The electron-phonon(e-p) interaction in Pentacene (Pn) films grown on Bi(001) was investigated using photoemission spectroscopy. The spectra reveal thermal broadening from which we determine an e-p mass enhancement factor of lambda = 0.36 +/- 0.05 and an effective Einstein energy of omega_E = 11 +/- 4 meV. From omega_E it is inferred that dominant contributions to the e-p effects observed in ARPES come from intermolecular vibrations. Based on the experimental data for lambda we extract an effective Peierls coupling value of g_eff = 0.55. The e-p coupling narrows the HOMO band width by 15 +/- 8% between 75K and 300K.
The crystal structure and phonon dynamics of pentacene is computed with the Quasi Harmonic Lattice Dynamics (QHLD) method, based on atom-atom potential. We show that two crystalline phases of pentacene exist, rather similar in thermodynamic stability and in molecular density. The two phases can be easily distinguished by Raman spectroscopy in the 10-100 cm-1 spectral region. We have not found any temperature induced phase transition, whereas a sluggish phase change to the denser phase is induced by pressure. The bandwidths of the two phases are slightly different. The charge carrier coupling t…
The band dispersion of the two highest occupied molecular orbital (HOMO)-derived bands in thin crystalline Pentacene films grown on Bi(001) was determined by photoemission spectroscopy. Compared to first-principles calculations our data show a significantly smaller band width and a much larger band separation indicating that the molecular interactions are weaker than predicted by theory--a direct contradiction to previous reports by Kakuta et al. [Phys. Rev. Lett. 98, 247601 (2007)]. The effective hole mass m* at M-bar is found to be anisotropic and larger than theoretically predicted. Compari…
We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a GW plus Bethe-Salpeter equation approach, we calculate the exciton--bi-exciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two non-interacting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay from a bright single…
Electrons and holes are locally injected in a single pentacene monolayer island. The two-dimensional distribution and concentration of the injected carriers are measured by electrical force microscopy. In crystalline monolayer islands, both carriers are delocalized over the whole island. On disordered monolayer, carriers stay localized at their injection point. These results provide insight into the electronic properties, at the nanometer scale, of organic monolayers governing performances of organic transistors and molecular devices.
Electron-phonon coupling plays a central role in the transport properties and photophysics of organic crystals. Successful models describing charge- and energy-transport in these systems routinely include these effects. Most models for describing photophysics, on the other hand, only incorporate local electron-phonon coupling to intramolecular vibrational modes, while nonlocal electron-phonon coupling is neglected. One might expect nonlocal coupling to have an important effect on the photophysics of organic crystals, because it gives rise to large fluctuation in the charge-transfer couplings, …
Application of the exact-factorization density-functional perturbation approach to pentacene crystal and monolayer MoS2
Weizmann Institute of Science（魏茨曼科学研究所）；The University of Texas at Austin（德克萨斯大学奥斯汀分校）；Tsientang Institute of Advanced Study（紫江高等研究院）；The Hebrew University of Jerusalem（耶路撒冷希伯来大学）；Ruđer Bošković Institute（鲁杰·博什科维奇研究所）
Potassium is introduced into the crystalline herringbone structure of pentacene searching for a compound showing metallic electronic transport properties and, hopefully, superconductivity at small enough temperatures. Several possible structures for stoichiometric KPentacene (1:1), K2Pentacene (2:1) and K3Pentacene (3:1) compounds are theoretically investigated. Detailed densities of states for all of them are presented. As a more prominent result, a new monoclinic structure has been stabilized for the potassium richer material that could correspond to the recently synthesized superconducting …
Charge-transfer excitons (CTX) at organic donor/acceptor interfaces are considered important intermediates for charge separation in photovoltaic devices. Crystalline model systems provide microscopic insights into the nature of such states as they enable microscopic structure-property investigations. Here, we use angular-resolved UV/Vis absorption spectroscopy to characterize the CTX of crystalline pentacene:perfluoro-pentacene (PEN:PFP) films allowing to determine the polarization of this state. This analysis is complemented by first-principles many-body calculations, performed on the three-d…
The spatial extent of excitons in molecular systems underpins their photophysics and utility for optoelectronic applications. Phonons are reported to lead to both exciton localization and delocalization. However, a microscopic understanding of phonon-induced (de)localization is lacking, in particular how localized states form, the role of specific vibrations, and the relative importance of quantum and thermal nuclear fluctuations. Here we present a first-principles study of these phenomena in solid pentacene, a prototypical molecular crystal, capturing the formation of bound excitons, exciton-…
