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Does chemistry need more physics?

  • Trond Saue ORCID logo EMAIL logo
Veröffentlicht/Copyright: 22. Juli 2025
Pure and Applied Chemistry
Aus der Zeitschrift Pure and Applied Chemistry Band 97 Heft 10

Abstract

In this mini-review I look into the physics underlying the theory of electronic structure of atoms and molecules. Quantum mechanics is needed to understand the structure of the periodic table. Special relativity is indispensable for a correct description of the chemistry of the heavy elements. With increased accuracy of quantum chemical calculations, it is natural to ask if chemistry needs more physics.

Keywords: Periodic table; quantum chemistry; quantum science and technology
Corresponding author: Trond Saue, Laboratoire de Chimie et Physique Quantique, UMR 5626 CNRS – Université Toulouse III-Paul Sabatier, 118 Route de Narbonne, F-31062 Toulouse, France, e-mail:
Article note: A collection of invited papers to celebrate the UN’s proclamation of 2025 as the International Year of Quantum Science and Technology.

Funding source: H2020 European Research Council

Award Identifier / Grant number: 101019907

Acknowledgments

I thank Dávid Ferenc for critical reading of the manuscript.

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: The author has accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The author states no conflict of interest.

  6. Research funding: This project received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant Agreement No. 101019907 HAMP-vQED).

  7. Data availability: Not applicable.

References

1. Hargittai, B.; Hargittai, I. Year of the Periodic Table: Mendeleev and the Others. Struct. Chem. 2019, 30, 1–7. https://doi.org/10.1007/s11224-018-1266-2.Suche in Google Scholar

2. Pyykkö, P. The Physics behind Chemistry and the Periodic Table. Chem. Rev. 2012, 112, 371–384. https://doi.org/10.1021/cr200042e.Suche in Google Scholar PubMed

3. Schwerdtfeger, P.; Smits, O. R.; Pyykkö, P. The Periodic Table and the Physics that Drives it. Nat. Rev. Chem. 2020, 4, 359–380. https://doi.org/10.1038/s41570-020-0195-y.Suche in Google Scholar PubMed

4. Geiger, H.; Marsden, E. On a Diffuse Reflection of the α-Particles. Proc. R. Soc. Lond. - Ser. A Contain. Pap. Math. Phys. Character 1909, 82, 495–500. https://doi.org/10.1098/rspa.1909.0054.Suche in Google Scholar

5. Rutherford, E. LXXIX. The Scattering of α and β Particles by Matter and the Structure of the Atom. London, Edinburgh Dublin Phil. Mag. J. Sci. 1911, 21, 669–688. https://doi.org/10.1080/14786440508637080.Suche in Google Scholar

6. Rutherford, E. XLIII. The Origin of β and γ Rays from Radioactive Substances. London, Edinburgh Dublin Phil. Mag. J. Sci. 1912, 24, 453–462. https://doi.org/10.1080/14786441008637351.Suche in Google Scholar

7. Moseley, H. XCIII. The High-Frequency Spectra of the Elements. London, Edinburgh Dublin Phil. Mag. J. Sci. 1913, 26, 1024–1034. https://doi.org/10.1080/14786441308635052.Suche in Google Scholar

8. Moseley, H. LXXX. The High-Frequency Spectra of the Elements. Part II. London, Edinburgh Dublin Phil. Mag. J. Sci. 1914, 27, 703–713. https://doi.org/10.1080/14786440408635141.Suche in Google Scholar

9. van den Broek, A. Die Radioelemente, das periodische System und die Konstitution der. Atome. Phys. Z. 1913, 14, 32–41.Suche in Google Scholar

10. Thomson, J. XXIV. On the Structure of the Atom: An Investigation of the Stability and Periods of Oscillation of a Number of Corpuscles Arranged at Equal Intervals Around the Circumference of a Circle; with Application of the Results to the Theory of Atomic Structure. London, Edinburgh Dublin Phil. Mag. J. Sci. 1904, 7, 237–265. https://doi.org/10.1080/14786440409463107.Suche in Google Scholar

11. Thomson, J. J. XL. Cathode Rays. London, Edinburgh Dublin Phil. Mag. J. Sci. 1897, 44, 293–316. https://doi.org/10.1080/14786449708621070.Suche in Google Scholar

12. Stoney, G. J. XLIX. Of the “Electron,” or Atom of Electricity. London, Edinburgh Dublin Phil. Mag. J. Sci. 1894, 38, 418–420. https://doi.org/10.1080/14786449408620653.Suche in Google Scholar

13. O’Hara, J. G. George Johnstone Stoney, F. R. S. and the Concept of the Electron. Notes Rec. R. Soc. Lond. 1975, 29, 265–276. https://doi.org/10.1098/rsnr.1975.0018.Suche in Google Scholar

14. Thomson, J. J. Carriers of Negative Electricity; Nobel lecture, 1906. https://www.nobelprize.org/prizes/physics/1906/thomson/lecture/.Suche in Google Scholar

15. Thomson, J. J. The Atomic Theory; Clarendon Press: Oxford, 1914. https://archive.org/details/atomictheorythom00thomrich/page/n3/mode/2up.Suche in Google Scholar

