Charge Reorganization Research Articles

Electronic Conductance and Current Modulation through Graphdiyne Nanopores for DNA Sequencing

Solid-state nanopore devices have emerged as one of the most promising technologies that may decode the sequence of DNA nucleobases by reading electronic conductance and electric current signals. Herein we study the potential of atomically thick graphdiyne (GDY) to act as an all-electronic nanopore (NP)-based DNA sequencing device. The first-principles density functional theory method is used to study the structural properties, interaction energy (Ei) values, translocation time (τ), charge transfer [Q(e)] values, charge density difference [Δρ(r)], molecular orbital (MO) positions, and electronic density of states (DOS) properties of the GDYNP and GDYNP + nucleobase (nucleobases: adenine (A), guanine (G), thymine (T), and cytosine (C)) systems. Our results suggest that the GDYNP system could be a suitable device for the detection of nucleobases due to their specific translocation times inside the GDYNP device. The Δρ(r) results reveal that the charge fluctuates around the GDYNP edges close to the target nucleobase. This charge reorganization causes the modulation of charge transport in the GDYNP device. Furthermore, the GDYNP device is used to read-out the conductance and current signals of each DNA nucleobase while located inside the GDYNP by using nonequilibrium Green’s functions formalism. Our findings show a change in conductance with respect to the reference bare “GDYNP” device for energy values below/above the Fermi energy. The conductance as well as current sensitivity (%) values (C > G > T > A) indicates that the nucleobases could possibly be sequenced through the GDYNP device. Further, each nucleobase transmits unique current signals when transported through the GDYNP device. A distinction between purine- and pyrimidine-type nucleobases seems possible due to their different current signals. Thus, our study highlights the potentials that would motivate research toward the development of the GDYNP device, which may be even a better DNA nucleobase detector compared to graphene-based devices.

Controlled Regulation of the Nitrile Activation of a Peroxocobalt(III) Complex with Redox-Inactive Lewis Acidic Metals.

Redox-inactive metal ions play vital roles in biological O2 activation and oxidation reactions of various substrates. Recently, we showed a distinct reactivity of a peroxocobalt(III) complex bearing a tetradentate macrocyclic ligand, [CoIII(TBDAP)(O2)]+ (1) (TBDAP = N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane), toward nitriles that afforded a series of hydroximatocobalt(III) complexes, [CoIII(TBDAP)(R-C(═NO)O)]+ (R = Me (3), Et, and Ph). In this study, we report the effects of redox-inactive metal ions on nitrile activation of 1. In the presence of redox-inactive metal ions such as Zn2+, La3+, Lu3+, and Y3+, the reaction does not form the hydroximatocobalt(III) complex but instead gives peroxyimidatocobalt(III) complexes, [CoIII(TBDAP)(R-C(═NH)O2)]2+ (R = Me (2) and Ph (2Ph)). These new intermediates were characterized by various physicochemical methods including X-ray diffraction analysis. The rates of the formation of 2 are found to correlate with the Lewis acidity of the additive metal ions. Moreover, complex 2 was readily converted to 3 by the addition of a base. In the presence of Al3+, Sc3+, or H+, 1 is converted to [CoIII(TBDAP)(O2H)(MeCN)]2+ (4), and further reaction with nitriles did not occur. These results reveal that the reactivity of the peroxocobalt(III) complex 1 in nitrile activation can be regulated by the redox-inactive metal ions and their Lewis acidity. DFT calculations show that the redox-inactive metal ions stabilize the peroxo character of end-on Co-η1-O2 intermediate through the charge reorganization from a CoII-superoxo to a CoIII-peroxo intermediate. A complete mechanistic model explaining the role of the Lewis acid is presented.

The phase diagram of carbon dioxide from correlation functions and a many-body potential.

The phase stability and equilibria of carbon dioxide are investigated from 125-325K and 1-10 000 atm using extensive molecular dynamics (MD) simulations and the Two-Phase Thermodynamics (2PT) method. We devise a direct approach for calculating phase diagrams, in general, by considering the separate chemical potentials of the isolated phase at specific points on the P-T diagram. The unique ability of 2PT to accurately and efficiently approximate the entropy and Gibbs energy of liquids allows for assignment of phase boundaries from relatively short (∼100ps) MD simulations. We validate our approach by calculating the critical properties of the flexible elementary physical model 2, showing good agreement with previous results. We show, however, that the incorrect description of the short-range Pauli force and the lack of molecular charge polarization lead to deviations from experiments at high pressures. We, thus, develop a many-body, fluctuating charge model for CO2, termed CO2-Fq, from high level quantum mechanics (QM) calculations that accurately capture the condensed phase vibrational properties of the solid (including the Fermi resonance at 1378cm-1) as well as the diffusional properties of the liquid, leading to overall excellent agreement with experiments over the entire phase diagram. This work provides an efficient computational approach for determining phase diagrams of arbitrary systems and underscores the critical role of QM charge reorganization physics in molecular phase stability.

