Abstract
Halide perovskites are semiconductors that exhibit sharp optical absorption edges and small Urbach energies allowing for efficient collection of sunlight in thinfilm photovoltaic devices. However, halide perovskites also exhibit large nuclear anharmonic effects and disorder, which is unusual for efficient optoelectronic materials and difficult to rationalize in view of the small Urbach energies that indicate a low amount of disorder. To address this important issue, the disorder potential induced for electronic states by the nuclear dynamics in various paradigmatic halide perovskites is studied with molecular dynamics and density functional theory. We find that the disorder potential is dynamically shortened due to the nuclear motions in the perovskite, such that it is shortrange correlated, which is shown to lead to favorable distributions of band edge energies. This dynamic mechanism allows for sharp optical absorption edges and small Urbach energies, which are highly desired properties of any solar absorber material.
Introduction
Halide perovskites (HaPs) have emerged as semiconducting materials that are solutionprocessable and show an outstanding potential for device applications, notably for photovoltaics, where powerconversion efficiencies already approach those of siliconbased cells^{1,2,3,4,5,6,7,8,9,10}. HaPs exhibit several physical properties that are key to their remarkable potential as solar materials, and in particular show a steep optical absorption rise that is required for an efficient capture of sunlight in a thinfilm device^{11}. Specifically, the Urbach energy, which quantifies the steepness of optical absorption rise, was found to be very small for HaPs at room temperature, on the order of 10 meV^{12}, which is close to highly efficient inorganic solar materials such as bulk Si and GaAs. A small Urbach energy implies that the material is ordered, since disorder would lead to tail states in the electronic structure and to a broadening of the optical absorption profile. Interestingly, however, ample experimental and theoretical evidence point to highly anharmonic nuclear motion and disorder being active in HaPs at room temperature, which also involves the ions in the crystal contributing to the frontier electronic band structure^{13,14,15,16,17,18,19,20,21,22,23,24,25}. Such anharmonic effects are uncommon for efficient optoelectronic materials^{26} and difficult to rationalize in view of the low Urbach energy. In particular, they can be suspected to result in a disordered potential for the electrons and holes in the crystal and, hence, in a high density of tail states and a broad optical absorption. Therefore, one must wonder how steep optical absorption edges, small Urbach energies and, hence, an efficient collection of sunlight can even be possible in thinfilms of HaP crystals at room temperature.
Here, we use firstprinciples based molecular dynamics (MD) calculations to study and quantify the spatial correlations in the disorder potential for electrons and holes that is induced by thermal vibrations. We find that the massive nuclear motions in HaPs lead to a dynamic shortening of the disorder potential for electrons and holes, such that is confined to one atomic bond and becomes similar to the length scales that were reported for classical inorganic semiconductors. Since the correlation length of the disorder potential is shortranged, thermal nuclear motion disturbs the electronic states in only small volumes of the crystal. Therefore, this is expected to lead to a low density of disorderinduced tail states, which we demonstrate from firstprinciples calculations. This dynamic mechanism allows the here studied CsPbBr_{3}, CsPbI_{3}, and MAPbI_{3} to exhibit narrow bandgap distributions, sharp optical absorption edges and small Urbach energies at elevated temperatures, which are highly desired properties of any solar absorber material used in thinfilm devices.
Results
Spatial correlations in the disorder potential of CsPbBr_{3}
Our theoretical approach employs MD calculations based on density functional theory (DFT), which treat the nuclear anharmonicity to all orders in the Taylor expansion of the crystal potential and thereby allow for monitoring and quantifying its consequences for physical observables in a straightforward manner. Specifically, long MD trajectories at various temperatures were computed in order to characterize the consequences of the thermallyinduced nuclear disorder potential for electronic states in the material, as illustrated in Fig. 1a. To this end, we firstly calculated the average electrostatic potential energy as
where \(V_i(x,y,z)\) is the electrostatic energy of the electrons for configuration i along the MD trajectory, and N is the total number of configurations we considered. Note that we chose N = 30 configurations, which were separated by 5 ps. We consider \(\bar V\) to represent the average crystal potential for the electronic states. From this, we calculated the instantaneous disorder potential as the deviation from \(\bar V\):
Finally, we computed the autocorrelation function of \(\Delta V_i\) along the y coordinate as
and owing to the cubic symmetry of the crystal, calculated the average of it over all x and z values, which we denote as \(C\left( {\Delta y} \right)\). Furthermore, the DFTMD simulations allow for characterizing phononquasiparticle properties by analyzing the velocityautocorrelation function (VACF) in the basis of the harmonic spectrum (see Methods section for details). As a paradigmatic case, we choose to focus first on the allinorganic HaP CsPbBr_{3} in its cubic phase (Fig. 1a), and subsequently report results on CsPbI_{3} and MAPbI_{3} in order to test the influence of ionic composition.
