Der Waals-corrected Density Functional Theory Research Articles

Fine-tuned MOF-74 type variants with open metal sites for high volumetric hydrogen storage at near-ambient temperature

Adsorbent-based hydrogen storage systems offer a potential solution to current challenges in hydrogen storage, particularly those requiring high pressures or cryogenic temperatures. Specifically, the use of metal–organic frameworks (MOFs) featuring open metal sites that strongly adsorb hydrogen represents a promising strategy for near-ambient-temperature hydrogen storage. This study investigates the hydrogen storage properties of M2(dondc) (M = Mg2+, Co2+, and Ni2+), an extended version of MOF-74. Among this series, Ni2(dondc) exhibits the second-highest volumetric hydrogen capacity of 10.74 g L−1 at 298 K under pressure swing adsorption conditions (100 to 5 bar) at ambient temperatures. The superior hydrogen storage performance of Ni2(dondc) is attributed to its highly polarizable Ni open metal sites and a significant heat of adsorption of 12.2 kJ mol−1. These findings are corroborated by temperature-programmed desorption spectroscopy and van der Waals-corrected density functional theory calculations. In addition to its exceptional hydrogen capacity, Ni2(dondc) exhibits robust structural stability and long-term durability, positioning it as a promising candidate for near-ambient-temperature hydrogen storage applications.

High ammonia storage capacity in LiCl nanoparticle-embedded metal-organic framework composites

Although porous adsorbents show potential for NH3 capture and storage, practical issues such as stability and limited gravimetric/volumetric capacity persist. Lithium chloride (LiCl), which possesses the highest theoretical NH3 capacity among metal halides, faces challenges such as a significantly high plateau pressure and inevitable volume expansion in the LiCl(NH3)4 complex, hindering static NH3 storage. Herein, we introduce a series of M2(dobpdc)-based composites, specifically LiCl@Mg2(dobpdc)-5, showcasing the highest gravimetric/volumetric NH3 adsorption capacity (48.3 mmol g−1/65.8 mmol cm−3) and superior NH3 storage density (1.12 g cm−3) at 298 K and 1 bar. Notably, the indirect gravimetric hydrogen storage capacity was calculated to be 14.6 wt%, which is comparable to the hydrogen storage capacity of NH3 itself (17.8 wt%). This remarkable performance stems from the presence of LiCl in the metal nodes, highly dispersed LiCl nanoparticles (NPs), and open metal sites. Additionally, the composite avoids volume expansion even after LiCl(NH3)4 formation at 273 K. Thorough analysis using van der Waals-corrected density functional theory calculations confirmed the efficacy of the LiCl impregnation method, suggesting its potential to advance NH3 storage systems for hydrogen carriers.

High-Capacity, Cooperative CO2 Capture in a Diamine-Appended Metal-Organic Framework through a Combined Chemisorptive and Physisorptive Mechanism.

Diamine-appended Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are promising candidates for carbon capture that exhibit exceptional selectivities and high capacities for CO2. To date, CO2 uptake in these materials has been shown to occur predominantly via a chemisorption mechanism involving CO2 insertion at the amine-appended metal sites, a mechanism that limits the capacity of the material to ∼1 equiv of CO2 per diamine. Herein, we report a new framework, pip2-Mg2(dobpdc) (pip2 = 1-(2-aminoethyl)piperidine), that exhibits two-step CO2 uptake and achieves an unusually high CO2 capacity approaching 1.5 CO2 per diamine at saturation. Analysis of variable-pressure CO2 uptake in the material using solid-state nuclear magnetic resonance (NMR) spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that pip2-Mg2(dobpdc) captures CO2 via an unprecedented mechanism involving the initial insertion of CO2 to form ammonium carbamate chains at half of the sites in the material, followed by tandem cooperative chemisorption and physisorption. Powder X-ray diffraction analysis, supported by van der Waals-corrected density functional theory, reveals that physisorbed CO2 occupies a pocket formed by adjacent ammonium carbamate chains and the linker. Based on breakthrough and extended cycling experiments, pip2-Mg2(dobpdc) exhibits exceptional performance for CO2 capture under conditions relevant to the separation of CO2 from landfill gas. More broadly, these results highlight new opportunities for the fundamental design of diamine-Mg2(dobpdc) materials with even higher capacities than those predicted based on CO2 chemisorption alone.

