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Comparison of quantum Monte Carlo with time-dependent and static density-functional theory calculations of diamondoid excitation energies and Stokes shifts

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Article number245315
<mark>Journal publication date</mark>19/12/2011
<mark>Journal</mark>Physical review B
Issue number24
Volume84
Number of pages11
Publication StatusPublished
<mark>Original language</mark>English

Abstract

We compute the absorption and emission energies and hence Stokes shifts of small diamondoids as a function of size using different theoretical approaches, including density-functional theory (DFT) and quantum Monte Carlo (QMC) calculations. The absorption spectra of these molecules are also investigated by time-dependent DFT and compared with experiment. We analyze the structural distortion and formation of a self-trapped exciton in the excited state, and we study the effects of these on the Stokes shift as a function of size. Compared to recent experiments, QMC overestimates the excitation energies by about 0.8(1) eV on average. Benefiting from a cancellation of errors, the optical gaps obtained in DFT calculations with the B3LYP functional are in better agreement with experiment. It is also shown that time-dependent B3LYP calculations can reproduce most of the features found in the experimental spectra. According to our calculations, the structures of diamondoids in the excited state show a distortion which is hardly noticeable compared to that found for methane. As the number of diamond cages is increased, the distortion mechanism abruptly changes character. We have shown that the Stokes shift is size dependent and decreases with the number of diamond cages. If we neglect orbital symmetry effects on the optical excitations, the rate of decrease in the Stokes shift is, on average, 0.1 eV per cage for small diamondoids.

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©2011 American Physical Society