Finite-temperature infrared and Raman spectra of high-pressure hydrogen from first-principles molecular dynamics

Zhang, Chunyi; Zhang, Cui; Chen, Mohan; Kang, Wei; Gu, Zhuowei; Zhao, Jun; Liu, Cangli; Sun, Chengwei; Zhang, Ping

doi:10.1103/physrevb.98.144301

Cited by 19 publications

(14 citation statements)

References 48 publications

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“…We believe this slight underestimation is a residual consequence of the choice of the exchange and correlation functional, even if the BLYP functional we use is recognized among the most accurate for predicting energies of high-pressure hydrogen 21 and it is commonly chosen for the calculation of the hydrogen phase-diagram 14,19 . The huge peak shift and the change in the slope of the vibron frequency caused by the zero-point motion question the validity of previous calculations that do not include both anharmonicity and quantum nuclear fluctuations [12][13][14]20,28 .…”

mentioning

confidence: 77%

Black metal hydrogen above 360 GPa driven by proton quantum fluctuations

et al. 2020

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confidence: 77%

Black metal hydrogen above 360 GPa driven by proton quantum fluctuations

et al. 2020

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“…Since the energy of the vibron is more than 3000 cm −1 , the temperature needed to populate excited states is above 4000 K. For this reason, there is no hope to sim-ulate this lattice vibration with standard AIMD, that neglects quantum fluctuations. For this reason, previous studies on high-pressure hydrogen that neglected quantum effects reported a much more modest anharmonicity in the Raman signal [60,61].…”

Section: B High-pressure Hydrogenmentioning

confidence: 99%

Time-Dependent Self Consistent Harmonic Approximation: Anharmonic nuclear quantum dynamics and time correlation functions

Monacelli,

Mauri

2020

Preprint

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Most material properties of great physical interest are directly related to nuclear dynamics, e.g. the ionic thermal conductivity, Raman/IR vibrational spectra, inelastic X-ray, and Neutron scattering. A theory able to compute from first principles these properties, fully accounting for the quantum nature of the nuclei and the anharmonicity in the nuclear energy landscape that can be implemented in systems with hundreds of atoms is missing. Here, we derive an approximated theory for the quantum time evolution of lattice vibrations at finite temperature. This theory introduces the time dynamics in the Self-Consistent Harmonic Approximation (SCHA) and shares with the static case the same computational cost. It is nonempirical, as pure states evolve according to the Dirac least action principle and the dynamics of the thermal ensemble conserves both energy and entropy. The static SCHA is recovered as a stationary solution of the dynamical equations. We apply perturbation theory around the static SCHA solution and derive an algorithm to compute efficiently quantum dynamical correlation functions. Thanks to this new algorithm, we have access to the response function of any general external time-dependent perturbation, enabling the simulation of phonon spectra without following any perturbative expansion of the nuclear potential or empirical methods. We benchmark the method on the IR and Raman spectroscopy of high-pressure hydrogen phase III, with a simulation cell of 96 atoms. Our work also explores the nonlinear regime of the dynamical nuclear motion, providing a paradigm to simulate the interaction with intense or multiple probes, as in pump-probe spectroscopy, or chemical reactions involving light atoms, as the proton transfer in biomolecules.I.

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“…Previous calculations of the vibrational properties of hydrogen were based on classical molecular dynamics (MD) [8,9], which cannot include quantum anharmonicity. To overcome the MD limitations and include nuclear quantum effects (NQE), more advanced methods have been developed, such as the vibrational self-consistent field (VSCF) method [10][11][12] and the stochastic selfconsistent harmonic approximation (SSCHA) [13][14][15].…”

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confidence: 99%

Hydrogen phase-IV characterization by full account of quantum anharmonicity

Morresi,

Vuilleumier,

Casula

2022

Preprint

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We devise a framework to compute accurate phonons in molecular crystals even in case of strong quantum anharmonicity. Our approach is based on the calculation of the static limit of the phononic Matsubara Green's function from path integral molecular dynamics simulations. Our method enjoys a remarkably low variance, which allows one to compute accurate phonon frequencies after a few picoseconds of nuclear dynamics, and it is further stabilized by the use of appropriate constrained displacement operators. We applied it to solid hydrogen at high pressure. For phase III, our predicted infrared (IR) and Raman active vibrons agree very well with experiments. We then characterize the crystalline symmetry of phase IV by direct comparison with vibrational data and we determine the character of its Raman and IR vibron peaks.

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Finite-temperature infrared and Raman spectra of high-pressure hydrogen from first-principles molecular dynamics

Cited by 19 publications

References 48 publications

Black metal hydrogen above 360 GPa driven by proton quantum fluctuations

Black metal hydrogen above 360 GPa driven by proton quantum fluctuations

Time-Dependent Self Consistent Harmonic Approximation: Anharmonic nuclear quantum dynamics and time correlation functions

Hydrogen phase-IV characterization by full account of quantum anharmonicity

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