Limits of the Creation of Electronic Wave Packets Using Time-Dependent Density Functional Theory

作者：Raghunathan Shampa; Nest Mathias^*

来源：Journal of Physical Chemistry A, 2012, 116(33): 8490-8493.

DOI：10.1021/jp3047483

Explicitly time-dependent density functional theory (TDDFT) has often been suggested as the method of choice for controlling the correlated dynamics of many electron systems. However, it is not yet clear which control tasks can be achieved reliably and how this depends on the functionals used. In this article, we show that the control task of creating a simple wave packet, having a population of 50% in the excited state, can indeed be achieved if a certain condition is fulfilled. This result is in contrast to the observation that a full population inversion is extremely difficult to achieve. In addition, we identify a rule to predict when TDDFT produces the correct wave packet. To illustrate our findings, we study the molecules Li2C2, Li7OH, and B2N2CO using two different functionals as well as time-dependent Hartree-Fock (TDHF). To assess the performance of TDDFT and TDHF, we compare with time-dependent configuration interaction calculations.

• 出版日期2012-8-23