16. Born, M. Obituary Notice of Sir J. J. Thomson. Proc. Phys. Soc. 1941, 53, 305–310. https://archive.org/details/proceedings-of-the-physical-society_1941-05-01_53_part-3/page/n127/mode/2up.Suche in Google Scholar

17. Perrin, J. Les Hypothèses Moléculaires. Rev. Sci. 1901, 15, 449–461. https://gallica.bnf.fr/ark:/12148/bpt6k215134v/f452.item.Suche in Google Scholar

18. Bohr, N. I. On the Constitution of Atoms and Molecules. London, Edinburgh Dublin Phil. Mag. J. Sci. 1913, 26, 1–25. https://doi.org/10.1080/14786441308634955.Suche in Google Scholar

19. Bohr, N. Atomic Structure. Nature 1921, 107, 104–107. https://doi.org/10.1038/107104a0.Suche in Google Scholar

20. Kossel, W. Über Molekülbildung als Frage des Atombaus. Ann. Phys. 1916, 354, 229–362. https://doi.org/10.1002/andp.19163540302.Suche in Google Scholar

21. Lewis, G. N. The Atom and the Molecule. J. Am. Chem. Soc. 1916, 38, 762–785. https://doi.org/10.1021/ja02261a002.Suche in Google Scholar

22. Kohler, R.Jr. The Origin of G. N. Lewis’s Theory of the Shared Pair Bond. Hist. Stud. Phys. Sci. 1971, 3, 343–376. https://doi.org/10.2307/27757322.Suche in Google Scholar

23. Bohr, N. Über die Anwendung der Quantentheorie auf den Atombau. Z. Phys. 1923, 13, 117–165. https://doi.org/10.1007/bf01328209.Suche in Google Scholar

24. Mulliken, R. S. The Assignment of Quantum Numbers for Electrons in Molecules. I. Phys. Rev. 1928, 32, 186–222. https://doi.org/10.1103/physrev.32.186.Suche in Google Scholar

25. Kragh, H. Niels Bohr and the Quantum Atom: The Bohr Model of Atomic Structure 1913–1925; Oxford University Press: Oxford, 2012.10.1093/acprof:oso/9780199654987.001.0001Suche in Google Scholar

26. Pauli, W. Über den Zusammenhang des Abschlusses der Elektronengruppen im aAtom mit der Komplexstruktur der Spektren. Z. Phys. 1925, 31, 765–783. https://doi.org/10.1007/bf02980631.Suche in Google Scholar

27. Curceanu, C.; Gillaspy, J. D.; Hilborn, R. C. Resource Letter SS-1: The Spin-Statistics Connection. Am. J. Phys. 2012, 80, 561–577. https://doi.org/10.1119/1.4704899.Suche in Google Scholar

28. Margenau, H.; Wightman, A. Atomic and Molecular Theory since Bohr: Historical Survey. Am. J. Phys. 1944, 12, 119–130. https://doi.org/10.1119/1.1990565.Suche in Google Scholar

29. Hylleraas, E. A. The Schrödinger Two-Electron Atomic Problem. Adv. Quantum Chem. 1964, 1, 1–33. https://doi.org/10.1016/S0065-3276(08)60373-1.Suche in Google Scholar

30. Scerri, E. The Periodic Table: Its Story and its Significance, 2nd ed; Oxford University Press: New York, 2020.10.1093/oso/9780190914363.001.0001Suche in Google Scholar

31. Hylleraas, E. A. Über den grundzustand des heliumatoms. Z. Phys. 1928, 48, 469–494. https://doi.org/10.1007/bf01340013.Suche in Google Scholar

32. Hylleraas, E. A. Neue Berechnung der Energie des Heliums im Grundzustande, sowie des tiefsten Terms von Ortho-Helium. Z. Phys. 1929, 54, 347–366. https://doi.org/10.1007/bf01375457.Suche in Google Scholar

33. Nakashima, H.; Nakatsuji, H. Solving the Schrödinger Equation for Helium Atom and its Isoelectronic Ions with the Free Iterative Complement Interaction (ICI) Method. J. Chem. Phys. 2007, 127, 224104. https://doi.org/10.1063/1.2801981.Suche in Google Scholar PubMed

34. Schwarz, W. H. E.; Rich, R. L. Theoretical Basis and Correct Explanation of the Periodic System: Review and Update. J. Chem. Educ. 2010, 87, 435–443. https://doi.org/10.1021/ed800124m.Suche in Google Scholar

35. Cao, C.-S.; Hu, H.-S.; Li, J.; Schwarz, W. H. E. Physical Origin of Chemical Periodicities in the System of Elements. Pure Appl. Chem. 2019, 91, 1969–1999. https://doi.org/10.1515/pac-2019-0901.Suche in Google Scholar

36. International Union of Pure and Applied Chemistry. IUPAC Compendium of Chemical Terminology – The Gold Book, 2019. https://goldbook.iupac.org/terms/view/C01248.Suche in Google Scholar

37. Mulliken, R. S. Electronic Structures of Polyatomic Molecules and Valence. II. General Considerations. Phys. Rev. 1932, 41, 49–71. https://doi.org/10.1103/physrev.41.49.Suche in Google Scholar

