Gap renormalization of molecular crystals from density-functional theory

Refaely-Abramson, Sivan; Sharifzadeh, Sahar; Jain, Manish; Baer, Roi; Neaton, Jeffrey B.; Kronik, Leeor

doi:10.1103/physrevb.88.081204

Cited by 296 publications

(432 citation statements)

References 82 publications

Supporting

Mentioning

408

Contrasting

Unclassified

Order By: Relevance

“…71 To allow for a direct comparison with the GW calculations from Refs. 17,18,23 , the molecular geometries (see Figure 1) were optimized using the PBE functional 72 and 6-31G(d,p) basis set. The optimization of the rangeseparation parameter ω was performed based on the LC-ωPBE 46, 73 functional and using the efficient "golden-ratio" algorithm, as described in our previous work 48,57 (see Supporting…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

“…65 Although this PBEh functional with an adjusted α parameter can reproduce reasonable solid-state gaps, gas-phase gaps and the solid-state polarization energy are not as well described. 17 Refaely-Abramson et al…”

mentioning

confidence: 99%

“…As a result, the solid-state polarization energies estimated for the TIPS-pentacene films are remarkably different: 0.44 eV by the Lichtenberger group vs. 1.24 eV by the Kahn group. 16 Generally speaking, several factors can contribute to such significant variations between experimentally determined values, [16][17][18][19] such as:…”

mentioning

confidence: 99%

“…[35][36][37] In molecular crystals, the surrounding environment is substantially different from that of isolated molecules due to polarization effects. 17 Polarization is essentially a phenomenon related to nonlocal correlation, which cannot be captured by semilocal XC functionals. Furthermore, as a consequence of the lack of derivative discontinuity (DD) [38][39][40] as well as the large electron delocalization error (DE) 36,41 or selfinteraction error (SIE) 35,42,43 of conventional XC functionals, the calculated orbital energies of 6 the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) obtained from standard XC functionals do not correspond to the IE and EA, respectively.…”

mentioning

confidence: 99%

“…17 Phillips et al used a rangeseparated functional with the same (IP-tuned) ω values for both molecule and crystal, but derived the solid-state IEs (EAs) by the PCM-∆SCF correction based on the orbital energies of the isolated molecule. 8 However, since the range-separation parameter ω is typically considered to 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 8 be a functional of the density, 39, 66 it should not be expected that the tuned ω value found for the molecule is also "optimal" for the crystal since the electron density will be influenced by polarization effects.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)-Tuned Range-Separated Density Functional Approach

Sun

Ryno

Zhong

et al. 2016

J. Chem. Theory Comput.

135

130

View full text Add to dashboard Cite

We propose a new methodology for the first-principles description of the electronic properties relevant for charge transport in organic molecular crystals. This methodology, which is based on the combination of a nonempirical, optimally tuned range-separated hybrid functional with the polarizable continuum model, is applied to a series of eight representative molecular semiconductor crystals. We show that it provides ionization energies, electron affinities, and transport gaps in very good agreement with experimental values, as well as with the results of many-body perturbation theory within the GW approximation at a fraction of the computational costs. Hence, this approach represents an easily applicable and computationally efficient tool to estimate the gas-to-crystal phase shifts of the frontier-orbital quasiparticle energies in organic electronic materials.

show abstract

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)-Tuned Range-Separated Density Functional Approach

Sun

Ryno

Zhong

et al. 2016

J. Chem. Theory Comput.

135

130

View full text Add to dashboard Cite

show abstract

First Principles Atomistic Theory of Halide Perovskites

Leppert

2023

Halide Perovskite Semiconductors

View full text Add to dashboard Cite

Relating the Physical Structure and Optoelectronic Function of Crystalline TIPS‐Pentacene

Sharifzadeh

Wong

et al. 2014

Adv Funct Materials

Self Cite

154

View full text Add to dashboard Cite

order provide an opportunity to understand many fundamental physical properties relevant to solar energy conversion. Additionally, organic crystals are promising in their own right due to the effi cient carrier and energy transport properties associated with their long-range order.In particular, crystalline and polycrystalline fi lms of pentacene (PEN) and its derivatives have high carrier mobility for charge transport (≈1−10 cm 2 /Vs hole mobility) [ 1 ] and signifi cant photoconductivity. [ 2,3 ] Moreover, PEN and many of its derivatives display a propensity for singlet fi ssion (SF), [ 4,5 ] a phenomenon that results in greater than 100% internal quantum effi ciency in organic photovoltaics. Numerous possible molecular functionalizations may modify solid-state structural and optoelectronic properties. [ 6 ] Therefore, elucidating the structure-property relation is important for the design of new functional molecular materials. 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-PEN), [ 7 ] shown in Figure 1 , has recently attracted much interest. The bulky groups functionalizing PEN enable solubility in organic solvents and allow for solution-processing of polycrystalline TIPS-PEN thin fi lms with high carrier mobility and photoconductivity. [ 2,3,7 ] While TIPS-PEN apparently retains optical properties similar to PEN, its enhanced carrier mobility [ 8 ] and Relating the Physical Structure and Optoelectronic Function of Crystalline TIPS-PentaceneSahar Sharifzadeh , * Cathy Y. Wong , Hao Wu , Benjamin L. Cotts , Leeor Kronik , Naomi S. Ginsberg , and Jeffrey B. Neaton * Theory and experiment are combined to investigate the nature of low-energy excitons within ordered domains of 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-PEN) polycrystalline thin fi lms. First-principles density functional theory and many-body perturbation theory calculations, along with polarizationdependent optical absorption spectro-microscopy on ordered domains, show multiple low-energy absorption peaks that are composed of excitonic states delocalized over several molecules. While the fi rst absorption peak is composed of a single excitonic transition and retains the polarization-dependent behavior of the molecule, higher energy peaks are composed of multiple transitions with optical properties that can not be described by those of the molecule. The predicted structure-dependence of polarization-dependent absorption reveals the exact inter-grain orientation within the TIPS-PEN fi lm. Additionally, the degree of exciton delocalization can be signifi cantly tuned by modest changes in the solid-state structure and the spatial extent of the excitations along a given direction is correlated with the degree of electronic dispersion along the same direction. These fi ndings pave the way for tailoring the singlet fi ssion effi ciency of organic crystals by solid-state structure.

show abstract

Gap renormalization of molecular crystals from density-functional theory

Cited by 296 publications

References 82 publications

Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)-Tuned Range-Separated Density Functional Approach

Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)-Tuned Range-Separated Density Functional Approach

First Principles Atomistic Theory of Halide Perovskites

Relating the Physical Structure and Optoelectronic Function of Crystalline TIPS‐Pentacene

Contact Info

Product

Resources

About