The optical properties of pentacene (PEN) and perfluoropentacene(PFP) thin films on various SiO2 substrates were studied using variable angle spectroscopic ellipsometry. Structural characterization was performed using X-ray reflectivity and atomic force microscopy. A uniaxial model with the optic axis normal to the sample surface was used to analyze the ellipsometry data. A Strong optical anisotropy was observed and enabled the direction of the transition dipole of the absorption bands to be determined. Furthermore, comparison of the optical constants of PEN and PFP thin films with the absorpt…
Quantum Computing of Phonon Spectra and Thermal Properties of Crystalline Solids
Central University of Punjab（旁遮普中央大学）；Siksha ’O’ Anusandhan University（锡卡奥安桑丹大学）；Bikash’s Quantum (OPC) Private Limited（比卡斯量子（单一成员私人有限公司））；Indian Institute of Science Education and Research (IISER) Kolkata（印度科学教育研究学院加尔各答分校）
We investigate the structure of mixed thin films composed of pentacene (PEN) and diindenoperylene (DIP) using X-ray reflectivity and grazing incidence X-ray diffraction. For equimolar mixtures we observe vanishing in-plane order coexisting with an excellent out-of-plane order, a yet unreported disordering behavior in binary mixtures of organic semiconductors, which are crystalline in their pure form. One approach to rationalize our findings is to introduce an anisotropic interaction parameter in the framework of a mean field model. By comparing the structural properties with those of other mix…
Phonon hydrodynamics is an exotic phonon transport phenomenon that challenges the conventional understanding of diffusive phonon scattering in crystalline solids. It features a peculiar collective motion of phonons with various unconventional properties resembling fluid hydrodynamics, facilitating non Fourier heat transport. Hence, it opens up several new avenues to enrich the knowledge and implementations on phonon physics, phonon engineering, and micro and nanoelectronic device technologies. This review aims at covering a comprehensive development as well as the recent advancements in this f…
We report that single interatomic potential, developed using Gaussian regression of density functional theory calculation data, has high accuracy and flexibility to describe phonon transport with ab initio accuracy in two different atomistic configurations: perfect crystalline Si and crystalline Si with vacancies. The high accuracy of second- and third-order force constants from the Gaussian approximation potential (GAP) are demonstrated with phonon dispersion, Grüneisen parameter, three-phonon scattering rate, phonon-vacancy scattering rate, and thermal conductivity, all of which are very clo…
Femtosecond spectroscopy is applied to study transient electronic and lattice processes in bismuth. Components with relaxation times of 1 ps, 7 ps and ~ 1 ns are detected in the photoinduced reflectivity response of the crystal. To facilitate the assignment of the observed relaxation to the decay of particular excited electronic states we use pump pulses with central wavelengths ranging from 400 nm to 2.3 mum. Additionally, we examine the variation of parameters of coherent A1g phonons upon the change of excitation and probing conditions. Data analysis reveals a significant wavevector dependen…
We propose a simple phenomenological model describing vibrational dynamics in a class of materials (like clathrates), which are crystalline compounds with closed cavities in their structures. In the spirit of a minimalist approach, our model includes only the minimum of ingredients necessary to capture the generic features of this class of compounds as brought to light by experiments. We consider only two kinds of particles: strongly coupled host atoms, which form the structural cavities, and guest atoms confined in the cavities. In spite of the confinement, for relatively small amplitude vibr…
We study the effect of characteristic size variation on the phonon thermal transport in crystalline GeTe for a wide range of temperatures using the first-principles density-functional method coupled with the kinetic collective model approach. The characteristic size dependence of phonon thermal transport reveals an intriguing collective phonon transport regime, located in between the ballistic and the diffusive transport regimes. Therefore, systematic investigations have been carried out to describe the signatures of phonon hydrodynamics via the competitive effects between grain size and tempe…
Polarized infrared reflectivity spectra of a (110)-oriented TbScO3 single crystal plate were measured down to 10 K. The number of observed polar phonons active along the crystallographic c axis at low temperatures is much higher than predicted by factor-group analysis for the orthorhombic Pbnm space group. Moreover, the lowest frequency phonons active in E||c as well as in E||[1-10] polarized spectra exhibit dramatic softening tending to a lattice instability at low temperatures. The dielectric permittivity at microwave frequencies does not show any ferroelectric-like anomaly, but the dielectr…
The optical reflectivity of Pb$_{0.865}$Sn$_{0.135}$Se and Pb$_{0.75}$Sn$_{0.25}$Se solid solutions was measured in the THz spectral region energetically corresponding to bulk optical phonon excitations and in the temperature range from 40 K to 280 K. The analysis of Pb$_{0.75}$Sn$_{0.25}$Se data performed within the dynamic dielectric function formalism revealed a new effect due to the electron-phonon coupling resulting in resonant changes of LO phonon frequency for energy gap equal to zero or to LO phonon energy. This effect is absent for Pb$_{0.865}$Sn$_{0.135}$Se that exhibits an open ener…
