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Physical Review Letters

Molecular Kramers degeneracy and non-Abelian adiabatic phase factors

C. Alden Mead

Published Jul 13, 1987• 121 citations
Publisher

Abstract

For a molecular system with an odd number of electrons, the electronic Hamiltonian possesses a twofold Kramers degeneracy for all nuclear configurations. It is shown that this leads to a non-Abelian gauge-field term in the effective nuclear Hamiltonian, with permissible gauge transformations belonging to SU(2). This should lead to observable effects analogous to the Berry phase for the nondegenerate case. In particular, an atom in a slowly rotating electric field exhibits changes in its component of angular momentum along the field because of the non-Abelian phase factor.

DOI
10.1103/physrevlett.59.161

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Physical review. D. Particles, fields, gravitation, and cosmology/Physical review. D. Particles and fields•Feb 15, 1990•35 citations
For a molecular system with an odd number of electrons, the electronic Hamiltonian possesses a twofold Kramers degeneracy for all nuclear configurations. It is shown that this leads to a non-Abelian gauge-field term in the effective nuclear Hamiltonian, with permissible gauge transformations belonging to SU(2). This should lead to observable effects analogous to the Berry phase for the nondegenerate case. In particular, an atom in a slowly rotating electric field exhibits changes in its component of angular momentum along the field because of the non-Abelian phase factor.
The full effect of adiabatically varying Hamiltonians on systems prepared in eigenstates of the stationary Hamiltonian often includes geometric Berry's phases. For degenerate systems these effects may result in transitions between distinct degenerate eigenstates that can be described in terms of a non-Abelian gauge potential. I demonstrate the explicit dynamic origin of such transitions between degenerate angular-momentum sublevels in an atom that is subject to collinear electric and magnetic fields that rotate adiabatically. The origin of the effects becomes clear when eigenstates of the total Hamiltonian, which includes the rotating fields, are calculated. The total Hamiltonian removes the degeneracy, and the eigenstates are in some cases linear combinations of the angular-momentum sublevels. Thus a system prepared in a specific sublevel may not remain in that sublevel, and the transition probability is exactly that given by an analysis of the geometric phase.
The fundamental theory of the geometric phase is summarized in a way suitable for use in molecular systems treated by the Born-Oppenheimer approach. Both Abelian and non-Abelian cases are considered. Applications discussd include the Abelian geometric phase associated with an intersection of two electronic potential-energy surfaces; screening of nuclei by the electrons from an external magnetic field; non-Abelian gauge potentials in molecular systems with Kramers degeneracy; and the coupling between different electronic levels (Born-Oppenheimer breakdown) represented as a gauge potential. Experimental tests for these systems are discussed, as well as a number of experiments on spin systems.
The non-Abelian Berry’s phase effect for a family of operators H0+k⋅V is considered, where H0 is rotationally invariant, V is a vector operator, and k varies over the unit vectors in R3. The parameter space is the two-sphere. The time evolution in the adiabatic limit is given by a connnection on a fiber bundle over the two-sphere. All connections consistent with the rotational symmetry are classified, and the time evolution is explicitly calculated for a nondegenerate Hamiltonian, as well as for a Hamiltonian with a double degeneracy. In the nondegenerate case, the connection is uniquely determined by the symmetry. In the doubly degenerate case, the connection is in some instances not determined by the symmetry. The case of approximate degeneracy is also discussed. A possible experimental test of this effect using optical pumping is described elsewhere.
Geometric phase is an interesting topic that is germane to numerous and varied research areas: molecules, optics, quantum computing, quantum Hall effect, graphene, and so on. It exists only when the system of interest interacts with something it perceives as exterior. An isolated system cannot display geometric phase. This article addresses geometric phase in polyatomic molecules from a gauge field theory perspective. Gauge field theory was introduced in electrodynamics by Fock and examined assiduously by Weyl. It yields the gauge field A(μ), particle-field couplings, and the Aharonov-Bohm phase, while Yang-Mills theory, the cornerstone of the standard model of physics, is a template for non-Abelian gauge symmetries. Electronic structure theory, including nonadiabaticity, is a non-Abelian gauge field theory with matrix-valued covariant derivative. Because the wave function of an isolated molecule must be single-valued, its global U(1) symmetry cannot be gauged, i.e., products of nuclear and electron functions such as χ(n)ψ(n) are forbidden from undergoing local phase transformation on R, where R denotes nuclear degrees of freedom. On the other hand, the synchronous transformations (first noted by Mead and Truhlar): ψ(n)→ψ(n)e(iζ) and simultaneously χ(n)→χ(n)e(-iζ), preserve single-valuedness and enable wave functions in each subspace to undergo phase transformation on R. Thus, each subspace is compatible with a U(1) gauge field theory. The central mathematical object is Berry's adiabatic connection i<n|∇n>, which serves as a communication link between the two subsystems. It is shown that additions to the connection according to the gauge principle are, in fact, manifestations of the synchronous (e(iζ)/e(-iζ)) nature of the ψ(n) and χ(n) phase transformations. Two important U(1) connections are reviewed: qA(μ) from electrodynamics and Berry's connection. The gauging of SU(2) and SU(3) is reviewed and then used with molecules. The largest gauge group applicable in the immediate vicinity of a two-state intersection is U(2), which factors to U(1) × SU(2). Gauging SU(2) yields three fields, whereas U(1) is not gauged, as the result cannot be brought into registry with electronic structure theory, and there are other problems as well. A parallel with spontaneous symmetry breaking in electroweak theory is noted. Loss of SU(2) symmetry as the energy gap between adiabats increases yields the inter-related U(1) symmetries of the upper and lower adiabats, with spinor character imprinted in the vicinity of the degeneracy.
A high-order adiabatic-approximation method is proposed to study the time evolution of degenerate quantum-mechanical systems with slowly changing Hamiltonians. We not only discuss the quantum adiabatic theorem, induced gauge structure, and non-Abelian Berry's phase factors in the first-order approximation, but we also give nonadiabatic corrections for problems in the second-order approximation. With the nuclear quadrupole resonance as an explicit example, we analyze the above-mentioned questions in detail and point out the observable effects of non-Abelian Berry's phase factors for nonadiabatic transitions between two instantaneous states in an improvement of Tycko's experiment.