First-principles study of the oxidation susceptibility of WS2, WSe2, and WTe2 monolayers.

The environmental stability of two-dimensional (2D) transition metal dichalcogenide monolayers is of great importance for their applications in electronic, photonic, and energy storage devices. In this study, we focus on understanding the susceptibility of WS2, WSe2, and WTe2 monolayers to oxygen exposure in the form of atomic oxygen and O2 and O3 molecules, respectively. Calculations based on the van der Waals-corrected density functional theory predicted that O2 and O3 molecules are weakly adsorbed on these monolayers, although atomic oxygen prefers chemisorption accompanied by a significant charge transfer from the surface to oxygen. In the physisorbed molecular configurations consisting of O2 and O3, the partially oxidized monolayers retain their geometrical and electronic structures. The calculated transition path as the oxygen approaches the surface shows a high-energy barrier for all cases, thus explaining the photo-induced formation of the oxidized configurations in the experiments. Furthermore, oxidizing the WS2 monolayer is predicted to modify its electronic structure, reducing the band gap with increasing oxygen coverage on the surface. Overall, the calculated results predict the resilience of WS2, WSe2, and WTe2 monolayers against oxygen exposure, thus ensuring stability for devices fabricated with these monolayers.

Order-Disorder Phase Transition and Ionic Conductivity in a Li2B12H12 Solid Electrolyte.

Temperature-induced phase transitions and ionic conductivities of Li2B12H12 and LiCB11H12 were simulated with the use of machine learning interatomic potentials based on van der Waals-corrected density functional theory (rev-vdW-DF2 functional). The simulated temperature of order-disorder phase transition, lattice parameters, diffusion, ionic conductivity, and activation energies are in good agreement with experimental data. Our simulations of Li2B12H12 uncover the importance of the reorientational motion of the [B12H12]2- anion. In the ordered α-phase (T < 625 K), these anions have well-defined orientations, while in the disordered β-phase (T > 625 K), their orientations are random. In vacancy-rich systems, its complete rotation was observed, while in the ideal crystal, the anions display limited vabrational motion, indicating the static nature of the phase transition without dynamic disordering. The use of machine learning interatomic potentials has allowed us to study large systems (>2000 atoms) in long (nanosecond-scale) molecular dynamics runs with ab initio quality.

Cooperative Carbon Dioxide Capture in Diamine-Appended Magnesium-Olsalazine Frameworks.

Diamine-appended Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks have emerged as promising candidates for carbon capture owing to their exceptional CO2 selectivities, high separation capacities, and step-shaped adsorption profiles, which arise from a unique cooperative adsorption mechanism resulting in the formation of ammonium carbamate chains. Materials appended with primary,secondary-diamines featuring bulky substituents, in particular, exhibit excellent stabilities and CO2 adsorption properties. However, these frameworks display double-step adsorption behavior arising from steric repulsion between ammonium carbamates, which ultimately results in increased regeneration energies. Herein, we report frameworks of the type diamine-Mg2(olz) (olz4- = (E)-5,5'-(diazene-1,2-diyl)bis(2-oxidobenzoate)) that feature diverse diamines with bulky substituents and display desirable single-step CO2 adsorption across a wide range of pressures and temperatures. Analysis of CO2 adsorption data reveals that the basicity of the pore-dwelling amine─in addition to its steric bulk─is an important factor influencing adsorption step pressure; furthermore, the amine steric bulk is found to be inversely correlated with the degree of cooperativity in CO2 uptake. One material, ee-2-Mg2(olz) (ee-2 = N,N-diethylethylenediamine), adsorbs >90% of the CO2 from a simulated coal flue stream and exhibits exceptional thermal and oxidative stability over the course of extensive adsorption/desorption cycling, placing it among top-performing adsorbents to date for CO2 capture from a coal flue gas. Spectroscopic characterization and van der Waals-corrected density functional theory calculations indicate that diamine-Mg2(olz) materials capture CO2 via the formation of ammonium carbamate chains. These results point more broadly to the opportunity for fundamentally advancing materials in this class through judicious design.