The optical properties of focused ion beam-engraved perfectly aligned and spatially controlled multi-quantum-well InGaN-GaN nanopillars were investigated. Crystalline MQW nanopillars with a diameter of 30 to 95 nm and high aspect ratios showed a maximum of three-fold enhancement in emission intensity per unit active area. A light emitting contour map of Taiwan is drawn with a nanopillar structure to demonstrate the site control of the technique adopted in the present study. Raman scattering studies were used to characterize the newly created surfaces. Unknown peaks in GaN and InGaN nanostructu…
A long-held belief is that shock energy induces initiation of an energetic material through an indirect energy up-pumping mechanism involving phonon scattering through doorway modes. In this paper, a 3-phonon theoretical analysis of energy up-pumping in RDX is presented that involves both direct and indirect pathways where the direct energy transfer dominates. The calculation considers individual phonon modes which are then analyzed in bands. Scattering is handled up to the third order term in the Hamiltonian based on Fermi's Golden Rule. On average, modes with frequencies up to 90 cm-1 scatte…
A first-principles density functional method along with the direct solution of linearized Boltzmann transport equations are employed to systematically analyze the low-temperature thermal transport in crystalline GeTe. The extensive thermal transport simulations, ranging from room temperature to cryogenic temperatures, reveal the emergence of a phonon hydrodynamic regime in GeTe at low temperature. The reduction of grain boundary scattering is found to play a crucial role along with the divergent trend of umklapp and normal scattering at low temperatures in accommodating the hydrodynamic regime…
Anomalous thermal expansion behaviour of several open frame-work compounds has been extensively investigated using the techniques of inelastic neutron scattering and lattice dynamics. These compounds involve increasing level of structural complexity and flexibility, which leads to increased values of thermal expansion coefficients approaching colossal values. In several compounds, neutron inelastic scattering experiments have produced quantitative estimates of the anharmonicity of phonons over a range of low energies, and thereby explained the observed thermal expansion quantitatively. The anh…
Spectral and transport properties of small molecule single-crystal organic semiconductors have been theoretically analyzed focusing on oligoacenes, in particular on the series from naphthalene to rubrene and pentacene aiming to show that the inclusion of different electron-phonon couplings is of paramount importance to interpret accurately the properties of prototype organic semiconductors. While, in the case of rubrene, the coupling between charge carriers and low frequency inter-molecular modes is sufficient for a satisfactory description of spectral and transport properties, the inclusion o…
Charge density wave (CDW) is a unique phenomenon mostly realized in two-dimensional (2D) metallic layered transition metal dichalcogenides (TMDCs). Here, we report on Raman spectroscopy of single crystal 1T-VSe2 and observed signature of commensurate CDW (C-CDW) and incommensurate (I-CDW) transition, in the temperature range of 50-120 K. The room temperature Raman spectra showed a sharp A1g mode ~ 206 cm-1 along with two new weak and broad Raman modes associated to Eg mode ~ 257 cm-1 and two-phonon mode (2ph) ~ 332 cm-1. The onset of I-CDW and C-CDW is estimated from resistance measurements su…
Point defects play a crucial role in crystalline materials as they do not only impact the thermodynamic properties but are also central to kinetic processes. While they are necessary in thermodynamic equilibrium spontaneous defect formation in the bulk is normally considered highly improbable except for temperatures close to the melting point. Here, we demonstrate by means of atomistic simulations that processes involving concerted atomic motion that give rise to defect formation are in fact frequent in body-centered cubic metals even down to about 50% of the melting temperature. It is shown t…
In this letter we derive a new method for direct calculation of the modal contributions to thermal conductivity, which is termed Green-Kubo modal analysis (GKMA). The GKMA method combines the lattice dynamics formalism with the Green-Kubo formula for thermal conductivity, such that the thermal conductivity becomes a direct summation of modal contributions, where one need not define the phonon velocity. As a result the GKMA method can be applied to any material/group of atoms where the atoms vibrate around stable equilibrium positions, which includes not only crystalline line compounds, but als…
Porous materials provide a large surface to volume ratio, thereby providing a knob to alter fundamental properties in unprecedented ways. In thermal transport, porous nanomaterials can reduce thermal conductivity by not only enhancing phonon scattering from the boundaries of the pores and therefore decreasing the phonon mean free path, but also by reducing the phonon group velocity. Here we establish a structure-property relationship by measuring the porosity and thermal conductivity of individual electrolessly etched single crystalline silicon nanowires using a novel electron beam heating tec…
We investigated optical absorption spectra near the fundamental absorption edge of beta-FeSi2 single crystals by transmission measurements. The phonon structure corresponding to the emission and absorption component was clearly observed in the low-temperature absorption spectra. Assuming exciton state in the indirect allowed transition, we determined a phonon energy of 0.031 +- 0.004 eV. A value of 0.814 eV was obtained for the exciton transition energy at 4K.
