The plasmonic properties of sphere-like bcc Na nanoclusters ranging from Na$_{15}$ to Na$_{331}$ have been studied by real-time time-dependent local density approximation calculations. The optical absorption spectrum, density response function and st
atic polarizability are evaluated. It is shown that the effect of the ionic background (ionic species and lattice) of the clusters accounts for the remaining discrepancy in the principal (surface plasmon) absorption peak energy between the experiments and previous calculations based on a jellium background model. The ionic background effect also pushes the critical cluster size where the maximum width of the principal peak occurs from Na$_{40}$ predicted by the previous jellium model calculations to Na$_{65}$. In the volume mode clusters (Na$_{27}$, Na$_{51}$, Na$_{65}$, Na$_{89}$ and Na$_{113}$) in which the density response function is dominated by an intense volume mode, a multiple absorption peak structure also appears next to the principal peak. In contrast, the surface mode clusters of greater size (Na$_{169}$, Na$_{229}$, Na$_{283}$ and Na$_{331}$) exhibit a smoother and narrower principal absorption peak because their surface plasmon energy is located well within that of the unperturbed electron-hole transitions, and their density responses already bear resemblance to that of classical Mie theory. Moreover, it is found that the volume plasmon that exist only in finite size particles, gives rise to the long absorption tail in the UV region. This volume plasmon manifests itself in the absorption spectrum even for clusters as large as Na$_{331}$ with an effective diameter of $sim$3.0 nm.
We systematically investigate the possible complex transition origin of electronic excitations of giant molecular systems by using the recently proposed QNTO analysis [J.-H. Li, J.-D. Chai, G. Y. Guo and M. Hayashi, Chem. Phys. Lett., 2011, 514, 362.
] combined with long-range corrected TDDFT calculations. Thymine (Thy) related excitations of biomolecule B-DNA are then studied as examples, where the model systems have been constructed extracting from the perfect or a X-ray crystal (PDB code 3BSE) B-DNA structure with at least one Thy included. In the first part, we consider the systems composed of a core molecular segment (e.g. Thy, di-Thy) and a surrounding physical/chemical environment of interest (e.g. backbone, adjacent stacking nucleobases) and examine how the excitation properties of the core vary in response to the environment. We find that the orbitals contributed from DNA backbone and surrounding nucleobases often participate in a transition of Thy-related excitations affecting their composition, absorption energy, and oscillator strength. In the second part, we take into account geometrically induced variation of the excitation properties of various B-DNA segments, e.g. di-Thy, dTpdT etc., obtained from different sources (ideal and 3BSE). It is found that the transition origin of several Thy-related excitations of these segments is sensitive to slight conformational variations, suggesting that DNA with thermal motions in cells may from time to time exhibit very different photo-induced physical and/or chemical processes.
We show that the origin of electronic transitions of molecular many-body systems can be revealed by a quantified natural transition orbitals (QNTO) analysis and the electronic excitations of the total system can be mapped onto a standard orbitals set
of a reference system. We further illustrate QNTO on molecular systems by studying the origin of electronic transitions of DNA moiety, thymine and thymidine. This QNTO analysis also allows us to assess the performance of various functionals used in time-dependent density functional response theory.