Molybdenum Carbide MXenes as Efficient Nanosensors toward Selected Chemical Warfare Agents

There has been budding demand for the fast, reliable, inexpensive, non-invasive, sensitive, and compact sensors with low power consumption in various fields, such as defense, chemical sensing, healthcare, and safe environmental monitoring units. Particularly, efficient detection of chemical warfare agents (CWAs) is of great importance for human safety and security. Inspired by this, we explored molybdenum carbide MXenes (Mo2CTx; Tx = O, F, and S) as efficient sensors toward selected CWAs, such as arsine (AsH3), mustard gas (C4H8Cl2S), cyanogen chloride (NCCl), and phosgene (COCl2) both in aqueous and non-aqueous media. Our calculations based on van der Waals-corrected density functional theory (DFT) revealed that the CWAs bind with Mo2CF2, and Mo2CS2 monolayers under strong chemisorption with binding energies in the range of −2.33 to −4.05 eV, whereas Mo2CO2 resulted in comparatively weak bindings of −0.29 to −0.58 eV. We further reported the variations in the electronic properties, electrostatic potentials, and work functions of Mo2CTx upon the adsorption of CWAs, which authenticated an efficient sensing mechanism toward CWA detection. Statistical thermodynamic analysis was applied to explore the sensing properties of Mo2CTx at various temperatures and pressures. These findings will pave the way to an innovative class of low-cost reusable sensors for the sensitive and selective detection of highly toxic CWAs in air as well as in aqueous media.

Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework.

Carbon capture at fossil fuel-fired power plants is a critical strategy to mitigate anthropogenic contributions to global warming, but widespread deployment of this technology is hindered by a lack of energy-efficient materials that can be optimized for CO2 capture from a specific flue gas. As a result of their tunable, step-shaped CO2 adsorption profiles, diamine-functionalized metal-organic frameworks (MOFs) of the form diamine-Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are among the most promising materials for carbon capture applications. Here, we present a detailed investigation of dmen-Mg2(dobpdc) (dmen = 1,2-diamino-2-methylpropane), one of only two MOFs with an adsorption step near the optimal pressure for CO2 capture from coal flue gas. While prior characterization suggested that this material only adsorbs CO2 to half capacity (0.5 CO2 per diamine) at 1 bar, we show that the half-capacity state is actually a metastable intermediate. Under appropriate conditions, the MOF adsorbs CO2 to full capacity, but conversion from the half-capacity structure happens on a very slow time scale, rendering it inaccessible in traditional adsorption measurements. Data from solid-state magic angle spinning nuclear magnetic resonance spectroscopy, coupled with van der Waals-corrected density functional theory, indicate that ammonium carbamate chains formed at half capacity and full capacity adopt opposing configurations, and the need to convert between these states likely dictates the sluggish post-half-capacity uptake. By use of the more symmetric parent framework Mg2(pc-dobpdc) (pc-dobpdc4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate), the metastable trap can be avoided and the full CO2 capacity of dmen-Mg2(pc-dobpdc) accessed under conditions relevant for carbon capture from coal-fired power plants.

Hydrogen storage capacity of Li-decorated borophene and pristine graphene slit pores: A combined ab initio and quantum-thermodynamic study

Among the two-dimensional materials of the post-graphene era, borophene has raised an enormous interest due to its unprecedented diversity of structures and the wide variety of potential applications, including its ability for hydrogen storage. In the present paper we use van der Waals-corrected density functional theory in conjunction with a quantum-thermodynamic model to investigate the hydrogen storage capacity of confining Li-decorated borophene sheets in its most stable Pmmn8 configuration. Our theoretical approach surpasses the standard density functional theory calculations only valid at zero temperature and no pressure, thus providing the gravimetric and volumetric capacities as well as the isotherms in real conditions. We show that narrow Li-decorated slit pores of borophene have a good volumetric hydrogen storage capacity particularly at low temperature. Accordingly, nanoporous boron frameworks could be optimal for hydrogen storage in applications at low temperature. We compare the results with those corresponding to pristine graphene slit pores.

Fluoroarene Separations in Metal-Organic Frameworks with Two Proximal Mg2+ Coordination Sites.

