Quantum and thermal fluctuation effects on the photoabsorption spectra of clusters -: art. no. 183401

A first principles approach for the calculation of photoabsorption cross sections of clusters and molecules is presented which includes both quantum and thermal fluctuations. The method relies on an ab initio path integral representation of the nuclear quantum motion in conjunction with time-dependent density-functional theory for electronic excitations. It is shown that quantum fluctuations of cold lithium clusters, such as Li-8 below 50 K, affect significantly their photoabsorption spectra.