Nonadiabatic transition probabilities in a time-dependent Gaussian pulse or plateau pulse: Toward experimental tests of the differences from Dirac's transition probabilities.
Anirban MandalKatharine L C HuntPublished in: The Journal of chemical physics (2018)
For a quantum system subject to a time-dependent perturbing field, Dirac's analysis gives the probability of transition to an excited state |k⟩ in terms of the norm square of the entire excited-state coefficient ck(t) in the wave function. By integrating by parts in Dirac's equation for ck(t) at first order, Landau and Lifshitz separated ck (1)(t) into an adiabatic term ak (1)(t) that characterizes the gradual adjustment of the ground state to the perturbation without transitions and a nonadiabatic term bk (1)(t) that depends explicitly on the time derivative of the perturbation at times t' ≤ t. Landau and Lifshitz stated that the probability of transition in a pulsed perturbation is given by |bk(t)|2, rather than by |ck(t)|2. We use the term "transition probability" to refer to the probability that a true excited-state component is present in the time-evolved wave function, as opposed to a smooth modification of the initial state. In recent work, we have examined the differences between |bk(t)|2 and |ck(t)|2 when a system is perturbed by a harmonic wave in a Gaussian envelope. We showed that significant differences exist when the frequency of the harmonic wave is off-resonance with the transition frequency. In this paper, we consider Gaussian perturbations and pulses that rise via a half Gaussian shoulder to a level plateau and later return to zero via a down-going half Gaussian. While the perturbation is constant, the transition probability |bk(t)|2 does not change. By contrast, |ck(t)|2 continues to oscillate while the perturbation is constant, and its time averaged value differs from |bk(t)|2. We suggest a general type of experiment to prove that the transition probability is given by |bk(t)|2, not |ck(t)|2. We propose a ratio test that does not require accurate knowledge of transition matrix elements or absolute field intensities.