Figure 1b shows an exemplary chargedensity response during the MD in CsPbBr_{3}, which was obtained as the difference of the density corresponding to a randomlychosen nuclear configuration along the MD run at 425 K and the mean density along the MD trajectory. The calculated chargedensity difference is such that it follows the nuclear displacements, and since all phonon modes are excited at the considered temperature (see section “vibrational characterization of CsPbBr_{3}”), it is essentially distributed throughout the entire simulation volume. What is perhaps more surprising is the fact that this chargedensity difference appears highly disordered, i.e., it does not show any obvious symmetry properties or directional features.
Such a charge density response results in an instantaneous disorder potential for the electronic states in CsPbBr_{3} via Eq. (2) that is spatially correlated by means of \(C\left( {\Delta y} \right)\) given in Eq. (3), which we calculated selfconsistently along the MD trajectory. \(C\left( {\Delta y} \right)\) is shown in Fig. 1c for multiple instantaneous nuclear configurations along the MD trajectory, together with the average of these snapshots, for the three temperatures considered in the MD simulations. Remarkably, it is found that the correlation in the disorder potential is confined to very short ranges, since it vanishes on length scales of atomic bonds in CsPbBr_{3}. Furthermore, we find that at the three considered temperatures, the disorder potential shows a similar overall behavior. With this, we establish that the spatial correlation in the disorder potential CsPbBr_{3} is shortranged, such that it appears to be similar to the one present in classical inorganic semiconductors, which is correlated also only over atomic distances^{27}.
Vibrational characterization of CsPbBr_{3}
The shortranged spatial correlations for the electronic states in CsPbBr_{3} are at first sight peculiar because the nuclear dynamics driving the disorder in HaPs were reported to be very different compared to the situation in classical inorganic semiconductors^{13,14,15,16,17,18,19,20,21,22,23,24,25}. We characterize the key vibrational features of CsPbBr_{3} in the following by first discussing results from the harmonic approximation. This description is valid for materials in which small nuclear displacements occur at finite temperature, as is the case in many of the classical inorganic semiconductors at room temperature. The harmonic phonon spectrum of CsPbBr_{3} (see Fig. 2a) is found to contain lowenergy features, especially due to Cs and Br motion, as was well as an intrinsic dynamic instability, which have been analyzed in previous theoretical work^{28,29}. Next, we consider finite temperature vibrational properties of CsPbBr_{3} obtained from a fully anharmonic treatment by means of DFTbased MD, analyzing the VACF as described in the Methods section. The structural instabilities, seen as imaginary features in the 0 K harmonic calculations of the phonon spectrum, vanish in the finite temperature dispersion relation (see Fig. 2a), which is expected. Figure 2b shows the power spectrum of the VACF, which represents the vibrational density of states (VDOS), at three temperatures. Overall, while the vibrational features appear strongly broadened in the finite temperature spectra, one can still appreciate that they are rather similar to the harmonic result. Hence, theoretical data obtained from lattice dynamics calculations in the harmonic approximation are not generally in contrast to those obtained with a fully anharmonic treatment.
This motivates us to study the consequences of anharmonicity in greater detail, especially because the importance of it for optoelectronic properties was discussed in several previous articles^{13,14,15,16,17,18,19,20,21,22,23,24,25}. Our approach is intrinsically based on firstprinciples information that is obtained at each timestep of the MD trajectory. Therefore, we are in a position to compute phonon quasiparticle properties and extract the vibrational lifetimes, which are key physical observables quantifying anharmonic nuclear effects. The phonon lifetimes, shown in Fig. 2c at different high symmetry points of the phonon branches as a function of frequency, are extremely short in CsPbBr_{3}, i.e., between 0.3 and 10 ps in a temperature range of 325–525 K. We also find that the phonon lifetime is shortest in the frequency range where the power spectrum exhibits the highest intensity, i.e., between 1 and 3 THz, which can be explained by considering that due to the presence of many phonons in this range the phononphonon interactions are strongest (cf. Fig. 2a–c). Table 1 establishes that both acoustic and optical phonons are very shortlived in CsPbBr_{3}, in agreement with recent experiments that studied the phonon lifetimes of acoustic modes in MAPbI_{3}^{25}.