Structural modifications in InP(111) due to 1.5 MeV implantation of Sb have been characterized using first order and second order Raman spectroscopy. With both Longitudinal Optical (LO) and Transverse Optical (TO) modes allowed for InP(111), we have investigated the evolution of both these modes as a function of fluence. Intensity, linewidth and shifts of the phonons, for both first order and second order Raman modes, display the increase in damage in the lattice with increasing fluence. The results suggest that the presence of a charge layer in the vicinity of the surface may be effecting the…
The coupling of electrons and phonons is governed wisely by the symmetry properties of the crystal structures. In particular, for two-dimensional (2D) systems, it has been suggested that the electrons do not couple to phonons with pure out-of-plane distortion, as long as there is a $σ_h$ symmetry. We show that such a statement is correct when constituents of the unit-cell layer are only located in the $σ_h$ symmetric plane; a prominent example of such a system is graphene. For those 2D crystals in which atoms are vertically located away from the horizontal symmetric plane (e.g., 1H transition …
A solid conducts heat through both transverse and longitudinal acoustic phonons, but a liquid employs only longitudinal vibrations. Here, we report that the crystalline solid AgCrSe2 has liquid-like thermal conduction. In this compound, Ag atoms exhibit a dynamic duality that they are exclusively involved in intense low-lying transverse acoustic phonons while they also undergo local fluctuations inherent in an order-to-disorder transition occurring at 450 K. As a consequence of this extreme disorder-phonon coupling, transverse acoustic phonons become damped as approaching the transition temper…
Low thermal conductivity is favorable for preserving the temperature gradient between the two ends of a thermoelectric material in order to ensure continuous electron current generation. In high-performance thermoelectric materials, there are two main low thermal conductivity mechanisms: the phonon anharmonic in PbTe and SnSe and phonon scattering resulting from the dynamic disorder in AgCrSe2 and CuCrSe2, which have been successfully revealed by inelastic neutron scattering. Using neutron scattering and ab initio calculations, we report here a mechanism of static local structure distortion co…
The magnetic susceptibility between 1.5 and 800 K, the infrared reflectivity at room temperature and the temperature dependence of the dielectric constant at mm-wavelengths are reported for single crystalline BiFeO3. A well developed anomaly in the magnetic susceptibility signals the onset of antiferromagnetic order close to 640 K. Beside this anomaly, no further indications of phase or spin-glass transitions are found in the susceptibility down to the lowest temperatures. From infrared reflectivity we were able to identify all 9 phonon modes which are expected to be infrared active within the…
Femtosecond laser excitation of solid-state systems creates non-equilibrium hot electrons that cool down by transferring their energy to other degrees of freedom and ultimately to lattice vibrations of the solid. By combining ab initio calculations with ultrafast diffuse electron scattering we gain a detailed understanding of the complex non-equilibrium energy transfer between electrons and phonons in laser-excited Ni metal. Our experimental results show that the wavevector resolved population dynamics of phonon modes is distinctly different throughout the Brillouin zone and are in remarkable …
We observe magnetic effects in ultra-high quality factor crystalline quartz Bulk Acoustic Wave resonators at milli-Kelvin temperature. The study reveals existence of hysteresis loops, jumps and memory effects of acoustical resonance frequencies. These loops arise as a response to the external magnetic field and span over few Hertz range for modes with linewidths of about $25$mHz, which constitute a frequency shift of order 60 linewidths. The effects are broadband but get stronger towards higher frequencies where both nonlinear effects and losses are limited by two level systems. This suggests …
Optical phonons in nanoparticles with the randomness of interatomic bonds are considered both analytically and numerically. For weak dilute disorder two qualitatively different regimes of separated and overlapped levels are observed, resembling the case of random atomic masses investigated previously. At stronger and/or more dense disorder, the particles become essentially inhomogeneous, thus constituting the minimal model to describe an amorphous phase, where the picture of vibrational modes becomes more subtle. We concentrate here on the experimentally relevant case of strong disorder locate…