38. Mulliken, R. S. Spectroscopy, Molecular Orbitals, and Chemical Bonding. Science 1967, 157, 13–24. https://doi.org/10.1126/science.157.3784.13.Suche in Google Scholar PubMed

39. Slater, J. C. The Theory of Complex Spectra. Phys. Rev. 1929, 34, 1293–1322. https://doi.org/10.1103/physrev.34.1293.Suche in Google Scholar

40. Boys, S. F. Electronic Wave Functions II. A Calculation for the Ground State of the Beryllium Atom. Proc. Roy. Soc. Lond. Math. Phys. Sci. 1950, 201, 125–137. https://doi.org/10.1098/rspa.1950.0047.Suche in Google Scholar

41. Shavitt, I. The History and Evolution of Configuration Interaction. Mol. Phys. 1998, 94, 3–17. https://doi.org/10.1080/002689798168303.Suche in Google Scholar

42. Savelyev, I. M.; Kaygorodov, M. Y.; Kozhedub, Y. S.; Malyshev, A. V.; Tupitsyn, I. I.; Shabaev, V. M. Ground State of Superheavy Elements with 120 ≤ Z ≤ 170: Systematic Study of the Electron-Correlation, Breit, and QED Effects. Phys. Rev. A 2023, 107, 042803. https://doi.org/10.1103/physreva.107.042803.Suche in Google Scholar

43. Rohrlich, F. Classical Charged Particles; Westview Press: New York, 1990.Suche in Google Scholar

44. Mendelejeff, D. Die periodische Gesetzmëssigkeit der chemischen Elemente. Ann. Chem. Pharm. Supplbd. 1871, 8, 133–229.Suche in Google Scholar

45. Goldschmidt, V. M.; Barth, T.; Lunde, G. Geochemische Verteilungsgesetzte der Elemente. 5. Isomorphie und Polymorphie der Sesquioxyde. Die Lanthaniden-Kontraktion und ihre Konsequenzen. Norske Vidensk. Akad. Skrifter I Mat. Naturv. Kl. 1925, 7, 1.Suche in Google Scholar

46. Tiesinga, E.; Mohr, P. J.; Newell, D. B.; Taylor, B. N. CODATA Recommended Values of the Fundamental Physical Constants: 2018. Rev. Mod. Phys. 2021, 93, 025010. https://doi.org/10.1103/revmodphys.93.025010.Suche in Google Scholar

47. Tuinstra, F. Rømer and the Finite Speed of Light. Phys. Today 2004, 57, 16–17. https://doi.org/10.1063/1.1878320.Suche in Google Scholar

48. Pyykkö, P. Relativistic Quantum Chemistry. Adv. Quantum Chem. 1978, 11, 353–409. https://doi.org/10.1016/S0065-3276(08)60241-5.Suche in Google Scholar

49. Pyykko, P.; Desclaux, J. P. Relativity and the Periodic System of Elements. Acc. Chem. Res. 1979, 12, 276–281. https://doi.org/10.1021/ar50140a002.Suche in Google Scholar

50. Pyykko, P. Relativistic Effects in Structural Chemistry. Chem. Rev. 1988, 88, 563–594. https://doi.org/10.1021/cr00085a006.Suche in Google Scholar

51. Burke, V. M.; Grant, I. P. The Effect of Relativity on Atomic Wave Functions. Proc. Phys. Soc. 1967, 90, 297. https://doi.org/10.1088/0370-1328/90/2/301.Suche in Google Scholar

52. Romaniello, P.; de Boeij, P. L. The Role of Relativity in the Optical Response of Gold within the Time-Dependent Current-Density-Functional Theory. J. Chem. Phys. 2005, 122, 164303. https://doi.org/10.1063/1.1884985.Suche in Google Scholar PubMed

53. Steenbergen, K. G.; Pahl, E.; Schwerdtfeger, P. Accurate, Large-Scale Density Functional Melting of Hg: Relativistic Effects Decrease Melting Temperature by 160 K. J. Phys. Chem. Lett. 2017, 8, 1407–1412. https://doi.org/10.1021/acs.jpclett.7b00354.Suche in Google Scholar PubMed

54. Ahuja, R.; Blomqvist, A.; Larsson, P.; Pyykkö, P.; Zaleski-Ejgierd, P. Relativity and the Lead-Acid Battery. Phys. Rev. Lett. 2011, 106, 018301. https://doi.org/10.1103/physrevlett.106.018301.Suche in Google Scholar PubMed

55. Saue, T. Relativistic Hamiltonians for Chemistry: A Primer. ChemPhysChem 2011, 12, 3077. https://doi.org/10.1002/cphc.201100682.Suche in Google Scholar PubMed

56. Lloyd, D. R. On the Lanthanide and “Scandinide” Contractions. J. Chem. Educ. 1986, 63, 502. https://doi.org/10.1021/ed063p502.Suche in Google Scholar

57. Bagus, P. S.; Lee, Y. S.; Pitzer, K. S. Effects of Relativity and of the Lanthanide Contraction on the Atoms from Hafnium to Bismuth. Chem. Phys. Lett. 1975, 33, 408–411. https://doi.org/10.1016/0009-2614(75)85741-1.Suche in Google Scholar

58. Fossgaard, O.; Gropen, O.; Eliav, E.; Saue, T. Bonding in the Homologous Series CsAu, CsAg, and CsCu Studied at the 4-Component Density Functional Theory and Coupled Cluster Levels. J. Chem. Phys. 2003, 119, 9355–9363. https://doi.org/10.1063/1.1615953.Suche in Google Scholar

59. Dirac, P. A. M. The´orie du positron. (French) [Theory of the positron]. In Structure et propriétés des noyaux atomiques. Rapports et discussions du septieme conseil de physique tenu à Bruxelles du 22 au 29 octobre 1933 sous les auspices de l’institut international de physique Solvay. Publies par la commission administrative de l’institut; de Physique Solvay, I. I., Ed., 1934; pp. 203–230.Suche in Google Scholar

60. Tamm, I. Über die Wechselwirkung der freien Elektronen mit der Strahlung nach der Diracsehen Theorie des Elektrons und nach der qQuantenelektrodynamik. Z. Phys. 1930, 62, 545–568. https://doi.org/10.1007/bf01339679.Suche in Google Scholar

61. Oppenheimer, J. R. On the Theory of Electrons and Protons. Phys. Rev. 1930, 35, 562–563. https://doi.org/10.1103/physrev.35.562.Suche in Google Scholar

62. Dirac, P. A. M. A Theory of Electrons and Protons. Proc. R. Soc. Lond. - Ser. A Contain. Pap. Math. Phys. Character 1930, 126, 360–365. https://doi.org/10.1098/rspa.1930.0013.Suche in Google Scholar

63. Dirac, P. A. M. Quantised Singularities in the Electromagnetic Field. Proc. R. Soc. Lond. - Ser. A Contain. Pap. Math. Phys. Character 1931, 133, 60–72. https://doi.org/10.1098/rspa.1931.0130.Suche in Google Scholar

64. Anderson, C. D. The Positive Electron. Phys. Rev. 1933, 43, 491–494. https://doi.org/10.1103/physrev.43.491.Suche in Google Scholar

65. Breit, G. An Interpretation of Dirac’s Theory of the Electron. Proc. Natl. Acad. Sci. 1928, 14, 553–559. https://doi.org/10.1073/pnas.14.7.553.Suche in Google Scholar PubMed PubMed Central

66. Moss, R. E. Advanced Molecular Quantum Mechanics; Chapmann and Hall: London, 1973.10.1007/978-94-009-5688-9Suche in Google Scholar

67. Schrödinger, E. Über die kräftefreie bewegung in der relativistischen quantenmechanik. Sitzungsber. Preuss. Akad. Wiss. Phys. Math. Kl. 1930, 24, 418–428.Suche in Google Scholar

68. Mattuck, R. D. A Guide to Feynman Diagrams in the Many-Body Problem, 2nd ed., Dover Books on Physics and Chemistry; Dover Publications: New York, 1992.Suche in Google Scholar

69. Gell-Mann, M. The Interpretation of the New Particles as Displaced Charge Multiplets. Il Nuovo Cimento 1956, 4, 848. https://doi.org/10.1007/bf02748000.Suche in Google Scholar

70. Schwarzschild, K. Zur Elektrodynamik: I. Zwei Formen des Princips der kleinsten Action in der Elektrontheorie. Nachr. Ges. Wiss. Göttingen, Math.-Phys. Kl. 1903, 126–131. https://eudml.org/doc/58546.Suche in Google Scholar

71. Kramers, H. A. The Use of Charge-Conjugated Wave-Functions in the Hole-Theory of the Electron. Proc. Roy. Acad. Amsterdam 1937, 40, 814. https://dwc.knaw.nl/DL/publications/PU00017118.pdf.Suche in Google Scholar

72. Darwin, C. G. The Dynamical Motion of Charged Particles. Phil. Mag. 1920, 39, 537–551. https://doi.org/10.1080/14786440508636066.Suche in Google Scholar

73. Jackson, J. D. Classical Electrodynamics; Wiley: New York, 1999.Suche in Google Scholar

74. Norman, P.; Ruud, K.; Saue, T. Principles and Practices of Molecular Properties: Theory, Modeling and Simulations; Wiley: Hoboken, NJ, 2018.10.1002/9781118794821Suche in Google Scholar

75. Breit, G. The Effect of Retardation on the Interaction of Two Electrons. Phys. Rev. 1929, 34, 553–573. https://doi.org/10.1103/physrev.34.553.Suche in Google Scholar

76. Saue, T. Spin-Interactions and the Non-Relativistic Limit of Electrodynamics. Adv. Quantum Chem. 2005, 48, 383–405. https://doi.org/10.1016/S0065-3276(05)48020-X.Suche in Google Scholar

77. Heisenberg, W. The Physical Principles of the Quantum Theory; Dover, 1930. https://archive.org/details/in.ernet.dli.2015.166273/page/n167/mode/2up?q=physic.Suche in Google Scholar

78. Dirac, P. A. M. Quantum Mechanics of Many-Electron Systems. Proc. R. Soc. Lond. Ser. A Contain. Pap. Math. Phys. Character 1929, 123, 714–733. https://doi.org/10.1098/rspa.1929.0094.Suche in Google Scholar

79. Kutzelnigg, W. Perspective on “Quantum Mechanics of Many-Electron System” – Dirac PAM (1929) Proc R Soc Lond Ser A 123: 714. Theor. Chem. Acc. 2000, 103, 182–186. https://doi.org/10.1007/s002149900029.Suche in Google Scholar

80. Lévy-Leblond, J. M. Nonrelativistic Particles and Wave Equations. Commun. Math. Phys. 1967, 6, 286–311. https://doi.org/10.1007/bf01646020.Suche in Google Scholar

81. Le Bellac, M.; Lévy-Leblond, J. M. Galilean Electromagnetism. Il Nuovo Cimento B 1973, 14, 217–234. https://doi.org/10.1007/bf02895715.Suche in Google Scholar

82. Kutzelnigg, W. Chapter 12 – Perturbation Theory of Relativistic Effects. In Relativistic Electronic Structure Theory; Schwerdtfeger, P., Ed.; Elsevier: Amsterdam, Vol. 11, 2002; pp 664–757.10.1016/S1380-7323(02)80038-3Suche in Google Scholar

83. Kutzelnigg, W. Fundamentals of Nonrelativistic and Relativistic Theory of NMR and EPR Parameters. In Calculation of NMR and EPR Parameters; John Wiley & Sons, Ltd: Weinheim, 2004, Chap. 5; pp. 43–82.10.1002/3527601678.ch5Suche in Google Scholar

84. Safronova, M.; Budker, D.; DeMille, D.; Kimball, D. F. J.; Derevianko, A.; Clark, C. W. Search for New Physics with Atoms and Molecules. Rev. Mod. Phys. 2018, 90, 025008. https://doi.org/10.1103/revmodphys.90.025008.Suche in Google Scholar

85. Bakasov, A.; Ha, T.-K.; Quack, M. Ab Initio Calculation of Molecular Energies Including Parity Violating Interactions. J. Chem. Phys. 1998, 109, 7263–7285. https://doi.org/10.1063/1.477360.Suche in Google Scholar

86. Sallembien, Q.; Bouteiller, L.; Crassous, J.; Raynal, M. Possible Chemical and Physical Scenarios Towards Biological Homochirality. Chem. Soc. Rev. 2022, 51, 3436–3476. https://doi.org/10.1039/d1cs01179k.Suche in Google Scholar PubMed

87. Berger, R. Chapter 4 – Parity-Violation Effects in Molecules. In Relativistic Electronic Structure Theory; Schwerdtfeger, P., Ed.; Elsevier: Amsterdam, Vol. 14, 2004; pp 188–288.10.1016/S1380-7323(04)80031-1Suche in Google Scholar

88. Bast, R.; Koers, A.; Gomes, A. S. P.; Iliaš, M.; Visscher, L.; Schwerdtfeger, P.; Saue, T. Analysis of Parity Violation in Chiral Molecules. Phys. Chem. Chem. Phys. 2011, 13, 864–876. https://doi.org/10.1039/c0cp01483d.Suche in Google Scholar PubMed

89. Cournol, A.; Manceau, M.; Pierens, M.; Lecordier, L.; Tran, D.; Santagata, R.; Argence, B.; Goncharov, A.; Lopez, O.; Abgrall, M.; Le Coq, Y.; Le Targat, R.; Alvarez Martinez, H.; Lee, W.; Xu, D.; Pottie, P.-E.; Hendricks, R.; Wall, T.; Bieniewska, J.; Sauer, B.; Tarbutt, M.; Amy-Klein, A.; Tokunaga, S.; Darquié, B. A New Experiment to Test Parity Symmetry in Cold Chiral Molecules Using Vibrational Spectroscopy. Quantum Electron. 2019, 49, 288. https://doi.org/10.1070/qel16880.Suche in Google Scholar

90. Berger, R.; Stohner, J. Parity Violation. WIREs Comput. Mol. Sci. 2019, 9, e1396. https://doi.org/10.1002/wcms.1396.Suche in Google Scholar

91. Greiner, W.; Peitz, H. Ist das Vakuum wirklich leer? Phys. Unserer Zeit 1978, 9, 165–183. https://doi.org/10.1002/piuz.19780090602.Suche in Google Scholar

92. Hutchison, J. A.; Schwartz, T.; Genet, C.; Devaux, E.; Ebbesen, T. W. Modifying Chemical Landscapes by Coupling to Vacuum Fields. Angew. Chem., Int. Ed. 2012, 51, 1592–1596. https://doi.org/10.1002/anie.201107033.Suche in Google Scholar PubMed

93. Ebbesen, T. W.; Rubio, A.; Scholes, G. D. Introduction: Polaritonic Chemistry. Chem. Rev. 2023, 123, 12037–12038. https://doi.org/10.1021/acs.chemrev.3c00637.Suche in Google Scholar PubMed

94. Ruggenthaler, M.; Sidler, D.; Rubio, A. Understanding Polaritonic Chemistry from Ab Initio Quantum Electrodynamics. Chem. Rev. 2023, 123, 11191–11229. https://doi.org/10.1021/acs.chemrev.2c00788.Suche in Google Scholar PubMed PubMed Central

95. Sakurai, J. J. Advanced Quantum Mechanics; Addison-Wesley: Reading, Massachusetts, 1967.Suche in Google Scholar

96. Craig, D. P.; Thirunamachandran, T. Molecular Quantum Electrodynamics; Dover: Mineola, New York, 1998.Suche in Google Scholar

97. Norman, P.; Bishop, D. M.; Jensen, H. J. Aa.; Oddershede, J. Near-Resonant Absorption in the Time-Dependent Self-Consistent Field and Multiconfigurational Self-Consistent Field Approximations. J. Chem. Phys. 2001, 115, 10323–10334. https://doi.org/10.1063/1.1415081.Suche in Google Scholar

98. Bander, M.; Itzykson, C. Group Theory and the Hydrogen Atom (I). Rev. Mod. Phys. 1966, 38, 330–345. https://doi.org/10.1103/revmodphys.38.330.Suche in Google Scholar

99. Lamb, W. E.; Retherford, R. C. Fine Structure of the Hydrogen Atom by a Microwave Method. Phys. Rev. 1947, 72, 241–243. https://doi.org/10.1103/physrev.72.241.Suche in Google Scholar

100. Hubbell, J. Electron-Positron Pair Production by Photons: A Historical Overview. Radiat. Phys. Chem. 2006, 75, 614–623. https://doi.org/10.1016/j.radphyschem.2005.10.008.Suche in Google Scholar

101. Yerokhin, V. A.; Shabaev, V. M. Lamb Shift of n = 1 and n = 2 States of Hydrogen-Like Atoms, 1 ≤ Z ≤ 110. J. Phys. Chem. Ref. Data 2015, 44, 033103. https://doi.org/10.1063/1.4927487.Suche in Google Scholar

102. Wilczek, F.; Devine, B. Fantastic Realities; World Scientific: Singapore, 2006.10.1142/6019Suche in Google Scholar

103. Wald, R. Advanced Classical Electromagnetism; Princeton University Press: New York, 2022.Suche in Google Scholar

104. Milonni, P. W. The Quantum Vacuum; Academic Press, Inc.: Boston, 1994.Suche in Google Scholar

105. Dyson, F. J. The Radiation Theories of Tomonaga, Schwinger, and Feynman. Phys. Rev. 1949, 75, 486–502. https://doi.org/10.1103/physrev.75.486.Suche in Google Scholar

106. Furry, W. H. On Bound States and Scattering in Positron Theory. Phys. Rev. 1951, 81, 115–124. https://doi.org/10.1103/physrev.81.115.Suche in Google Scholar

107. Helgaker, T.; Jørgensen, P.; Olsen, J. Molecular Electronic Structure Theory; John Wiley & Sons, Ltd: Chichester, 2000.10.1002/9781119019572Suche in Google Scholar

108. Crawford, T. D.; Schaefer, H. An Introduction to Coupled Cluster Theory for Computational Chemists. Rev. Comput. Chem. 2000, 14, 33–136. https://doi.org/10.1002/9780470125915.ch2.Suche in Google Scholar

109. Wick, G. C. The Evaluation of the Collision Matrix. Phys. Rev. 1950, 80, 268–272. https://doi.org/10.1103/physrev.80.268.Suche in Google Scholar

110. Dirac, P. A. M. Relativistic Quantum Mechanics. Proc. R. Soc. Lond. - Ser. A Contain. Pap. Math. Phys. Character 1932, 136, 453–464.10.1098/rspa.1932.0094Suche in Google Scholar

111. Sunaga, A.; Salman, M.; Saue, T. 4-Component Relativistic Hamiltonian with Effective QED Potentials for Molecular Calculations. J. Chem. Phys. 2022, 157, 164101. https://doi.org/10.1063/5.0116140.Suche in Google Scholar PubMed

112. Blundell, S. A.; Mohr, P. J.; Johnson, W. R.; Sapirstein, J. Evaluation of Two-Photon Exchange Graphs for Highly Charged Heliumlike Ions. Phys. Rev. A 1993, 48, 2615–2626. https://doi.org/10.1103/physreva.48.2615.Suche in Google Scholar PubMed

113. Uehling, E. A. Polarization Effects in the Positron Theory. Phys. Rev. 1935, 48, 55–63. https://doi.org/10.1103/physrev.48.55.Suche in Google Scholar

114. Pyykkö, P.; Zhao, L.-B. Search for Effective Local Model Potentials for Simulation of Quantum Electrodynamic Effects in Relativistic Calculations. J. Phys. B 2003, 36, 1469–1478. https://doi.org/10.1088/0953-4075/36/8/302.Suche in Google Scholar

115. Flambaum, V. V.; Ginges, J. S. M. Radiative Potential and Calculations of QED Radiative Corrections to Energy Levels and Electromagnetic Amplitudes in Many-Electron Atoms. Phys. Rev. A 2005, 72, 052115. https://doi.org/10.1103/physreva.72.052115.Suche in Google Scholar