Figure 2d shows histograms of the phonon lifetimes as a function of temperature. Some temperatureinduced changes are indeed observed in the phonon lifetimes, e.g., certain modes do shift to lower lifetimes at higher temperatures, and the mean value of the distribution is lowered by approximately 0.3 ps from 325 to 525 K. Notably, however, the shape of the distribution remains largely similar and there is no apparent shift of the distribution to lower lifetimes with increase in temperature. Likewise, Table 1 shows the lower end of the range in the phonon lifetimes to remain largely constant (within a reasonable statistical error of approximately 80 fs) at different temperatures, while the upper end changes significantly. This finding can be explained by considering that in order to be physically meaningful, the period of a phonon with a given frequency presents a reasonable lower limit to its lifetime. We find that for CsPbBr_{3}, this limit has been reached already at 325 K, which again signals massive anharmonic effects in the nuclear displacements approaching the limit of a breakdown of the phonon picture. To put these findings in perspective, recall that in bulk Si the phonon lifetimes are two orders of magnitude higher for a similar range of temperature and frequency^{30}. These findings strongly suggest that anharmonicity is an important phenomenon in the nuclear dynamics of HaPs, in agreement with previous studies on different HaPs^{13,14,15,16,17,18,19,20,21,22,23,24,25}. It will now be shown that the mechanism underlying anharmonicity in HaPs renders the presence of a shortrange correlated disorder potential particularly interesting.
Longrange resonant bonding effect in the disorder potential
Resonant bonding was recently studied as a potential origin of the nuclear anharmonicity occurring in HaPs^{14}. Such a mechanism was suggested 40 years ago for hybrid HaPs^{31} and originates from the fact that multiple configurations of the sphybridized leadhalide framework are close in energy, as was discussed in previous work on HaPs^{14,17} and other materials^{32,33}. Importantly, resonant bonding causes longrange effects in the dynamical matrix^{32}, which we illustrate with an example that was recently studied in the literature^{14}. In Fig. 3a we plot the change in the charge density that is induced to the system upon displacing a single Pb atom showing that the response is clearly longranged in CsPbBr_{3}. Furthermore, in Fig. 3b we show that such a resonant bonding response would result in a longrange correlated disorder potential for electrons and holes in CsPbBr_{3} by computing \(C\left( {\Delta y} \right)\) for this specific case: the longrange effect in the density immediately translates into longrange correlations of the disorder potential that are induced upon the displacement, which exceed the 5.8 Å unit cell of CsPbBr_{3} by far. In contrast, the full MD calculations discussed above have established a shortrange correlated disorder potential that was confined to distances of one atomic bond.
Resolving the discrepancy between longrange disorder effects implied by a resonant bonding mechanism and the appearance of shortrange correlated disorder in the actual MD calculations is important. While the role of disorder for properties of solar materials has been long known^{34}, revealing the origin and consequences of the shortrange correlated disorder present in HaPs will provide a fresh view on the interrelation of nuclear dynamics and optoelectronic properties in these materials. Consider the case of longrange correlated disorder (see Fig. 4a), defined as being correlated across several atomic bond distances, which would perturb the electronic states in large fractions of the crystal volume. A macroscopic sample of such a material would therefore contain a high density of tail states if longrange correlated disorder was indeed active. The Urbach energy would then be large, since it scales with the square of the correlation length of the disorder potential^{27}. In contrast, the type of shortrange correlated disorder we found in CsPbBr_{3}, which is correlated only across distances on the order of one atomic bond, perturbs the electronic states in only small fractions of the crystal volume (see Fig. 4b). Hence, in a macroscopic sample of CsPbBr_{3}, different regions of the crystal are perturbed electronically only independently of one another by the nuclear dynamics. Importantly, while locally and temporally the nuclear configuration may generally be strongly perturbed from the ideal lattice, this effect is expected to induce tail states in only a relatively small crystal volume. Therefore, a large crystal sample of CsPbBr_{3} is expected to on average containing only a small density of disorderinduced tail states, the distribution of available band gaps will be narrow, and the optical absorption edge will be sharp. This is a prerequisite for the small Urbach energy that was recorded experimentally for this^{35} and other HaPs^{12}, which is a highly desired property of any solar material. It also implies that the impact of thermal nuclear disorder on the optoelectronic properties of Csbased HaPs is such that the optical absorption onset is still sharp. Hence, an efficient collection of sunlight in thinfilm devices should be possible given the intrinsic properties of these materials. The mechanism underlying the shortrange disorder potential, however, is expected to be different in HaPs compared to classical inorganic semiconductors such as bulk Si and GaAs. For Si, it was shown that even for a statically displaced structure the response is shortranged^{14}, i.e., in Si it does not require any nuclear dynamics to find a shortrange correlated disorder potential.
