chemical applications of group theory (3rd ed.). New York: Wiley.
Dirac, P. A. M. (1928a). The quantum theory of the electron. Proceedings of the Royal Society (London), A117, 610.
Dirac, P. A. M. (1928b). The quantum theory of the electron. Part II. Proceedings of the Royal Society (London), A118, 351.
Feynman, R. P. (1939). Forces in molecules. Physical Review, 56, 340.
Fock, V. (1930a). Näherungsmethode zur Lösung des quantenmechanischen Mehrkörperproblems. Zeitschrift für Physik, 61, 126.
Fock, V. (1930b). “Selfconsistent field” mit Austausch für Natrium. Zeitschrift für Physik, 62, 795.
Fukui, K., & Fujimoto, H. (1968). An MO-theoretical interpretation of nature of chemical reactions. I. Partitioning analysis of interaction energy. Bulletin of the Chemical Society of Japan, 41, 1989.
Hartree, D. R. (1928). The wave mechanics of an atom with a non-coulomb central field. Part I. Theory and methods. Proceedings of the Cambridge Philosophical Society, 24, 89.
Heitler, W., & London, F. W. (1927). Wechselwirkung neutraler Atome und homöopolare Bindung nach der Quantenmechanik. Zeitschrift fü Physik, 44, 455.
Hellmann, H. (1937). Einführung in die quantenchemie. Leipzig: Deuticke.
Hund, F. (1927a). Zur Deutung der Molekelspektren. I. Zeitschrift für Physik, 40, 742.
Hund, F. (1927b). Zur Deutung der Molekelspektren. II. Zeitschrift für Physik, 42, 93.
Hund, F. (1927 c). Zur Deutung der Molekelspektren. III. Zeitschrift für Physik, 43, 805.
Hylleraas, E. A. (1929). Neue Berechnung der Energie des Heliums im Grundzustande, sowie des tiefsten Terms von Ortho-Helium. Zeitschrift für Physik, 54, 347.
James, H. M., & Coolidge, A. S. (1933). The ground state of the hydrogen molecule. Journal of Chemical Physics, 1, 825.
Kato, T. (1957). On the eigenfunctions of many-particle systems in quantum mechanics. Communications on Pure and Applied Mathematics, 10, 151.
Koopmaans, T. C. (1933/1934). Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den Einzelnen Elektronen Eines Atoms. Physica, 1, 104.
Kołos, W., & Roothaan, C. C. J. (1960). Accurate electronic wave functions for the H\(_{2}\) molecule. Reviews of Modern Physics, 32, 219.
Łach, G., Jeziorski, B., & Szalewicz, K. (2004). Radiative corrections to the polarizability of helium. Physical Review Letters, 92, 233001.
Pestka, G., Bylicki, M., & Karwowski, J. (2008). Frontiers in quantum systems in chemistry and physics. In P. J. Grout, J. Maruani, G. Delgado-Barrio, & P. Piecuch (Eds.), Dirac-Coulomb equation: Playing with artifacts (pp. 215–238). Springer, New York/Heidelberg.
Piela, L. (2007). Ideas of quantum chemistry. Amsterdam: Elsevier.
Roos, B. O. (1972). A new method for large-scale CI calculations. Chemical Physics Letters, 15, 153.
Schrödinger, E. (1926a). Quantisierung als Eigenwertproblem. Annalen Physik, 384, 361.
Schrödinger, E. (1926b). Quantisierung als Eigenwertproblem. Annalen Physik, 384, 489.
Schrödinger, E. (1926 c). Quantisierung als Eigenwertproblem. Annalen Physik, 385, 437.
Schrödinger, E. (1926 d). Quantisierung als Eigenwertproblem. Annalen Physik, 386, 109.
Slater, J. (1930). Cohesion in monovalent metals. Physical Review, 35, 509.
Woodward, R. B., & Hoffmann, R. (1965). Selection rules for sigmatropic reactions. Journal of the American Chemical Society, 87, 2511.
Acknowledgments
The author is very grateful to his friends, Professor Andrzej J. Sadlej and Professor Leszek Z. Stolarczyk, for the joy of being with them, discussing all exciting aspects of chemistry, science and beyond; a part of them is included in the present chapter.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2012 Springer Science+Business Media B.V.
About this entry
Cite this entry
Piela, L. (2012). From Quantum Theory to Computational Chemistry. A Brief Account of Developments. In: Leszczynski, J. (eds) Handbook of Computational Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0711-5_1
Download citation
DOI: https://doi.org/10.1007/978-94-007-0711-5_1
Published:
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-007-0710-8
Online ISBN: 978-94-007-0711-5
eBook Packages: Chemistry and Materials ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics