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Remarks on the signs of g factors in atomic and molecular Zeeman spectroscopy
Authors:J M BROWN  R J BUENKER  A CARRINGTON  C DI LAURO  R N DIXON  R W FIELD
Institution:1. Physical and Theoretical Chemistry Laboratory , Oxford University , South Parks Road, Oxford, OX1 3QZ, UK;2. Bergische Universit?t-Gesamthochschule Wuppertal , Theoretische Chemie, Gau?stra?e 20, D-42097, Wuppertal, Germany;3. Department of Chemistry , University of Southampton , Southampton, SO9 5NH, UK;4. Université degli Studi Federico II, Dipartimento di Chimica Farmaceutica e Tossicologica , Via Domenico Montesano 49, I-80131, Napoli, Italy;5. School of Chemistry, University of Bristol , Bristol, BS8 1TS, UK;6. Department of Chemistry , MIT , 77 Massachusetts Ave., Cambridge, MA, 02139, USA
Abstract:This paper draws attention to the advantages that would be obtained by adopting a new convention for the sign of g factors that would make the g factor for electron spin a negative quantity (g ≈ ?2), rather than a positive quantity as generally adopted at present. The editors are aware that the proposal made in this paper concerning the conventional sign of the g factor for electron spin will be seen by some readers as controversial. We have nonetheless agreed to publish this paper in the hope that it will stimulate discussion. The editors would welcome comments on this proposal in the form of short papers, which they will then be happy to consider for publication together at a later date.

Various magnetic moments, associated with rotational, vibrational, nuclear spin, electron orbital and electron spin angular momenta, can contribute to the Zeeman effect in atoms and molecules. They are considered in this paper in the context of the effective Hamiltonian where relativistic and other corrections as well as the effects of mixing with other electronic states are absorbed in appropriate g factors. In spherically symmetric systems, the magnetic dipole moment arising from a specific angular momentum can be written as the product of three factors: the nuclear or Bohr magneton (which is positive), the g factor (which may be positive or negative), and the corresponding angular momentum (which is a vector). A convention is discussed, in which the sign of the g factor is positive when the dipole moment is parallel to its angular momentum and negative when it is antiparallel. This would have the advantage that it could be applied consistently in any situation. Such a choice would require the g factors for the electron orbital and electron spin angular momenta to be negative. This concept can easily be extended to the case of a general molecule where the relation between the dipole and angular momentum vectors has tensorial character.
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