116. Shabaev, V. M.; Tupitsyn, I. I.; Yerokhin, V. A. Model Operator Approach to the Lamb Shift Calculations in Relativistic Many-Electron Atoms. Phys. Rev. A 2013, 88, 012513. https://doi.org/10.1103/physreva.88.012513.Suche in Google Scholar

117. Pašteka, L.; Eliav, E.; Borschevsky, A.; Kaldor, U.; Schwerdtfeger, P. Relativistic Coupled Cluster Calculations with Variational Quantum Electrodynamics Resolve the Discrepancy Between Experiment and Theory Concerning the Electron Affinity and Ionization Potential of Gold. Phys. Rev. Lett. 2017, 118, 023002. https://doi.org/10.1103/physrevlett.118.023002.Suche in Google Scholar PubMed

118. Brown, C. M.; Ginter, M. L. Absorption Spectrum of Au i Between 1300 and 1900 Å. J. Opt. Soc. Am. 1978, 68, 243–246. https://doi.org/10.1364/josa.68.000243.Suche in Google Scholar

119. Andersen, T.; Haugen, H. K.; Hotop, H. Binding Energies in Atomic Negative Ions: III. J. Phys. Chem. Ref. Data 1999, 28, 1511–1533. https://doi.org/10.1063/1.556047.Suche in Google Scholar

120. Pyykkö, P.; Tokman, M.; Labzowsky, L. N. Estimated Valence-Level Lamb Shifts for Group 1 and Group 11 Metal Atoms. Phys. Rev. A 1998, 57, R689–R692. https://doi.org/10.1103/physreva.57.r689.Suche in Google Scholar

121. Pyykkö, P. Davidson Lecture, Delivered for University of North Texas for 25 October 2013. http://www.chem.helsinki.fi/∼pyykko/Videos/UNT.mp4. AuCN is discussed at 47:44 of the video.Suche in Google Scholar

122. Zaleski-Ejgierd, P.; Patzschke, M.; Pyykkö, P. Structure and Bonding of the MCN Molecules, M = Cu, Ag, Au, Rg. J. Chem. Phys. 2008, 128, 224303. https://doi.org/10.1063/1.2937148.Suche in Google Scholar PubMed

123. Grant Hill, J.; Mitrushchenkov, A. O.; Peterson, K. A. Ab Initio Ro-Vibrational Spectroscopy of the Group 11 Cyanides: CuCN, AgCN, and AuCN. J. Chem. Phys. 2013, 138, 134314. https://doi.org/10.1063/1.4798638.Suche in Google Scholar PubMed

124. Okabayashi, T.; Okabayashi, E. Y.; Koto, F.; Ishida, T.; Tanimoto, M. Detection of Free Monomeric Silver (I) and Gold (I) Cyanides, AgCN and AuCN: Microwave Spectra and Molecular Structure. J. Am. Chem. Soc. 2009, 131, 11712–11718. https://doi.org/10.1021/ja808153g.Suche in Google Scholar PubMed

125. Saue, T.; Bast, R.; Gomes, A. S. P.; Jensen, H. J. Aa.; Visscher, L.; Aucar, I. A.; di Remigio, R.; Dyall, K. G.; Eliav, E.; Fasshauer, E.; Fleig, T.; Halbert, L.; Hedegård, E. D.; Helmich-Paris, B.; Iliaš, M.; Jacob, C. R.; Knecht, S.; Laerdahl, J. K.; Vidal, M. L.; Nayak, M. K.; Olejniczak, M.; Olsen, J. M. H.; Pernpointner, M.; Senjean, B.; Shee, A.; Sunaga, A.; van Stralen, J. N. P. The DIRAC Code for Relativistic Molecular Calculations. J. Chem. Phys. 2020, 152, 204104; https://doi.org/10.1063/5.0004844.Suche in Google Scholar PubMed

126. Skripnikov, L. V. Approaching meV Level for Transition Energies in the Radium Monofluoride Molecule RaF and Radium Cation Ra+ by Including Quantum-Electrodynamics Effects. J. Chem. Phys. 2021, 154, 201101. https://doi.org/10.1063/5.0053659.Suche in Google Scholar PubMed

127. Demaison, J.; Boggs, J. E.; Császár, A. G. Equilibrium Molecular Structures: From Spectroscopy to Quantum Chemistry; CRC Press: Boca Raton, 2016.10.1201/b10374Suche in Google Scholar

128. Liu, W.; Lindgren, I. “Going Beyond” No-Pair Relativistic Quantum Chemistry. J. Chem. Phys. 2013, 139, 014108. https://doi.org/10.1063/1.4811795.Suche in Google Scholar PubMed

129. Toulouse, J. Relativistic Density-Functional Theory Based on Effective Quantum Electrodynamics. SciPost Chem. 2021, 1, 002. https://doi.org/10.21468/scipostchem.1.1.002.Suche in Google Scholar

