title: Adiabatic and nonadiabatic contributions to the energy of a system subject to a time-dependent perturbation: complete separation and physical interpretation.
abstract: 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.
authors.affiliation: Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA.
authors.forename: Anirban
authors.initials: A
authors.lastname: Mandal
authors.forename: Katharine L C
authors.initials: KL
authors.lastname: Hunt