Comparing thermal wave function methods for multi-configuration time-dependent Hartree simulations

Lorenz, Ulf; Saalfrank, Peter

doi:10.1063/1.4862739

Cited by 21 publications

(15 citation statements)

References 20 publications

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“…This can perhaps be done in the spirit of the GLO method, for instance using a density matrix formalism 68−70 or using stochastic wave function approaches. 71−74 Before such QD calculations are carried out, it might be useful to test whether it is necessary to retain all three degrees of freedom of the surface atom or whether it might be enough just to model its motion perpendicular to the surface. Finally, the GLO+F method clearly suffices for modeling the effect of surface phonons and ehp excitation on dissociative chemisorption (Figure 3) and to calculate energy loss to the surface (Tables 2 and 3).…”

Section: Resultsmentioning

confidence: 99%

Vibrational Excitation of H₂ Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface

2017

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In scattering of H2 from Cu(111), vibrational excitation has so far defied an accurate theoretical description. To expose the causes of the large discrepancies with experiment, we investigate how the feature due to vibrational excitation (the “gain peak”) in the simulated time-of-flight spectrum of (v = 1, j = 3) H2 scattering from Cu(111) depends on the surface temperature (Ts) and the possibility of energy exchange with surface phonons and electron–hole pairs (ehp’s). Quasi-classical dynamics calculations are performed on the basis of accurate semiempirical density functionals for the interaction with H2 + Cu(111). The methods used include the quasi-classical trajectory method within the Born–Oppenheimer static surface model, the generalized Langevin oscillator (GLO) method incorporating energy transfer to surface phonons, the GLO + friction (GLO+F) method also incorporating energy exchange with ehp’s, and ab initio molecular dynamics with electronic friction (AIMDEF). Of the quasi-classical methods tested, comparison with AIMDEF suggests that the GLO+F method is accurate enough to describe vibrational excitation as measured in the experiments. The GLO+F calculations also suggest that the promoting effect of raising Ts on the measured vibrational excitation is due to an electronically nonadiabatic mechanism. However, by itself, enabling energy exchange with the surface by modeling surface phonons and ehp’s leads to reduced vibrational excitation, further decreasing the agreement with experiment. The simulated gain peak is quite sensitive to energy shifts in calculated vibrational excitation probabilities and to shifts in a specific experimental parameter (the chopper opening time). While the GLO+F calculations allow important qualitative conclusions, comparison to quantum dynamics results suggests that, with the quasi-classical way of describing nuclear motion and the present box quantization method for assigning the final vibrational state, the gain peak is not yet described with quantitative accuracy. Ways in which this problem might be resolved in the future are discussed.

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Section: Resultsmentioning

confidence: 99%

Vibrational Excitation of H₂ Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface

2017

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“…89,90,94,97 When the system adopts a finite temperature, vibrationally excited states become populated with temperature-dependent probabilities, that can be obtained, e.g., from statistical sampling. 214 Despite its simplicity, there are no wave packet/MCTDH dynamics simulations of transition metal complexes including temperature.…”

Section: Temperaturementioning

confidence: 99%

The quest to simulate excited-state dynamics of transition metal complexes

Zobel,

Gonzalez

2021

Preprint

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This Perspective describes current computational efforts in the field of simulating photodynamics of transition metal complexes. We present the typical workflows and feature the strengths and limitations of the different contemporary approaches.From electronic structure methods suitable to describe transition metal complexes to approaches able to simulate their nuclear dynamics under the effect of light, we lay particular attention to build a bridge between theory and experiment by critically discussing the different models commonly adopted in the interpretation of spectroscopic experiments and the simulation of particular observables. Thereby, we review all the studies of excited state dynamics on transition metal complexes, both in gas phase and in solution from reduced to full dimensionality.

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“…This should be contrasted with the methodology of Refs. [] which, along with the propagation of wave functions in β and t in the

{| x ⟩}

space require sampling of the initial states, so that

⟨ A (t) ⟩

is calculated upon averaging over all

β - t

“trajectories”.…”

Section: Thermal Transformations For Correlated Statesmentioning

confidence: 99%

“…The methods of the group (i) perform excellently at zero temperature. At room temperature, they require a statistical sampling of the initial conditions followed, in some procedures, by a double propagation in real and imaginary time . Recently, we have suggested an alternative and computationally efficient wave‐function‐based method for the simulation of time‐dependent properties of quantum systems with many degrees of freedom at finite temperature .…”

Section: Introductionmentioning

confidence: 99%

Thermal Schrödinger Equation: Efficient Tool for Simulation of Many‐Body Quantum Dynamics at Finite Temperature

Gelin

Borrelli

2017

Annalen der Physik

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We develop a wave-function-based method for the simulation of quantum dynamics of systems with many degrees of freedom at finite temperature. The method is inspired by the ideas of Thermo Field Dynamics (TFD). As TFD, our method is based on the doubling of the system's degrees of freedom and thermal Bogoliubov transformation. As distinct from TFD, our method implements the doubling of thermalized degrees of freedom only, and relies upon the explicitly constructed generalized thermal Bogoliubov transformation, which is not restricted to fermionic and bosonic degrees of freedom. This renders the present approach computationally efficient and applicable to a large variety of systems.

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Comparing thermal wave function methods for multi-configuration time-dependent Hartree simulations

Cited by 21 publications

References 20 publications

Vibrational Excitation of H₂ Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface

Vibrational Excitation of H₂ Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface

The quest to simulate excited-state dynamics of transition metal complexes

Thermal Schrödinger Equation: Efficient Tool for Simulation of Many‐Body Quantum Dynamics at Finite Temperature

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Comparing thermal wave function methods for multi-configuration time-dependent Hartree simulations

Cited by 21 publications

References 20 publications

Vibrational Excitation of H2 Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface

Vibrational Excitation of H2 Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface

The quest to simulate excited-state dynamics of transition metal complexes

Thermal Schrödinger Equation: Efficient Tool for Simulation of Many‐Body Quantum Dynamics at Finite Temperature

Contact Info

Product

Resources

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Vibrational Excitation of H₂ Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface

Vibrational Excitation of H₂ Scattering from Cu(111): Effects of Surface Temperature and of Allowing Energy Exchange with the Surface