TY - JOUR

T1 - Identifying Electronic Modes by Fourier Transform from δ-Kick Time-Evolution TDDFT Calculations

AU - Sinha-Roy, Rajarshi

AU - García-González, Pablo

AU - López Lozano, Xóchitl

AU - Whetten, Robert L.

AU - Weissker, Hans Christian

N1 - Publisher Copyright:
© 2018 American Chemical Society.

PY - 2018/12/11

Y1 - 2018/12/11

N2 - Time-dependent density-functional theory (TDDFT) is widely used for calculating electron excitations in clusters and large molecules. For optical excitations, TDDFT is customarily applied in two distinct approaches: transition-based linear-response TDDFT (LR-TDDFT) and the real-time formalism (RT-TDDFT). The former directly provides the energies and transition densities of the excitations, but it requires the calculation of a large number of empty electron states, which makes it cumbersome for large systems. By contrast, RT-TDDFT circumvents the evaluation of empty orbitals, which is especially advantageous when dealing with large systems. A drawback of the procedure is that information about the nature of individual spectral features is not automatically obtained, although it is of course contained in the time-dependent induced density. Fourier transform of the induced density has been used in some simple cases, but the method is, surprisingly, not widely used to complement the RT-TDDFT calculations; although the reliability of RT-TDDFT spectra is now widely accepted, a critical assessment for the corresponding transition densities and a demonstration of the technical feasibility of the Fourier-transform evaluation for general cases is still lacking. In the present work, we show that the transition densities of the optically allowed excitations can be efficiently extracted from a single δ-kick time-evolution calculation even in complex systems like noble metals. We assess the results by comparison with the corresponding LR-TDDFT ones and also with the induced densities arising from RT-TDDFT simulations of the excitation process.

AB - Time-dependent density-functional theory (TDDFT) is widely used for calculating electron excitations in clusters and large molecules. For optical excitations, TDDFT is customarily applied in two distinct approaches: transition-based linear-response TDDFT (LR-TDDFT) and the real-time formalism (RT-TDDFT). The former directly provides the energies and transition densities of the excitations, but it requires the calculation of a large number of empty electron states, which makes it cumbersome for large systems. By contrast, RT-TDDFT circumvents the evaluation of empty orbitals, which is especially advantageous when dealing with large systems. A drawback of the procedure is that information about the nature of individual spectral features is not automatically obtained, although it is of course contained in the time-dependent induced density. Fourier transform of the induced density has been used in some simple cases, but the method is, surprisingly, not widely used to complement the RT-TDDFT calculations; although the reliability of RT-TDDFT spectra is now widely accepted, a critical assessment for the corresponding transition densities and a demonstration of the technical feasibility of the Fourier-transform evaluation for general cases is still lacking. In the present work, we show that the transition densities of the optically allowed excitations can be efficiently extracted from a single δ-kick time-evolution calculation even in complex systems like noble metals. We assess the results by comparison with the corresponding LR-TDDFT ones and also with the induced densities arising from RT-TDDFT simulations of the excitation process.

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U2 - 10.1021/acs.jctc.8b00750

DO - 10.1021/acs.jctc.8b00750

M3 - Article

C2 - 30404453

AN - SCOPUS:85058157694

SN - 1549-9618

VL - 14

SP - 6417

EP - 6426

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 12

ER -