First principles electron-correlated calculations of optical absorption in magnesium clusters

Abstract

In this paper, we report large-scale configuration interaction (CI) calculations of linear optical absorption spectra of various isomers of magnesium clusters Mg${}_n$ (n=2--5), corresponding to valence transitions. Geometry optimization of several low-lying isomers of each cluster was carried out using coupled-cluster singles doubles (CCSD) approach, and these geometries were subsequently employed to perform ground and excited state calculations using either the full-CI (FCI) or the multi-reference singles-doubles configuration interaction (MRSDCI) approach, within the frozen-core approximation. Our calculated photoabsorption spectrum of magnesium dimer (Mg${}_2$) isomer is in excellent agreement with the experiments both for peak positions, and intensities. Owing to the sufficiently inclusive electron-correlation effects, these results can serve as benchmarks against which future experiments, as well as calculations performed using other theoretical approaches, can be tested.

23 pages and 21 figures of main text

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Cited by in corpus (4)

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• First Principles Study of Structural and Optical Properties of B${}_{12}$ Isomers