Dynamic shortening of spatial correlations
We now explore the impact of nuclear dynamics on the spatial correlation in the disorder potential of electrons and holes in more detail. To this end, we consider several relevant constrained scenarios of nuclear motion that occur in the full MD of CsPbBr_{3} at T = 425 K. For each considered case, we calculate how it impacts the spatial correlations in the disorder potential of the material. Figure 5a shows data for \(C\left( {\Delta y} \right)\) corresponding to three cases: (i) configurations of Pb atoms chosen from the MD trajectory, but Cs and Br atoms being fixed to their ideal lattice positions; (ii) configurations of Pb and Br atoms chosen from the MD trajectory, but only Cs atoms being fixed to their ideal lattice positions; and (iii) configurations of Pb and Cs atoms chosen from the MD trajectory, but only Br atoms being fixed to their ideal lattice positions. It is found that Pb displacements induce a disorder potential for the electronic states showing a spatial correlation that significantly exceeds atomic distances, in line with the expectation borne from the resonant bonding mechanism discussed above. Most importantly, the correlation length of the disorder potential for electrons and holes is massively shortened by activating either Cs or Br displacements. Cs displacements already cause a substantial reduction of the correlation length, but it is the presence of displaced Br atoms that reduces spatial correlations in the disorder potential such that it becomes similar to the result obtained in fullyunconstrained MD (see Fig. 1c). Hence, the disorder potential for electrons and holes is dynamically shortened by the large nuclear motions of Cs and especially Br at elevated temperatures in CsPbBr_{3}.
Narrowing of dynamical bandedge distributions
A manifestation of electronphonon interactions in CsPbBr_{3}, namely the impact of spatial correlations in the disorder potential on the density of tail states (see Fig. 4), can now be tested explicitly. The investigation of this effect is based on the above finding that when only Pb displacements are active, the correlation length was found to be longer than in the full MD calculation (cf. Figs. 5a and 1c). In Fig. 5b, we therefore report normalized histograms of DFTcalculated bandedge energies that occur during constrained MD calculations in which only Pb displacements were considered, and those of the full MD run (see Methods section for details). First, all finite temperature distributions for the valence band maximum (VBM) and conduction band minimum (CBM) are broadened compared to the static DFT result. This is expected because multiple nuclear configurations are sampled at elevated temperature, which affects the orbital overlap in the perovskite lattice and leads to fluctuations in the instantaneous VBM and CBM energies. Second, considering the case where only Pb displacements are active (blue curve in Fig. 5b), it can be seen that the distribution of CBM energies is wider than the one of VBM energies. This finding can be explained by the antibonding character of the valence band^{36} and the fact that the longrange nature of resonant bonding is mostly due to Pb pstates, which contribute strongly to the CBM states^{6}. Hence, the effect of just Pb displacements being active in CsPbBr_{3} leads to tails in the CBM energy distribution, which is again expected. Third and most important, when we now consider the result of the full MD calculation (redfilled curve in Fig. 5b), we find that the distribution of CBM energies becomes much narrower compared to the case where only Pb displacements were active. This finding reveals that the shortening of the disorder potential (cf. Figs. 5a and 1c) manifests itself in a reduction of the density of tails in the CBM energy distribution.