Magnesium Selenide (MgSe) is a wide bandgap semiconductor with applications in optoelectronics and energy conversion technologies. Understanding thermal conductivity (k) of MgSe is critical for optimum design of thermal transport in these applications. In this work, we report the temperature and length dependence lattice thermal conductivity of magnesium selenide (MgSe) with different crystallographic phases; zincblende, rocksalt, wurtzite and nickel arsenic, using first principles computations. Computations reveal significant differences in thermal conductivity (k) of MgSe for different phase…
Organic molecular crystals are expected to feature appreciable electron-phonon interactions that influence their electronic properties at zero and finite temperature. In this work, we report first-principles calculations and an analysis of the electron-phonon self-energy in naphthalene crystals. We compute the zero-point renormalization and temperature dependence of the fundamental band gap, and the resulting scattering lifetimes of electronic states near the valence- and conduction-band edges employing density functional theory. Further, our calculated phonon renormalization of the $GW$-corre…
The Born effective charges of component atoms and phonon spectra of a tetrahedrally coordinated crystalline ice are calculated from the first principles method based on density functional theory within the generalized gradient approximation with the projected augmented wave method. Phonon dispersion relations in a 3x1x1 supercell were evaluated from Hellmann-Feynman forces with the direct method. This calculation is an additional work to the direct method in calculating the phonon spectra which does not take into account the polarization charges arising from dipole interaction of molecules of …
It is suggested that at the melting temperature the thermal phonon vibration is in self-resonance with the lattice vibration of the surface atomic/molecular layer. This self resonance occurs at a well defined temperature and triggers the detachment of the atomic/molecular sheet or platelets from the surface of the crystal. Thermodynamic data of five substances is used to test this hypothesis. The calculated average phonon vibrational wavelengths are equal with or harmonics of the d-spacing of the atomic/molecular sheets. The proposed model is able to explain all of the features of melting.
The heat transfer properties of the organic molecular crystal $α$-RDX were studied using three phonon-based thermal conductivity models. It was found that the widely used Peierls-Boltzmann model for thermal transport in crystalline materials breaks down for $α$-RDX. We show this breakdown is due to a large degree of anharmonicity that leads to a dominance of diffusive-like carriers. Despite being developed for disordered systems, the Allen-Feldman theory for thermal conductivity actually gives the best description of thermal transport. This is likely because diffusive carriers contribute to ov…
We present inelastic neutron scattering results of phonons in (Pb$_{0.5}$Sn$_{0.5}$)$_{1-x}$In$_x$Te powders, with $x=0$ and 0.3. The $x=0$ sample is a topological crystalline insulator, and the $x=0.3$ sample is a superconductor with a bulk superconducting transition temperature $T_c$ of 4.7 K. In both samples, we observe unexpected van Hove singularities in the phonon density of states at energies of 1--2.5 meV, suggestive of local modes. On cooling the superconducting sample through $T_c$, there is an enhancement of these features for energies below twice the superconducting-gap energy. We …
Structural, magnetic, and dielectric properties of Sm$_2$CoMnO$_6$ have been studied. X-ray diffraction and Rietveld analysis show that the sample crystallizes in the monoclinic structure with \textit{P2$_1$/n} space group. Magnetic study shows that the sample undergoes a paramagnetic to ferromagnetic phase transition around $T_c$ $\sim$148 K and a low-temperature ordering of Sm$^{3+}$ moments. Temperature-dependent Raman study shows spin-phonon coupling present in this material. Dielectric response of Sm$_2$CoMnO$_6$ shows strong frequency dependence with large dispersion and large dielectric…
The nucleation mechanisms during solution deposition of organic semiconductor thin films determine the grain morphology and may influence the crystalline packing in some cases. Here, in-situ optical spectromicroscopy in reflection mode is used to study the growth mechanisms and thermal stability of 6,13-bis(trisopropylsilylethynyl)-pentacene thin films. The results show that the films form in a supersaturated state before transforming to a solid film. Molecular aggregates corresponding to subcritical nuclei in the crystallization process are inferred from optical spectroscopy measurements of t…
We show that the temperature dependence of conductivity of high mobility organic crystals Pentacene and Rubrene can be quantitatively described in the framework of the model where carriers are scattered by quenched local impurities and interact with phonons by Su-Schrieffer-Hegger (SSH) coupling. Within this model, we present approximation free results for mobility and optical conductivity obtained by world line Monte Carlo, which we generalize to the case of coupling both to phonons and impurities. We find fingerprints of carrier dynamics in these compounds which differ from conventional meta…
