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arXiv:quant-ph/0201123

Space-adiabatic Decoupling to All Orders

Gianluca Panati, Herbert E. Spohn, Stefan Teufel

Published Jan 28, 2002• 3 citations
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Abstract

A systematic perturbation scheme is developed for approximate solutions to the time-dependent Schroedinger equation with a space-adiabatic Hamiltonian. For a particular isolated energy band, the basic approach is to separate kinematics from dynamics. The kinematics is defined through a subspace of the full Hilbert space for which transitions to other band subspaces are suppressed to all orders and the dynamics operates in that subspace in terms of an effective intraband Hamiltonian. As novel applications we discuss the Born-Oppenheimer theory to second order and derive the nonperturbative definition of the g-factor of the electron within nonrelativistic quantum electrodynamics.

DOI
10.48550/arxiv.quant-ph/0201123

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A systematic perturbation scheme is developed for approximate solutions to the time-dependent Schroedinger equation with a space-adiabatic Hamiltonian. For a particular isolated energy band, the basic approach is to separate kinematics from dynamics. The kinematics is defined through a subspace of the full Hilbert space for which transitions to other band subspaces are suppressed to all orders and the dynamics operates in that subspace in terms of an effective intraband Hamiltonian. As novel applications we discuss the Born-Oppenheimer theory to second order and derive the nonperturbative definition of the g-factor of the electron within nonrelativistic quantum electrodynamics.
A systematic perturbation scheme is developed for approximate solutions to the time-dependent Schrödinger equation with a space-adiabatic Hamiltonian. For a particular isolated energy band, the basic approach is to separate kinematics from dynamics. The kinematics is defined through a subspace of the full Hilbert space for which transitions to other band subspaces are suppressed to all orders, and the dynamics operates in that subspace in terms of an effective intraband Hamiltonian. As novel applications, we discuss the Born-Oppenheimer theory to second order and derive for the first time the nonperturbative definition of the g factor of the electron within nonrelativistic quantum electrodynamics.
We reconsider the time-dependent Born-Oppenheimer theory with the goal to carefully separate between the adiabatic decoupling of a given group of energy bands from their orthogonal subspace and the semiclassics within the energy bands. Band crossings are allowed and our results are local in the sense that they hold up to the rst time when a band crossing is encountered. The adiabatic decoupling leads to an eective Schrodinger equation for the nuclei, including contributions from the Berry connection. 1
Time-dependent and stationary wave operators are presented as tools to define active spaces and simplified dynamics for the integration of the time-dependent Schrödinger equation in large quantum spaces. Within this framework a new light is thrown on the duality between time-dependent and time-independent approaches and a generalized version of the adiabatic theorem is given. For the Floquet treatment of photodissociation processes, the choice of the relevant subspaces and the construction of the effective Hamiltonians are carried out using the Bloch wave operator techniques. Iterative solutions of the basic equations associated with these wave operators are given, based on Jacobi, Gauss-Seidel and variational schemes.
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.
A molecule in the presence of a radiation field is described by a non-Hermitian reduced effective Hamiltonian and its eigenvectors, the effective system states. These states form a natural basis for the evaluation of spectroscopic properties; its use requires a generalized formulation of quantum dynamics. The mathematical structure of the vector space defined by those states is investigated; that vector space is found to be a Banach space which reduces to Hilbert space if the energies of the effective system states become real. Time reversal symmetry is found to be an important feature of the overall problem. The generalized time development operator and the Schrödinger equation which defines it are deduced, and the effect of that operator on the effective system states is discussed. The proper generalization of time-dependent perturbation theory in the interaction picture is then derived and its use in applications is discussed in general terms.
When a time-dependent perturbation acts on a quantum system that is initially in the nondegenerate ground state ∣0> of an unperturbed Hamiltonian H(0), the wave function acquires excited-state components ∣k> with coefficients c(k)(t) exp(-iE(k)t/ℏ), where E(k) denotes the energy of the unperturbed state ∣k>. It is well known that each coefficient c(k)(t) separates into an adiabatic term a(k)(t) that reflects the adjustment of the ground state to the perturbation--without actual transitions--and a nonadiabatic term b(k)(t) that yields the probability amplitude for a transition to the excited state. In this work, we prove that the energy at any time t also separates completely into adiabatic and nonadiabatic components, after accounting for the secular and normalization terms that appear in the solution of the time-dependent Schrödinger equation via Dirac's method of variation of constants. This result is derived explicitly through third order in the perturbation. We prove that the cross-terms between the adiabatic and nonadiabatic parts of c(k)(t) vanish, when the energy at time t is determined as an expectation value. The adiabatic term in the energy is identical to the total energy obtained from static perturbation theory, for a system exposed to the instantaneous perturbation λH'(t). The nonadiabatic term is a sum over excited states ∣k> of the transition probability multiplied by the transition energy. By evaluating the probabilities of transition to the excited eigenstates ∣k'(t)> of the instantaneous Hamiltonian H(t), we provide a physically transparent explanation of the result for E(t). To lowest order in the perturbation parameter λ, the probability of finding the system in state ∣k'(t)> is given by λ(2) ∣b(k)(t)∣(2). At third order, the transition probability depends on a second-order transition coefficient, derived in this work. We indicate expected differences between the results for transition probabilities obtained from this work and from Fermi's golden rule.