Photoabsorption spectra of Na(+)(n) clusters: thermal line-broadening mechanisms

Phys Rev Lett. 2001 Jul 30;87(5):053401. doi: 10.1103/PhysRevLett.87.053401. Epub 2001 Jul 13.

Abstract

Photoabsorption cross sections of small sodium cluster cations ( Na(+)(n), n = 3, 5, 7, and 9) were calculated at various temperatures with the time-dependent local-density approximation in conjunction with ab initio molecular dynamics simulations, yielding spectra that agree with measured ones without ad hoc line broadening or renormalization. Three thermal line-broadening mechanisms are revealed: (I) lifting of level degeneracies caused by symmetry-breaking ionic motions, (II) oscillatory shifts of the entire spectrum caused by breathing vibrations, and (III) cluster structural isomerizations.