Therefore, we have explicitly established the connection between the shortrange correlated disorder potential and favorable distribution of electronic states in CsPbBr_{3}. The finding implies that in absence of defect states and other static perturbations of the crystal, such a shortrange correlated disorder potential will result in the recovery of one of the hallmark optoelectronic properties of HaPs, namely a sharp optical absorption edge and small Urbach energy at elevated temperatures. These are key properties of any solar material since they allow for efficient collection of sunlight in thinfilm crystalline materials.
Influence of ionic composition
A variety of ionic compositions are compatible with the ABX_{3} stoichiometry of HaP crystals. Several recent experimental and theoretical data showed strong anharmonic and disorder effects for HaP compounds containing various Asite cations and Xsite anions^{13,14,15,16,17,18,19,20,21,22,23,24,25}, which nevertheless exhibit favorable optoelectronic properties including a small Urbach energy. Therefore, it is interesting to examine whether the abovedescribed shortrange correlated disorder for the electronic states in CsPbBr_{3} is present also in alternative HaP compounds. To this end, in a first step we exchange bromine by iodine, and then cesium by the organic methylammonium (MA) molecule, to investigate the disorder potential in the CsPbI_{3} and MAPbI_{3} crystal, respectively.
In Fig. 6a, we show \(C\left( {\Delta y} \right)\) of CsPbI_{3}, calculated for multiple instantaneous nuclear configurations along the MD trajectory (T = 425 K) together with their average. It is found that the disorder potential is markedly shortranged, since it vanishes on the length scale of atomic bonds in CsPbI_{3}, similar to the situation in CsPbBr_{3} (see Fig. 1c). To investigate the effect of the nuclear dynamics on the disorder in CsPbI_{3}, we perform the same procedure that was described above for CsPbBr_{3} and consider constrained scenarios of nuclear motion. The results (see Fig. 6b) show that the mechanism of a dynamic shortening of the disorder potential is indeed active also in CsPbI_{3}. In particular, the longerrange disorder induced by Pb displacements is shortened strongly by activating Cs and especially I displacements. While the mechanism of dynamically shortening the disorder in CsPbI_{3} is thus remarkably similar to the situation in CsPbBr_{3} (cf. Figs. 5a and 6b), there is also one interesting difference. The partially negative correlation induced by activating only Pb displacements in CsPbBr_{3}, at a distance of approximately two lattice constants (see Fig. 5a), is hardly visible for the averaged curve in case of CsPbI_{3} (see Fig. 6b). This suggests that a static lattice of iodine atoms provides more screening of the disorder potential than the one of bromines, which is reasonable given the larger atomic polarizability of the former. Similar to the case of CsPbBr_{3}, in Fig. 6c we demonstrate explicitly that the shortening of the disorder potential corresponds to reducing the spread of CBM energies in CsPbI_{3}. Note that an interesting difference compared to CsPbBr_{3} is that Pb displacements induce a more symmetric tailing of CBM energies.
Finally, we consider the hybrid organicinorganic HaP MAPbI_{3}, which is interesting because first of all it was recently demonstrated that longrange effects due to a resonant bonding mechanism are active in this material^{14}. Furthermore, the anisotropy and dipole moment of the MA molecule could provide means for both, additional longrange order due to oriented dipoles, as well as additional disorder and screening due to disarranged dipoles. In Fig. 7 we show \(C\left( {\Delta y} \right)\) of MAPbI_{3} calculated by combining trajectories obtained in forcefield MD with DFT calculations, as described in the Methods section. Our results for MAPbI_{3} establish that also in this compound the disorder potential due to thermally activated nuclear displacements is shortranged. This is in line with the established fact that at higher temperatures, the orientation of MA is largely disordered. Note that it is the lacking dipolar order in MAPbI_{3}, which renders the subsequent analysis of constrained MD scenarios shown above for the Csbased compounds very challenging. With this, we conclude that the dynamically shortranged disorder potential is present in all considered HaP compounds, which is relevant for their favorable optoelectronic characteristics.
