Compactness of molecular reaction paths in quantum mechanics

Variational methods for second-order elliptic equations (35J20) Abstract critical point theory (Morse theory, Lyusternik-Shnirel'man theory, etc.) in infinite-dimensional spaces (58E05) Selfadjoint operator theory in quantum theory, including spectral analysis (81Q10) Molecular physics (81V55)

Abstract: We study isomerizations in quantum mechanics. We consider a neutral molecule composed of N quantum electrons and M classical nuclei and assume that the first eigenvalue of the corresponding N-particle Schr"odinger operator possesses two local minima with respect to the locations of the nuclei. An isomerization is a mountain pass problem between these two local configurations, where one minimizes over all possible paths the highest value of the energy along the paths. Here we state a conjecture about the compactness of min-maxing sequences of such paths, which we then partly solve in the particular case of a molecule composed of two rigid sub-molecules that can move freely in space. More precisely, under appropriate assumptions on the multipoles of the two molecules, we are able to prove that the distance between them stays bounded during the whole chemical reaction. We obtain a critical point at the mountain pass level, which is called a transition state in chemistry. Our method requires to study the critical points and the Morse indices of the classical multipole interactions, as well as to improve existing results about the van der Waals force. This paper generalizes previous works by the second author in several directions.

Review text

The authors study isomerizations in quantum mechanics. They consider a neutral molecule composed of \(N\) quantum electrons and \(M\) classical nuclei and assume that the first eigenvalue of the corresponding \(N\)-particle Schrödinger operator possesses two local minima with respect to the locations of the nuclei. By definition, \textit{An isomerization is a mountain pass problem between these two local configurations, where one minimizes over all possible paths the highest value of the energy along the path. Critical points at the mountain pass level, are called in chemistry a transition state}. They state a conjecture about the compactness of min-maxing sequences of such paths. They then give a positive answer in the particular case of a molecule composed of two rigid sub-molecules that can move freely in space. Under appropriate assumptions on the multipoles of the two molecules, they are able to prove that the distance between them stays bounded during the whole chemical reaction. They obtain a critical point at the mountain pass level. This paper generalizes previous works by the second author [Ann. Henri Poincaré 5, No. 3, 477--521 (2004; Zbl 1062.81158)] in several directions.

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