Electronic circular dichroism with real time time dependent density functional theory: Propagator formalism and gauge dependence

Mattiat, Johann; Luber, Sandra

doi:10.1016/j.chemphys.2019.110464

Cited by 23 publications

(49 citation statements)

References 84 publications

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“…as discussed for RT-TDDFT in Ref. 82. This also affects the definition of the magnetic dipole moment operator in Eq.…”

Section: Representations Magnetic Response and Nonlocal Potentialsmentioning

confidence: 99%

“…The RT-TDDFT calculations were carried out with the package CP2K. [68][69][70]108 Continuing our previous efforts for the implementation of G in various representations, 82 the velocity representation of A was also implemented into CP2K. For the numerical integration of the time dependent Kohn-Sham equations, the Hamiltonian is extrapolated in time by the always-stable predictor corrector algorithm and several options are available for the approximation of the propagator and the calculation of the matrix exponential.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Another complexity that is covered naturally in the propagator formulation is a description of the coupling of nonlocal pseudopotentials to electromagnetic fields, where the operators have to be transformed consistently to their pseudopotential representation. [79][80][81][82] It can be shown that this transformation is necessarily gauge dependent. In practice, this leads to the introduction of the so called generalized momentum instead of the canonical momentum.…”

Section: Introductionmentioning

confidence: 99%

“…In practice, this leads to the introduction of the so called generalized momentum instead of the canonical momentum. 82,83 The focus of this work is on the theoretical description of our approach. Calculations are presented for (R)-methyloxirane.…”

Section: Introductionmentioning

confidence: 99%

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Vibrational (resonance) Raman optical activity with real time time dependent density functional theory

Mattiat

Luber

2019

The Journal of Chemical Physics

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We present a novel approach for the calculation of vibrational (resonance) Raman optical activity (ROA) spectra based on real time propagation. The ROA linear electronic response tensors are formulated in a propagator formalism in order to treat linear response (LR-) and real time time dependent density functional theory (RT-TDDFT) on equal footing. The length, mixed, and velocity representations of these tensors are discussed with respect to the potential origin dependence of the ROA invariants in the calculations. The propagator formalism allows a straight forward extension of the optical LR tensors in a mixed or velocity representation to a coupling with nonlocal potentials, where an extra term appears in the definition of the momentum operator, in order to maintain the gauge invariance. Using RT-TDDFT paves the way for an innovative, efficient calculation of both on-and offresonance ROA spectra. Exemplary results are given for the off-resonance and (pre-)resonance spectra of (R)-methyloxirane, considering the resonance effects due to one or more electronically excited states. Moreover, the developed real time propagation approach allows us to obtain entire excitation profiles in a computationally efficient way.

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“…as discussed for RT-TDDFT in Ref. 82. This also affects the definition of the magnetic dipole moment operator in Eq.…”

Section: Representations Magnetic Response and Nonlocal Potentialsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Vibrational (resonance) Raman optical activity with real time time dependent density functional theory

Mattiat

Luber

2019

The Journal of Chemical Physics

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“…All calculations presented in this paper assume the gauge origin to be placed in the centre of mass of the molecule. We note that the present methodology is gauge dependent, this dependence for ECD and ORD having been studied at the non-relativistic and relativistic levels of theory [93][94][95] , and we have not explored this further in this work.…”

Section: [X Smentioning

confidence: 99%

Relativistic four-component linear damped response TDDFT for electronic absorption and circular dichroism calculations

Konecny

Repiský

Ruud

et al. 2019

The Journal of Chemical Physics

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We present a detailed theory, implementation, and a benchmark study of a linear damped response time-dependent density functional theory (TDDFT) based on the relativistic four-component (4c) Dirac-Kohn-Sham formalism using the restricted kinetic balance condition for the small-component basis and a non-collinear exchangecorrelation kernel. The damped response equations are solved by means of a multifrequency iterative subspace solver utilizing decomposition of the equations according to hermitian and time-reversal symmetry. This partitioning leads to robust convergence and the detailed algorithm of the solver for relativistic multicomponent wavefunctions is also presented. The solutions are then used to calculate the linear electricand magnetic-dipole responses of molecular systems to an electric perturbation, leading to frequency-dependent dipole polarizabilities, electronic absorption and circular dichroism (ECD), and optical rotatory dispersion (ORD) spectra. The methodology has been implemented in the relativistic spectroscopy DFT program ReSpect, and its performance assessed on a model series of dimethylchalcogeniranes, C 4 H 8 X (X = O, S, Se, Te, Po, Lv) and on larger transition metal complexes that have been studied experimentally, [M(phen) 3 ] 3+ (M = Fe, Ru, Os). These are the first 4c damped linear response TDDFT calculations of ECD and ORD presented in the literature.

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Recent Progress in the Simulation of Chiral Systems with Real Time Propagation Methods

Mattiat

Luber

2021

Helvetica Chimica Acta

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In this brief review, an overview about recent efforts to simulate the spectroscopic signatures of chiral molecules is given with focus on real time propagation approaches to solve the time-dependent Schrödinger equation. In particular the simulation of electric circular dichroism spectra and vibrational Raman optical activity is discussed. In comparison to linear absorption spectra, where only the response of the electric dipole moment is necessary, the response of the magnetic dipole moment and electric quadrupole moment is more intricate. Issues such as gauge origin dependence, basis set dependence, non-local potentials and the dipole approximation are addressed.

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Electronic circular dichroism with real time time dependent density functional theory: Propagator formalism and gauge dependence

Cited by 23 publications

References 84 publications

Vibrational (resonance) Raman optical activity with real time time dependent density functional theory

Vibrational (resonance) Raman optical activity with real time time dependent density functional theory

Relativistic four-component linear damped response TDDFT for electronic absorption and circular dichroism calculations

Recent Progress in the Simulation of Chiral Systems with Real Time Propagation Methods

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