Discussion
By means of MD calculations we have reported a theoretical analysis of the disorder potential that is induced by thermal vibrations in HaPs in order to characterize spatial correlation properties. The latter are key for understanding the microscopic origin of the small Urbach energies that were recorded experimentally for HaP compounds, which enable these materials to be used as efficient solar absorbers in thinfilm devices. We found that the correlation length of the disorder potential for electrons and holes is markedly shortranged in the considered compounds CsPbBr_{3}, CsPbI_{3} and MAPbI_{3}, since it was found to be confined to distances of only one atomic bond, which is similar to the lengthscales that were reported for bulk Si and GaAs^{27}. Notably, this is in agreement with previous findings, which studied the nuclear motion contributing to the central peak in the CsPbBr_{3} Raman spectrum^{16} and quantified the correlation length of the disorder potential in MAPbI_{3} using classical MD^{37}. The presence of such a shortrange correlated disorder potential in HaPs is peculiar since strongly anharmonic nuclear motions and disorder effects were reported for these systems at room temperature^{13,14,15,16,17,18,19,20,21,22,23,24,25}, which may be suspected to perturb the electronic disorder in a profound way.
In search for the origin of the shortrange correlated disorder potential in HaPs, we considered the microscopic modulations of the electrostatic potential in the material that are induced by the nuclear displacements. Our data showed that a resonant bonding mechanism, which was suggested to be active in HaPs already 40 years ago^{31}, is present in these compounds. This result is in strong contrast to the case of classical inorganic semiconductors such as bulk Si or GaAs, but similar to previous findings related to HaPs^{14,17} and thermoelectric compounds^{32,33}. Resonant bonding in HaPs stems from the fact that multiple nuclear configurations of the sphybridized leadhalide framework are energetically very close, such that nuclear displacements cause longrange effects in the charge density of the system. Since we have also demonstrated that a resonant bonding mechanism would establish longrange correlated disorder potentials for electrons and holes, one must ask how it is possible that HaPs dynamically exhibit a disorder potential that is shortranged.
To address this question, we could show that it is the massive nuclear motion of the Asite cation and especially the halides leading to a dynamic shortening of the disorder potential induced for electrons and holes. The results from our firstprinciples calculations explicitly established that the dynamically shortranged disorder potential leads to favorable dynamic distributions of band edge energies. We conclude that it is this dynamic effect, which leads to large crystalline samples of HaPs containing only few disorderinduced tail states. This implies sharp optical absorption edges and low Urbach energies, which are key physical properties of any solar absorber material since they allow for efficient collection of sunlight in thinfilm devices.
Methods
Density functional theory calculations
Density functional theory (DFT) calculations were performed with the planewave code VASP^{38}, using the projector augmented wave (PAW) method to treat corevalence interactions^{39}. Unless stated otherwise, we employed the “normal” version of the codesupplied PAW potentials. Exchangecorrelation was described with the PBE functional^{40}, augmented by dispersive corrections computed in the TkatchenkoScheffler scheme^{41}, which was shown to provide an accurate description of static and dynamic structural properties of HaPs^{42}. Unless stated otherwise, an energy threshold of 10^{−8} eV, a Γcentered kpoint grid of 6 × 6 × 6, and a planewave cutoff energy set to 500 eV were used. The cubic lattice structure of all compounds were optimized with these settings such that residual forces were below 10^{−3} eVÅ^{−1}, for which improved convergence thresholds did not result in any significant changes. This structure was used in our subsequent calculations. Structural representations of CsPbBr_{3} were visualized using the VESTA program^{43}.
Lattice dynamics
To obtain the phonon dispersion relation and vibrational density of states, lattice dynamics calculations were performed using the finite displacement method as implemented in the phonopy package^{44}. In these calculations, a 2 × 2 × 2 supercell of the optimized CsPbBr_{3} structure was used, and all numerical parameters were kept as before, applying a kpoint grid that was reduced according to the enlarged cell size.
DFTbased molecular dynamics
Firstprinciples MD calculations were performed using a canonical (NVT) ensemble with a NoséHoover thermostat, as implemented in the VASP code, employing a timestep of 8 fs. We have chosen a larger 4 × 4 × 2 (160 atom) supercell in the MD simulations in order to improve the statistical sampling of the nuclear dynamics. For making these simulations computationally tractable, more efficient numerical settings were employed: the “GW” PAW potentials were used, since this improved the numerical convergence of the selfconsistent calculations of the MD runs, together with a planewave cutoff energy of 250 eV, an energy threshold of 10^{−6} eV, and a single k point. We verified that the latter was sufficiently accurate, by monitoring the power spectrum of the velocityautocorrelation function calculated with more k points. The system was equilibrated for at least 5 ps at each temperature, and the subsequent nuclear dynamics were analyzed along trajectories of 150 ps, which is more than ten times longer than the longest calculated phonon lifetime.