130. Mátyus, E.; Ferenc, D.; Jeszenszki, P.; Margócsy, Á. The Bethe-Salpeter QED Wave Equation for Bound-State Computations of Atoms and Molecules. ACS Phys. Chem. Au 2023, 3, 222–240. https://doi.org/10.1021/acsphyschemau.2c00062.Suche in Google Scholar PubMed PubMed Central

131. Flynn, D. J.; Quiney, H. M.; Grant, I. P. Vacuum Polarization in Molecules. I. Uehling Interaction. Phys. Rev. A 2025, 111, 042810. https://doi.org/10.1103/physreva.111.042810.Suche in Google Scholar

132. Boys, S. F. Electronic Wave Functions. I. A General Method of Calculation for the Stationary States of Any Molecular System. Proc. Roy. Soc. Lond. Math. Phys. Sci. 1950, 200, 542–554.10.1098/rspa.1950.0036Suche in Google Scholar

133. Hall, G. G. Samuel Francis Boys 1911–1972. Mol. Phys. 1996, 88, 309–314. https://doi.org/10.1080/00268979609482418.Suche in Google Scholar

134. Salman, M.; Saue, T. Calculating the Many-Potential Vacuum Polarization Density of the Dirac Equation in the Finite-Basis Approximation. Phys. Rev. A 2023, 108, 012808. https://doi.org/10.1103/physreva.108.012808.Suche in Google Scholar

135. Ferenc, D.; Salman, M.; Saue, T. Gaussian Basis Set Approach to One-Loop Self-Energy. Phys. Rev. A 2025, 111, L040802. https://doi.org/10.1103/physreva.111.l040802.Suche in Google Scholar

136. Lehn, J.-M. Perspectives in Chemistry – Aspects of Adaptive Chemistry and Materials. Angew. Chem., Int. Ed. 2015, 54, 3276–3289. https://doi.org/10.1002/anie.201409399.Suche in Google Scholar PubMed

137. Feynman, R. P.; Leighton, R. B.; Sands, M. L. The Feynman Lectures on Physics, Vol. 3; Addison-Wesley: Reading, MA, USA, 1963–1965; p. xii + 513.Suche in Google Scholar
Received: 2025-04-26
Accepted: 2025-06-29
Published Online: 2025-07-22
Published in Print: 2025-10-27

© 2025 IUPAC & De Gruyter

Artikel in diesem Heft

  1. Frontmatter
  2. Review Articles
  3. Minimum energy path methods and reactivity for enzyme reaction mechanisms: a perspective
  4. The quantum revolution in enzymatic chemistry: combining quantum and classical mechanics to understand biochemical processes
  5. A quantum chemical perspective of photoactivated biological functions
  6. Does chemistry need more physics?
  7. Rotational dynamics of ATP synthase: mechanical constraints and energy dissipative channels
  8. Transforming dreams into reality: a fairy-tale wedding of chemistry with quantum mechanics
  9. The quantum chemistry revolution and the instrumental revolution as evidenced by the Nobel Prizes in chemistry
  10. Influence of symmetry on the second-order NLO properties: insights from the few state approximations
  11. The dichotomy between chemical concepts and numbers after almost 100 years of quantum chemistry: conceptual density functional theory as a case study
  12. How ‘de facto variational’ are fully iterative, approximate iterative, and quasiperturbative coupled cluster methods near equilibrium geometries?
  13. Electronic structure of methyl radical photodissociation
  14. Bridging experiment and theory: a computational exploration of UMG-SP3 dynamics
  15. Research Articles
  16. O–Li⋯O and C–Li⋯C lithium bonds in small closed shell and open shell systems as analogues of hydrogen bonds
  17. Metal–ligand bonding and noncovalent interactions of mutated myoglobin proteins: a quantum mechanical study
https://doi.org/10.1515/pac-2025-0497
Schlagwörter für diesen Artikel
Periodic table; quantum chemistry; quantum science and technology

Artikel in diesem Heft

  1. Frontmatter
  2. Review Articles
  3. Minimum energy path methods and reactivity for enzyme reaction mechanisms: a perspective
  4. The quantum revolution in enzymatic chemistry: combining quantum and classical mechanics to understand biochemical processes
  5. A quantum chemical perspective of photoactivated biological functions
  6. Does chemistry need more physics?
  7. Rotational dynamics of ATP synthase: mechanical constraints and energy dissipative channels
  8. Transforming dreams into reality: a fairy-tale wedding of chemistry with quantum mechanics
  9. The quantum chemistry revolution and the instrumental revolution as evidenced by the Nobel Prizes in chemistry
  10. Influence of symmetry on the second-order NLO properties: insights from the few state approximations
  11. The dichotomy between chemical concepts and numbers after almost 100 years of quantum chemistry: conceptual density functional theory as a case study
  12. How ‘de facto variational’ are fully iterative, approximate iterative, and quasiperturbative coupled cluster methods near equilibrium geometries?
  13. Electronic structure of methyl radical photodissociation
  14. Bridging experiment and theory: a computational exploration of UMG-SP3 dynamics
  15. Research Articles
  16. O–Li⋯O and C–Li⋯C lithium bonds in small closed shell and open shell systems as analogues of hydrogen bonds
  17. Metal–ligand bonding and noncovalent interactions of mutated myoglobin proteins: a quantum mechanical study
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