Efficient electron dynamics with the planewave-based real-time time-dependent density functional theory: Absorption spectra, vibronic electronic spectra, and coupled electron-nucleus dynamics

Min, Seung Kyu; Cho, Yeonchoo; Kim, Kwang S.

doi:doi:10.1063/1.3671952

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An algebraic operator approach to electronic structure

In this paper, we introduce an algebraic approach to electronic structure calculations. Our approach constructs a Jordan algebra based on the second-quantized electronic Hamiltonian. From the structure factor of this algebra, we show that we can calculate the energy of the ground electronic state of the Hamiltonian operator. We apply our method to several generalized Hubbard models and show that we can usually obtain a significant fraction of the correlation energy for low-to-moderate values of ...

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of ¹⁴N¹⁵N

The first comprehensive high-resolution photoabsorption spectrum of 14N15N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet and span 100 000–109 000 cm−1 (100–91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N2 that simu...

The electron dynamics with complex third-order Suzuki-Trotter propagator (ST₃) has been implemented into a planewave (PW) based density functional theory program, and several applications including linear absorption spectra and coupled electron-nucleus dynamics have been calculated. Since the ST₃ reduces the number of Fourier transforms to less than half compared to the fourth-order Suzuki-Trotter propagator (ST₄), more than twice faster calculations are possible by exploiting the ST₃. We analyzed numerical errors of both the ST₃ and the ST₄ in the presence/absence of an external field for several molecules such as Al₂, N₂, and C₂H₄. We obtained that the ST₃ gives the same order of numerical errors (10⁻⁵ Ry after 100 fs) as the ST₄. Also, the time evolution of dipole moments, hence the absorption spectrum, is equivalent for both ST₃ and ST₄. As applications, the linear absorption spectrum for an ethylene molecule was studied. From the density difference analysis, we showed that the absorption peaks at 6.10 eV and 7.65 eV correspond to the π → 4a_g and π → π* excitation bands, respectively. We also investigated the molecular vibrational effect to the absorption spectra of an ethylene molecule and the dynamics of a hydrogen molecule after the σ → σ* transition by formulating coupled electron-nucleus dynamics within the Ehrenfest regime. The trajectory of nuclei follows the excited state potential energy curve exactly.

Article Outline

INTRODUCTION
METHODS
1. Theoretical basis
2. Calculations
RESULTS
1. Accuracy and stability
2. Linear absorption spectrum
3. The effect of nucleus motion on absorption spectrum
4. Excited state dynamics
CONCLUSION

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KEYWORDS and PACS

Keywords

aluminium, density functional theory, excited states, Fourier transforms, molecular moments, nitrogen, organic compounds, potential energy surfaces, ultraviolet spectra, vibrational states, vibronic states, visible spectra

PACS

31.15.ee

Time-dependent density functional theory
33.20.Tp

Vibrational analysis
33.15.Kr

Electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
31.50.Df

Potential energy surfaces for excited electronic states
33.20.Lg

Ultraviolet spectra
33.20.Kf

Visible spectra

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3671952

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

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