Fluoroarenes are widely used in medicinal, agricultural, and materials chemistry, and yet their production remains a critical challenge in organic synthesis. Indeed, the nearly identical physical properties of these vital building blocks hinders their purification by traditional methods, such as flash chromatography or distillation. As a result, the Balz-Schiemann reaction is currently employed to prepare fluoroarenes instead of more atom-economical C-H fluorination reactions, which produce inseparable mixtures of regioisomers. Herein, we propose an alternative solution to this problem: the purification of mixtures of fluoroarenes using metal-organic frameworks (MOFs). Specifically, we demonstrate that controlling the interaction of fluoroarenes with adjacent coordinatively unsaturated Mg2+ centers within a MOF enables the separation of fluoroarene mixtures with unparalleled selectivities. Liquid-phase multicomponent equilibrium adsorption data and breakthrough measurements coupled with van der Waals-corrected density functional theory calculations reveal that the materials Mg2(dobdc) (dobdc4- = 2,5-dioxidobenzene-1,4-dicarboxylate) and Mg2(m-dobdc) (m-dobdc4- = 2,4-dioxidobenzene-1,5-dicarboxylate) are capable of separating the difluorobenzene isomers from one another. Additionally, these frameworks facilitate the separations of fluoroanisoles, fluorotoluenes, and fluorochlorobenzenes. In addition to enabling currently unfeasible separations for the production of fluoroarenes, our results suggest that carefully controlling the interaction of isomers with not one but two strong binding sites within a MOF provides a general strategy for achieving challenging liquid-phase separations.

Theoretical Investigation of Water Adsorption Chemistry of CeO2(111) Surfaces by Density Functional Theory

Cerium oxide (ceria, CeO2) is one of the most wide-spread oxide supporting materials for the precious metal nanoparticle class of heterogeneous catalysts. Because ceria can store and release oxygen ions, it is an essential catalytic component for various oxidation reactions such as CO oxidation (2CO + O2 2CO2). Moreover, reduced ceria is known to be reactive for water activation, which is a critical step for activation of water-gas shift reaction (CO + H2O → H2 + CO2). Here, we apply van der Waals-corrected density functional theory (DFT) calculations combined with U correction to study the mechanism of water chemisorption on CeO2(111) surfaces. A stoichiometric CeO2(111) and a defected CeO2(111) surface showed different water adsorption chemistry, suggesting that defected CeO2 surfaces with oxygen vacancies are responsible for water binding and activation. An appropriate level of water-ceria chemisorption energy is deduced by vdW-corrected non-local correlation coupled with the optB86b exchange functional, whereas the conventional PBE functional describes weaker water-ceria interactions, which are insufficient to stabilize (chemisorb) water on the ceria surfaces.

Cooperative Carbon Dioxide Adsorption in Alcoholamine- and Alkoxyalkylamine-Functionalized Metal-Organic Frameworks.

A series of structurally diverse alcoholamine- and alkoxyalkylamine-functionalized variants of the metal-organic framework Mg2 (dobpdc) are shown to adsorb CO2 selectively via cooperative chain-forming mechanisms. Solid-state NMR spectra and optimized structures obtained from van der Waals-corrected density functional theory calculations indicate that the adsorption profiles can be attributed to the formation of carbamic acid or ammonium carbamate chains that are stabilized by hydrogen bonding interactions within the framework pores. These findings significantly expand the scope of chemical functionalities that can be utilized to design cooperative CO2 adsorbents, providing further means of optimizing these powerful materials for energy-efficient CO2 separations.

Water Enables Efficient CO2 Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal-Organic Framework.

