التفاصيل البيبلوغرافية
| العنوان: |
Variance of the energy of a quantum system in a time-dependent perturbation: Determination by nonadiabatic transition probabilities. |
| المؤلفون: |
Mandal, Anirban, Hunt, Katharine L. C. |
| المصدر: |
Journal of Chemical Physics; 3/14/2020, Vol. 152 Issue 10, p1-12, 12p, 7 Graphs |
| مصطلحات موضوعية: |
EXCITED state energies, EXCITED states, VARIANCES, PROBABILITY theory, MASS transfer coefficients, QUANTUM states, GROUND state energy |
| مستخلص: |
For a quantum system in a time-dependent perturbation, we prove that the variance in the energy depends entirely on the nonadiabatic transition probability amplitudes bk(t). Landau and Lifshitz introduced the nonadiabatic coefficients for the excited states of a perturbed quantum system by integrating by parts in Dirac's expressions for the coefficients ck(1)(t) of the excited states to first order in the perturbation. This separates ck(1)(t) for each state into an adiabatic term ak(1)(t) and a nonadiabatic term bk(1)(t). The adiabatic term follows the adiabatic theorem of Born and Fock; it reflects the adjustment of the initial state to the perturbation without transitions. If the response to a time-dependent perturbation is entirely adiabatic, the variance in the energy is zero. The nonadiabatic term bk(1)(t) represents actual excitations away from the initial state. As a key result of the current work, we derive the variance in the energy of the quantum system and all of the higher moments of the energy distribution using the values of |bk(t)|2 for each of the excited states along with the energy differences between the excited states and the ground state. We prove that the same variance (through second order) is obtained in terms of Dirac's excited-state coefficients ck(t). We show that the results from a standard statistical analysis of the variance are consistent with the quantum results if the probability of excitation Pk is set equal to |bk(t)|2, but not if the probability of excitation is set equal to |ck(t)|2. We illustrate the differences between the variances calculated with the two different forms of Pk for vibration–rotation transitions of HCl in the gas phase. [ABSTRACT FROM AUTHOR] |
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