Forcefield molecular dynamics
Forcefield MD calculations were performed for a 4 × 4 × 2 supercell of cubic MAPbI_{3} (384 atoms) with the LAMMPS code^{45}, applying the force field by Mattoni et al.^{46}. We used a canonical (NVT) ensemble with a NoséHoover thermostat, employing a timestep of 0.5 fs. The system was equilibrated for 1 ns followed by a production run of 150 ps.
Phononquasiparticle properties
Phononquasiparticle properties of CsPbBr_{3} were calculated using the dynaphopy package^{47}. Specifically, the MDcalculated velocityautocorrelation functions were analyzed by means of a projection of them onto the harmonic modes which were calculated as described above. Fitting the power spectrum of these moderesolved projections with Lorentzian functions provided welldefined frequencies and lifetimes of each phonon mode as a function of the phonon wavevector, q, at high symmetry points. Note that the acoustic phonons at the Γpoint were not included in this analysis, since these are zerofrequency modes. The finitetemperature phonon dispersion was then obtained by calculating renormalized force constants that correspond to the quasiparticle phonon frequencies at the high symmetry points, which provided an updated dynamical matrix that was then interpolated in q, akin to lattice dynamic calculations. Note that the timefrequency transform was achieved by means of standard FastFouriertransform. Further theoretical details can be found in refs. ^{47,48}.
Disorder potential and bandedge histogram calculations
To calculate the disorder potential and bandedge histograms, we selected instantaneous nuclear configurations along the MD trajectories and computed the electrostatic potential energy and electronic structure of the system selfconsistently with DFT. To enhance the accuracy of these calculations, compared to the DFTMD simulations we increased the cutoff energy to 500 eV and used a kpoint grid of 1 × 1 × 2 in accordance with the realspace dimensions of the supercell. The autocorrelation function, which we denoted as \(C\left( {\Delta y} \right)\), was calculated as described above (see Eqs. 1–3). \(C\left( {\Delta y} \right)\) shown in Fig. 3b was obtained in an equivalent way, namely by calculating the disorder potential as the deviation of the electrostatic potential energy of the considered nuclear configuration (one Pb atom displaced by 5% of the primitive lattice constant) from the potential energy of the ideal one. In the latter calculations, we used a 5 × 5 × 2 supercell to minimize boundary effects that are induced by the longrange nature of the density response.\(C\left( {\Delta y} \right)\) shown in Figs. 5a, 6b, and 7 was also obtained equivalently, namely by calculating the disorder potential as the deviation of the electrostatic potential energy of the considered nuclear configuration (see Figs. 5a, 6b, and 7) from the potential energy of the one averaged for all considered configurations. To compute the bandedge distributions, 90 structures separated by 200 steps or 1.6 ps in the MD were considered. The normalization of the histograms was performed for the valence band maximum and conduction band minimum of each type of MD calculation separately. To sacrifice detail for clarity, we have shown the histograms as a function of a dimensionless parameter.
Data availability
The data that support the findings of this study are available from the corresponding author upon reasonable request.
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Acknowledgements
We thank Omer Yaffe and David Cahen (both Weizmann Institute of Science) for fruitful discussions. Funding provided by the Alexander von HumboldtFoundation in the framework of the Sofja Kovalevskaja Award, endowed by the German Federal Ministry of Education and Research, is acknowledged. The authors gratefully acknowledge the Gauss Centre for Supercomputing e.V. for funding this project by providing computing time through the John von Neumann Institute for Computing on the GCS Supercomputer JUWELS at Jülich Supercomputing Centre.
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C.G. performed the theoretical calculations and analyzed the data. D.A.E. conceived and supervised the project. C.G. and D.A.E. interpreted the results and wrote the paper.
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Gehrmann, C., Egger, D.A. Dynamic shortening of disorder potentials in anharmonic halide perovskites. Nat Commun 10, 3141 (2019). https://doi.org/10.1038/s4146701911087y
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