Supported by increasingly available reserves, natural gas is achieving greater adoption as a cleaner-burning alternative to coal in the power sector. As a result, carbon capture and sequestration from natural gas-fired power plants is an attractive strategy to mitigate global anthropogenic CO2 emissions. However, the separation of CO2 from other components in the flue streams of gas-fired power plants is particularly challenging due to the low CO2 partial pressure (∼40 mbar), which necessitates that candidate separation materials bind CO2 strongly at low partial pressures (≤4 mbar) to capture ≥90% of the emitted CO2. High partial pressures of O2 (120 mbar) and water (80 mbar) in these flue streams have also presented significant barriers to the deployment of new technologies for CO2 capture from gas-fired power plants. Here, we demonstrate that functionalization of the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) with the cyclic diamine 2-(aminomethyl)piperidine (2-ampd) produces an adsorbent that is capable of ≥90% CO2 capture from a humid natural gas flue emission stream, as confirmed by breakthrough measurements. This material captures CO2 by a cooperative mechanism that enables access to a large CO2 cycling capacity with a small temperature swing (2.4 mmol CO2/g with ΔT = 100 °C). Significantly, multicomponent adsorption experiments, infrared spectroscopy, magic angle spinning solid-state NMR spectroscopy, and van der Waals-corrected density functional theory studies suggest that water enhances CO2 capture in 2-ampd-Mg2(dobpdc) through hydrogen-bonding interactions with the carbamate groups of the ammonium carbamate chains formed upon CO2 adsorption, thereby increasing the thermodynamic driving force for CO2 binding. In light of the exceptional thermal and oxidative stability of 2-ampd-Mg2(dobpdc), its high CO2 adsorption capacity, and its high CO2 capture rate from a simulated natural gas flue emission stream, this material is one of the most promising adsorbents to date for this important separation.

Layer-sliding-mediated controlled tuning of physical properties of intercalated silicene/hBN heterostructure

Finding approaches capable of tuning material properties in a controlled manner are highly desirable for obtaining next generation devices. In this work, we have simultaneously performed layer-sliding and Li-intercalation in modeled two dimensional heterostructure consisting of a layer of puckered silicene and hexagonal boron nitride (hBN). Van der Waals-corrected density functional theory calculations have been carried out to reveal the aforementioned tuning strategy, which offers pronounced potential interms of applied perspective. After identifying the most stable layout of silicene over hBN and site for Li-insertion, silicene is slided over hBN in regular intervals and corresponding total-energy is collected with and without Van der Waals (vdW) contribution. Role of vdW interactions have been revealed during the course of sliding. We further investigated the potential energy surface along the sliding path and found that the sliding barrier is much high for the intercalated system than for the unintercalated heterostructure by three orders of magnitude. We also described the interfacial electronic properties of the hBN/silicene heterostructure and discussed the variation of planar average charge density difference, dipole charge transfer and interface dipole moment. The proposed method can lead to a general technique for tuning the properties of layered materials, which is completely reversible, controllable and can be monitored in real time.

Tetrel bonding on graphene

Many experimental detections and theoretical calculations have shown that the small molecules CO2, N2, CO, H2O and NH3 can be adsorbed on the graphene-family nanomaterials. The molecule CO2 can form tetrel bonds with N2, CO, H2O and NH3, respectively. Hence, it is significant to study the adsorption behavior of the tetrel bonding on graphene. In this work, the van der Waals-corrected density functional theory calculations have been carried out to study the adsorption behavior of the tetrel-bonded complexes CO2∙∙∙N2, CO2∙∙∙CO, CO2∙∙∙H2O and CO2∙∙∙NH3 on graphene. The results clearly show that, from a free state to the state on graphene, the length of the tetrel bond becomes longer and the strength of the tetrel bond becomes weaker, although the changes are not very large for both quantities. The energy decomposition analysis reveals that the effects of graphene on the tetrel bonds are largely dependent on both electrostatic and dispersion type interactions.

Li-decorated Pmmn8 phase of borophene for hydrogen storage. A van der Waals corrected density-functional theory study

We performed standard and van der Waals-corrected density functional theory calculations to investigate the hydrogen storage capacity of a phase of borophene with Pmmn symmetry and nonzero thickness. This borophene sheet (Pmmn8) has 8 atoms in its unit cell and is more stable than the planar α sheet and that the corrugated Pmmn2 sheet (2 atoms in the unit cell). Our results show that, in pristine form, the Pmmn8 sheet is not suited for hydrogen storage applications. However, decoration with Li atoms and strain increase the hydrogen storage ability of the sheet. We performed also a detailed quantum chemical topological analysis that shows that the BLi interaction in the hydrogenated Li-decorated Pmmn8 sheet is ionic. Our results for the adsorption of H2 on the Li-decorated Pmmn8 sheet are compared with those obtained for the adsorption of H2 on Ti-decorated zigzag graphene nanoribbons.

