First principles study of the electronic structure and phonon dispersion of naphthalene under pressure

Fedorov, I. A.; Marsusi, Farah; Fedorova, T. P.; Zhuravlev, Yu. N.

doi:10.1016/j.jpcs.2015.03.018

Cited by 17 publications

(12 citation statements)

References 59 publications

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“…Then, we concentrate our analysis on the intramolecular modes at higher frequencies calculated with DF-cx and compare our results to IR and Raman measurements. In accord with prior work 49,59,71 , we find that the phonon band structure shows a gap of roughly 40 cm −1 between the intermolecular and intramolecular modes. While we do confirm the observation of Coropceanu et al 59 that all translational modes show slight internal bending motion, the mixing between inter-and intramolecular modes is very small and can be neglected for the purpose of classification.…”

Section: Resultssupporting

confidence: 91%

“…To our knowledge, only two ab initio phonon band structures of acene crystals have been reported to date 71,72 . The full phonon dispersion of tetracene has recently been calculated using the local density approximation (LDA), capitalizing on the tendency of LDA to overbind to partially compensate for the lack of vdWcorrections 72 .…”

Section: Introductionmentioning

confidence: 99%

“…The full phonon dispersion of tetracene has recently been calculated using the local density approximation (LDA), capitalizing on the tendency of LDA to overbind to partially compensate for the lack of vdWcorrections 72 . Band structures of solid naphthalene calculated at different pressures have been presented by Fedorov et al 71 using the DFT-D3 approach 40 but without any detailed comparison with experiment. Considering the fundamental importance of phonons in organic crystals, there remains a need to assess and understand the efficacy of existing approaches for calculating phonon dispersions over the entire Brillouin zone in vdW-bound solids, particularly in the context of a well-characterized system such as naphthalene.…”

Section: Introductionmentioning

confidence: 99%

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Ab initiophonon dispersion in crystalline naphthalene using van der Waals density functionals

2016

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Acene molecular crystals are of current interest in organic optoelectronics, both as active materials and for exploring and understanding new phenomena. Phonon scattering can be an important facilitator and dissipation mechanism in charge separation and carrier transport processes. Here, we carry out density functional theory (DFT) calculations of the structure and the full phonon dispersion of crystalline naphthalene, a well-characterized acene crystal for which detailed neutron diffraction measurements, as well as infrared and Raman spectroscopy, are available. We evaluate the performance, relative to experiments, of the local density approximation (LDA); the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE); and a recent van der Waalscorrected non-local correlation functional (vdW-DF-cx). We find that the vdW-DF-cx functional accurately predicts lattice parameters of naphthalene within 1%. Intermolecular and intramolecular phonon frequencies across the Brillouin zone are reproduced within 7.8% and 1%, respectively. As expected, LDA (PBE) underestimates (overestimates) the lattice parameters and overestimates (underestimates) phonon frequencies, demonstrating their shortcomings for predictive calculations of weakly-bound materials. Additionally, if the unit cell is fixed to the experimental lattice parameters, PBE is shown to lead to improved phonon frequencies. Our study provides a detailed understanding of the phonon spectrum of naphthalene, and highlights the importance of including van der Waals dispersion interactions in predictive calculations of lattice parameters and phonon frequencies of molecular crystals and related organic materials.

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Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ab initiophonon dispersion in crystalline naphthalene using van der Waals density functionals

2016

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“…Since all Crystal-AFED trajectories of naphthalene at high pressure produced supercells with stacking faults or misaligned domains, we suggest that formation of these partially disordered structures is responsible for the volume changes observed as naphthalene is compressed (Bridgman, 1938;Block et al, 1970;Likhacheva et al, 2014). The computational cost of larger supercells prohibits sampling the full entropic effect of disordered domains, but we note that previous work on naphthalene polymorphs based on single unit cells was inherently unable to identify this type of longrange disorder (Likhacheva et al, 2014;Fedorov et al, 2015). The Crystal-AFED approach is therefore a valuable tool to determine the likely polymorphs, and types of local disorder, found in molecular crystals.…”

Section: Pressure Effects On Naphthalene Crystal Structure Stabilitymentioning

confidence: 81%

Exploring polymorphism of benzene and naphthalene with free energy based enhanced molecular dynamics

Schneider

Vogt

Tuckerman

2016

Acta Crystallogr Sect B

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Prediction and exploration of possible polymorphism in organic crystal compounds are of great importance for industries ranging from organic electronics to pharmaceuticals to high-energy materials. Here we apply our crystal structure prediction procedure and the enhanced molecular dynamics based sampling approach called the Crystal-Adiabatic Free Energy Dynamics (Crystal-AFED) method to benzene and naphthalene. Crystal-AFED allows the free energy landscape of structures to be explored efficiently at any desired temperature and pressure. For each system, we successfully predict the most stable crystal structures at atmospheric pressure and explore the relative Gibbs free energies of predicted polymorphs at high pressures. Using Crystal-AFED sampling, we find that mixed structures, which typically cannot be discovered by standard crystal structure prediction methods, are prevalent in the solid forms of these compounds at high pressure.

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“…Crystalline naphthalene has a structure with the P2 1 /a space group, and with two molecules in the monoclinic unit cell, each situated at inversion centers [107]. Both the infrared spectrum [93,108,109] and the phonon dispersion curves [110,111] of naphthalene were measured in laboratory and are well understood [112].…”

Section: Polycyclic Aromatic Hydrocarbonsmentioning

confidence: 99%

Light Dark Matter Detection with Hydrogen-rich Crystals and Low-Tc TES Detectors

Wang,

Chang,

Lisovenko

et al. 2022

Preprint

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Direct detection of nuclear scatterings of sub-GeV Dark Matter (DM) particles favors low-Z nuclei. Hydrogen nucleus, which has a single proton, provides the best kinematic match to a light dark matter particle. The characteristic nuclear recoil energy is boosted by a factor of a few tens from those for larger nuclei used in traditional Weakly Interacting Massive Particle (WIMP) searches. Furthermore, hydrogen is optimal not only for spin-independent nuclear scattering of a sub-GeV DM, but also for spin-dependent nuclear scatterings, where large parameter space remains unconstrained yet. In this paper, we first introduce hydrogen-rich crystals, which emit two classes of signals under kinetic excitations. One class of the signals is infrared photons, which are from optically active fundamental vibrational modes of molecules and at several characteristic wavelengths. Another is acoustic phonons, and optical phonons that decay into acoustic phonons. We then discuss the technical status and future researches of low-Tc Transition-Edge Sensor (TES) detectors, which measure single infrared photons and a small flux of acoustic phonons with desirable sensitivities. With theoretical modeling to select hydrogen-rich crystals for the optimized science reach, ultra-sensitive low-Tc TES detectors for readout, and experimental prototyping of a light DM detection scheme, a detection experiment can be built for measuring the large unexplored parameter space of light DM particles.

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First principles study of the electronic structure and phonon dispersion of naphthalene under pressure

Cited by 17 publications

References 59 publications

Ab initiophonon dispersion in crystalline naphthalene using van der Waals density functionals

Ab initiophonon dispersion in crystalline naphthalene using van der Waals density functionals

Exploring polymorphism of benzene and naphthalene with free energy based enhanced molecular dynamics

Light Dark Matter Detection with Hydrogen-rich Crystals and Low-Tc TES Detectors

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