Journal of Physical Chemistry A, Vol.113, No.16, 4445-4450, 2009
Electronic Structure and TDDFT Optical Absorption Spectra of Silver Nanorods
Density functional theory calculations are employed to determine optimized geometries and excitation spectra for small pentagonal silver nanorods Ag-n with n = 13, 19, 25, 31, 37, 43, 49, 55, 61, and 67 in various charge states. The asymptotically correct SAOP functional is utilized in the excitation calculations. Silver nanorods exhibit a sharp longitudinal excitation that results from a mixture of orbital transitions; the wavelength for this excitation depends linearly on the length of the nanorod. The broad transverse excitation arises from multiple excited states. A particle-in-a-box model is employed to explain the linear dependence of the longitudinal excitation wavelength on nanorod length.