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Physical Review

Solution of the Schrödinger Equation with a Hamiltonian Periodic in Time

J.H. Shirley

Published May 24, 1965• 2,888 citations
Publisher

Abstract

The interaction of a quantum system with an oscillating field is studied in a formalism which replaces the semiclassical time-dependent Hamiltonian with a time-independent Hamiltonian represented by an infinite matrix. The formalism is developed as a mathematical equivalent to the semiclassical treatment, and interpreted as a classical approximation to the quantum treatment of the field. Combined with a perturbation theory for two nearly degenerate states, the formalism provides a convenient method for determining resonance transition probabilities including frequency shifts and multiple quantum transitions. The theory is illustrated by a detailed study of the simple case of a two-state system excited by a strong oscillating field.

DOI
10.1103/physrev.138.b979

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The interaction of a quantum system with an oscillating field is studied in a formalism which replaces the semiclassical time-dependent Hamiltonian with a time-independent Hamiltonian represented by an infinite matrix. The formalism is developed as a mathematical equivalent to the semiclassical treatment, and interpreted as a classical approximation to the quantum treatment of the field. Combined with a perturbation theory for two nearly degenerate states, the formalism provides a convenient method for determining resonance transition probabilities including frequency shifts and multiple quantum transitions. The theory is illustrated by a detailed study of the simple case of a two-state system excited by a strong oscillating field.
The problem of the interaction of a quantum system having discrete states, with a classical oscillating field, is reexamined as a problem in the solution of the time-dependent Schrodinger equation with a periodic Hamiltonian. A method is presented for approximating the time-dependent Hamiltonian with a time-independent one in the weak oscillating field case. With the aid of Floquet's theorem the problem is exactly converted to one with a time-independent Hamiltonian represented by an infinite matrix. The approximation of only two states then permits finding the resonance line shape by perturbation theory for both single and multiple quantum transitions with equal ease. The simple case of only two states connected by an off diagonal sinusoidal perturbation is studied in detail, and a complete description of the average transition probability is found for the strong oscillating field case. A few more complex cases are discussed. A deeper understanding of the analysis is obtained by examining the theory with the oscillating field quantized. Experimental verification of the theory could best be obtained by the methods of atomic beam spectroscopy at radio frequencies.
Abstract This chapter the reviews essential concepts and methods of time-dependent quantum mechanics. (1) Formal solutions of the time-dependent Schrödinger equation. (2) The two-level system. (3) Interacting systems: The time-dependent self-consistent field approximation and the Ehrenfest approximation. (4) The Born–Oppenheimer approximation and nuclear potential surfaces. (5) Time-dependent Hamiltonians: A two-level system in a time-dependent field. (6) Non-adiabatic dynamics: The surface-hopping method. (7) Expressing the time evolution in terms of the Green operator. (8) Representations (the Schrödinger and Heisenberg representations, the interaction representation). (9) Time-dependent perturbation theory. (10) Quantum dynamics of the free particles. (11) Quantum dynamics of the harmonic oscillator. (12) The raising/lowering operators formalism. (13) Tunneling.
The Schrodinger equation for the interaction of a decaying two-level atom with an external oscillating field is separated via a series of matrix transformations into a time independent and a time dependent part; the former yields the radiofrequency Stark shift for decaying states, the latter is normally negligible for atomic beam resonance experiments. In the limit of stable states, or for the case of two levels of equal lifetime, the shift reduces to that of the Bloch-Siegert effect. Exact analytical expressions for the state amplitudes are obtained for the case when the time dependent matrix can be neglected; the resulting transition probabilities are investigated as functions of frequency, time, and interaction strength and are compared with the rotating field theory and the exact numerical solutions.
This report discusses two new ideas for using perturbation methods to solve the time-independent Schrödinger equation. The first concept begins with rewriting the perturbation equations in a form that is closely related to matrix diagonalization methods. That allows a simple, compact derivation of the standard (Rayleigh-Schrödinger) equations. But it also leads to a new iterative solution method that is not based on the usual power series expansion. The iterative method can also be used when the unperturbed system is two-fold degenerate. The second concept is quite different from the first but compatible with it. It is based on the fact that one can replace the true Hamiltonian with a synthetic Hamiltonian having the same eigenvalues. This approach allows one to cancel part of the perturbation and to reduce the size of the off-diagonal matrix elements, giving better convergence of the series. These methods are illustrated by application to three perturbed harmonic oscillator problems--a 1-D oscillator with a linear perturbation, a 1-D oscillator with a quartic perturbation, and a perturbed 2-D oscillator, which involves degenerate states. The iterative method and the synthetic Hamiltonian method are shown to give significantly better results than the standard method.
Abstract Quantum perturbation is an important tool for developing approximate solutions to quantum problems that cannot be solved exactly. This chapter provides a brief, systematic development of both time-independent and time-dependent quantum perturbation theory and the physical interpretation of its results, including both first- and second-order corrections. A quartic perturbation of the simple harmonic oscillator is used to illustrate time-independent perturbation theory. A spin-1/2 system subject to an oscillating field is used in time-dependent perturbation theory to describe the absorption and emission of energy from the quantum system.
Explicitly time-dependent Hamiltonians are ubiquitous in applications of quantum theory. It is therefore necessary to solve the time-dependent Schrödinger equation directly. The system’s dynamics is associated with a unitary time-evolution operator (a propagator), formally given as an infinite Dyson series. Time-dependent observables are invariant under unitary time-dependent transformations, where it is sometimes useful to transform the time-evolution from the states into the corresponding operators. This is carried out in part (in full) by transforming to the interaction (Heisenberg) picture. The corresponding equations of motion for the time-dependent operators are introduced. For quadratic potential energy functions, the time evolution of quantum expectation values coincides with the corresponding classical dynamics. This is demonstrated and analyzed in detail for Gaussian wave packets and a coherent state. Finally, we derive exact and approximate expressions for time-dependent transition probabilities and transition rates between quantum states. The validity of time-dependent perturbation theory is analyzed by comparison to exact dynamics.