A strain-controlled C2N monolayer membrane for gas separation in PEMFC application

Ultrathin membranes with controllable pore sizes have great potential to realize high-selectivity gas separation at low energy cost, especially for those mixtures with narrow size distributions. Using a combination of van der Waals-corrected density functional theory (DFT) calculations and molecular dynamics (MD) simulation, we examine the separation ability of biaxial stretched monolayer C2N nanosheets which is applied to the O2 separation from CO/CO2/O2 mixtures in the cathode of proton exchange membrane fuel cells (PEMFC). The DFT calculations show that the diffusion energy barrier for molecules passing through the membrane followed by CO, CO2 and O2 in descending order, and an overall decrease of energy barriers due to the widen the pore size is observed with the increase of applied strains. Furthermore, MD results show that the nanosheet can effectively purify O2 from CO2 and CO with a strain from 8% to 10%. It confirms that the selectivity is determined by the electronic structure related interaction in addition to the kinetic diameter of individual molecules. The O2 permeability is improved progressively with further increase of strain, and small amount of CO2 begins to permeate through the nanosheet at relatively large strain, while the excellent CO isolation is not compromised until the theoretical maximum strain.

Roles of spin-orbit coupling in tetragonal hybrid halide perovskite for photovoltaics light-absorber

Hybrid halide perovskite has been gain appropriate attraction because of their relatively high efficiency in most recently solid-state solar cell development. In this work, A first-principle calculation based on non-local van der Waals-corrected Density Functional Theory (vdW-DFT) is performed to investigate high accuracy atomic structures of a tetragonal structure methyl ammonium (CH3NH3) metal (Pb, Sn) halide (Br3, Cl3, I3). The calculated electronic structures were systematically studied using semi-local exchange-correlation functional (GGA-PBE), non-local functional (hybrid HSE06) and post-DFT approximation (GW). A relativistic effect in metal ion was taken into account by incorporating spin-orbit coupling (SOC) effect to obtain more accurate band gap properties of these materials. Our results shown that SOC corrected the electronic structures about 0.92 eV and 0.19 eV in case of lead ion and tin ion, respectively. The combination between GW approximation and spin-orbit coupling show a good agreement between DFT calculations and experimental studies. This computational scheme is necessary for high accuracy organic-inorganic solar cell design.

First-principles investigation of the structural and electronic properties of self-assemblies of functional molecules on graphene

Graphene-based two-dimensional materials have attracted an increasing attention these last years. Among them, the system formed by molecular adsorption on, aim of modifying the conductivity of graphene and make it semiconducting, is of particular interest. We use here hierarchical first-principles simulations to investigate the energetic and electronic properties of an electron-donor, melamine, and an acceptor, NaphtaleneTetraCarboxylic DiImide (NTCDI), and the assembly of their complexes on graphene surface. In particular, the van der Waals-corrected density functional theory (DFT) method is used to compute the interaction and adsorption energies during assembly. The effect of dispersion interactions on both geometries and energies is investigated. Depending on the surface coverage and the molecular organization, there is a significant local deformation of the graphene surface. Self-assembly is driven by the competition between hydrogen bonds in the building blocks and their adsorption on the surface. The dispersion contribution accounts significantly in both intermolecular and adsorption energies. The electron transfer mechanism and density of states (DOS) calculations show the electron-donor and acceptor characters of melamine and NTCDI, respectively. Molecular adsorption affects differently the energy levels around the Fermi level differently, leading to band gap opening. These results provide information about the new materials obtained by controlling molecular assembly on graphene.

Effect of exchange-correlation and GW approximations on electrical property of cubic, tetragonal and orthorhombic CH3NH3PbI3

ABSTRACTA first-principle calculations based on van der Waals-corrected Density Functional Theory (vdW-DFT) is performed to investigate atomic structure of methyl ammonium lead iodine (CH3NH3PbI3) which is a key material for high efficiency solid-state solar cell. A temperature dependent symmetry was previously reported which also included in this study. DFT calculation of electronic and optical properties are systematically studied with semi-local, non-local exchange-correlation and post-DFT approximation including PBE, HSE06 hybrid functional and GW. Relativistic effect in lead ion was taken into account by incorporating spin-orbit coupling (SOC) effect to obtain more accurate band gap of this material. With GW-SOC functional, our results of band gap calculations showed good agreement between DFT calculations and experimental studies which confirmed that this computational scheme is suitable for high accuracy material design, e.g. for solar cell applications.