Casimir -Lifshitz: LESSONS from CHEMISTRY

Barry W. Ninham

Department of Chemistry and CSGI,
University of Florence
via della Lastruccia 3, Sesto Fiorentino
50019 Florence, Italy

1. The QED Derivation of Dzyaloshinski, Lifshitz, Pitaevski is exactly equivalent to semiclassical theory. In the presence of an intervening plasma the temperature dependent contribution is exactly equivalent to the linearised version of Onsager Samaris theory for the change of interfacial tension with dissolved salt. A consequence is that the DLVO and Debye Huckel type theories of molecular interactions are deeply flawed-- They violate the gauge condition on the electromagnetic field and the Gibbs adsorption isotherms. Electrostatic double layer forces and dispersion forces can not be separated and have to taken together the same level. When the theory is remedied a slew of conceptual locks that inhibited the application of physical chemistry to biology are removed.
The same is true for Casimir between metal plates.

2. The text book retarded Casimir Polder interaction between atoms is correct only at zero temperature. At any finite temperature a different form obtains. This has consequences for interpretation of retardation which is not due to the finite velocity of light , but due to the quantisation of light.

3. A fortiori is this so for the retarded resonance ground state excited state interaction which is incorrect even at zero temperature. The correct form will be given. This probably implications for catalysis and insect pheremone recognition. As for 1 above the same comment holds for the classical Forster interaction in biophysics where the separation of electron transfer from photon transfer is routine.

4. Nuclear Forces from Casimir: The Casimir plate problem with an intervening plasma at high T or large distance is discussed. It has a Yukawa like form. The pi meson mass, lifetime, range and strength of nuclear forces seem to emerge naturally from Casimir as excitations in a virtual electron positron pair sea whose density can be predicted.


B.W. Ninham, V.A. Parsegian, Van der Waals forces across triple-layer films, Journal of Chemical Physics 52, no. 9 (1970) 4578-4587.

B.W. Ninham, V.A. Parsegian , Van der Waals forces: special characteristics in lipid-water systems and a general
method of calculation based on the Lifshitz theory , Biophysical Journal 10, no. 7 (1970) 646-663.

V.A. Parsegian, B.W. Ninham, Temperature-dependent van der Waals forces, Biophysical Journal 10, no. 7 (1970) 664-674.

B.W. Ninham, V.A. Parsegian, Van der Waals interactions in multilayer systems, Journal of Chemical Physics 53, no. 9 (1970) 3398-3402.

B.W. Ninham, V.A. Parsegian, G.H. Weiss, On the macroscopic theory of temperature-dependent van der Waals forces, Journal of Statistical Physics 2, no. 4 (1970) 323-328.

B.W. Ninham, N.E. Frankel, M.L. Glasser, B.D. Hughes, Möbius, Mellin and Mathematical physics, Physica A 186 (1992) 441-481.

B.W. Ninham, V.V. Yaminsky, Ion binding and ion specificity-The Hofmeister effect, Onsager and Lifschitz theories, Langmuir 13 (1997) 2097-2108

B.W. Ninham, J. Daicic, Lifschitz theory of Casimir forces at finite temperature , Physical Review A 57 (1998) 1870-1880.

H. Wennerstrom, J. Daicic, B.W. Ninham, Temperature dependence of atom-atom interactions, Physical Review A 60 (1999) 2581-2584

Surface Tension of Electrolytes: Specific Ion Effects Explained by Dispersion Forces, M. Boström, D.R.M. Williams and B.W. Ninham, Langmuir (2001) 17, 4475

Physical Chemistry: The Loss of Certainty, B.W. Ninham,Progress in Colloid and Polymer Science 120 (2002) 1-12

Atom-atom interactions at and between metal surfaces at non-zero temperature, M. Boström, J. Longdell and B.W. Ninham, Phys Rev A 64 D622702 (2001)

Resonance Interaction between Atoms in an Excited State, M.Bostrom, J.J. Longdell D.J.Mitchell and B.W.Ninham,European Journal of Physics D, in press.

Specific Ion Effects in Colloid Interactions: Why DLVO Theory fails for Biology, M.Bostrom, D.R.M Williams and B.W.Ninham, Phys.Rev.Letts. (2001) 87, 168103

Ion Specificity of Micelles and Microemulsions Explained by Ionic Dispersion Forces , M.Bostrom D.R.Williams B.W.Ninham , Langmuir 2002, 18, 6010-6014;

Resonance Interaction in Channels, M Bostrom J Longdell B. W .Ninham, Europhys Letters 2002, 59, 21

Influence of Hofmeister effects on surface pH and binding of peptides to membranes, M Bostrom , D.R Williams B.W.Ninham Langmuir vol 018 issue 22 in press.

Why Colloid Science failed to contribute to biology, M Bostrom , D.R Williams B.W.Ninham, Progress in Colloid and Polymers Science Special ECIS 2001 Edition

Influence of ionic dispersion potentials on counterion condensation on polyelectrolytes, M. Bostrom, D.R. Williams and B.W Ninham ,J. Phys. Chem. B 2002, 106, 7908-7912.

Hofmeister Effects and the Role of Coions in pH Measurements, M. Bostrom, V.J. S. Craig, R. Albion, D.R.M .Williams and B.W.Ninham, J Phys Chem submitted

A Mechanism of Insect Pheromone Action via Photon Transfer, Barry W. Ninham*, M. Boström, J. J. Longdell, A. Carnerup and Z. Blum, Chem Evolution, submitted

Specific Ion Effects: why the properties of Lysozyme in Salt Solutions follows a Hofmeister Series, M Bostrom, D.R.W. Williams, B.W. Ninham, Biophys J. submitted.

The role of Coions in Biology;The Influence of Salts on Conformational Equilibria in Rhodopsin, M Bostrom, D.R W. Williams, B.W. Ninham European Journal of Physics D. Submitted

Specific Ion Effects: the Role of Salt & Buffer on Protonation of Cytochrome C., M Bostrom, D.R.W. Williams, B.W. Ninham J Mol. Biology submitted

Screened Casimir Forces at Finite Temperature: A possible role for Nuclear Interactions, B W Ninham and M Bostrom Phys Rev A Rapid communications submitted