Uncovering photo-induced hydrogen bonding interaction and proton transfer mechanism for the novel salicylaldehyde azine derivative with para-position electrophilic cyano group

In this work, we mainly focus on exploring the excited state hydrogen bonding dynamics and excited state intramolecular proton transfer (ESIPT) mechanism for a SAA derivative with para-position electron-withdrawing cyano group (CN-SAA). Insight into the geometrical changes, infrared (IR) spectra, and atomic charge populations, we infer dual intramolecular hydrogen bonds of CN-SAA can be enhanced in S1 state. Adopting three manners to estimate hydrogen bonding energies, we further confirm S1-state hydrogen bonding strengthening, which triggers ESIPT reaction. In view of photo-induced excitation, we find charge reorganization plays important roles in promoting ESIPT behavior for CN-SAA. Combining core-valence bifurcation (CVB) index and energy gap between HOMO and LUMO orbitals in solvents with different polarities, we predict nonpolar solvents contribute to facilitate ESIPT process. To clarify detailed ESIPT mechanism, we construct potential energy surface (PES), search transition state (TS) form, perform intrinsic reaction coordinate (IRC) energetic profile calculations and Born-Oppenheimer molecular dynamics simulations. We not only clarify the excited state intramolecular single proton transfer (ESISPT) reaction mechanism for CN-SAA compound, but also present the ESISPT regulating mechanism via solvent polarity.

Crossover from static to dynamic Non-Condon effecton charge Transport in Organic Semiconductors

The computed charge transport key parameters like, charge transfer integral, site energy and reorganization energy are used to study the hole and electron transport in dialkyl substituted thienothiophene caped benzobisthiazole (BDHTT-BBT) and methyl-substituted dicyanovinyl-capped quinquethiophene (DCV5T-Me) molecular crystals. The effect of structural fluctuation on charge transport in these molecules is analysed by Monte-Carlo simulations. To estimate the equilibrium speed during the charge transport process in these molecular solids, we have introduced the parameters such as, potential equilibrium rate and density flux rate. Here, the density flux rate is directly related with the drift force which facilitates the charge transfer along the consequential hopping sites. Our theoretical study reveals that the charge transfer up to the crossover point (or disorder drift time) is exponential, non-dispersive and it follows the static non-Condon effect. Beyond the disorder drift time, the charge transfer is partially exponential, dispersive and it follows the dynamic non-Condon principle. The expressions of density flux and diffusion shows their dependency on dynamic disorder and is in agreement with the Troisi’s model on diffusion limited by thermal disorder.

Simultaneous High-Purity Enantiomeric Resolution of Conglomerates Using Magnetic Substrates

Applying magnetic substrates, magnetized perpendicular to the surface, we were able to crystallize from racemic solution pure conglomerates of several molecules. The resolution is based on the spin-dependent charge reorganization (SDCR) effect. By having two surfaces with opposite magnetization, it was possible to simultaneously crystallize on each surface a different enantiomer. The method does not require any seeding or chemical modification and is generally employable to any conglomerate. A system is presented for performing the separation, while the racemic mixture flows between the two magnetic surfaces.

Electrostatic tip effects in scanning probe microscopy of nanostructures

Electrical scanning probe microscopies (SPM) use ultrasharp metallic tips to obtain nanometer spatial resolution and are a key tool for characterizing nanoscale semiconducting materials and systems. However, these tips are not passive probes; their high work functions can induce local band bending whose effects depend sensitively on the local geometry and material properties and thus are inherently difficult to quantify. We use sequential finite element simulations to first explore the magnitude and spatial distribution of charge reorganization due to tip-induced band bending (TIBB) for planar and nanostructured geometries. We demonstrate that tip-induced depletion and accumulation of carriers can be significantly modified in confined geometries such as nanowires compared to a bulk planar response. This charge reorganization is due to finite size effects that arise as the nanostructure size approaches the Debye length, with significant implications for a range of SPM techniques. We then use the reorganized charge distribution from our model to describe experimentally measured quantities, using in operando scanning microwave impedance microscopy measurements on axial p-i-n silicon nanowire devices as a specific example. By incorporating TIBB, we reveal that our experimentally observed enhancement (absence) of contrast at the p-i (i-n) junction is explained by the tip-induced accumulation (depletion) of carriers at the interface. Our results demonstrate that the inclusion of TIBB is critical for an accurate interpretation of electrical SPM measurements, and is especially important for weakly screening or low-doped materials, as well as the complex doping patterns and confined geometries commonly encountered in nanoscale systems.

Theoretical insights into photochemical behavior and ESIPT mechanism for 2,6-dimethyl phenyl derivatives

Belonging to derivatives of 2-(2-hydroxyphenyl)benzothiazole, two novel excited state intramolecular proton transfer (ESIPT)-active 2,6-dimethylphenyls derivative dyes (HBT-Py and HBT-Py-DMP) are investigated theoretically. We mainly focus on the excited state photochemical behaviors and ESIPT mechanisms for these two compounds. Photo-induced intramolecular hydrogen bond has been confirmed to be enhanced, which is the first premise for excited state dynamics. Charge reorganizations and electronical densities changes resulting from photoexcitation reveal ESIPT tendency. We further perform potential energy curves (PECs) simulations, which verifies the ultrafast ESIPT mechanism for these two compounds. Particularly, we present that nonpolar solvents could accelerate ESIPT behaviors.

Ultrafast spectroscopic investigation of the artificial photosynthetic activity of CuAlS2/ZnS quantum dots

AbstractCuAlS2/ZnS Quantum dots (QDs) are known to directly convert aqueous solutions of bicarbonate ions to oxygen and organic molecules such as formate with a remarkable efficiency even under sunlight. In cases, fairly complicated organic reaction products such as acetate and methanol have been observed when reactions are allowed to continue for longer periods of time. Here, we investigate the electron dynamics that occurs within CuAlS2/ZnS QDs and show that it is essentially dominated by ultrafast electron transfer (560 fs for 0.4 excitons per dot) to the surface. The electron dwell time in the conduction band increases exponentially (for example 872 fs for 1.4 excitons per dot) with the excitation fluence. This is reverse of the auger limited response of conventional QDs and is hypothesized to exhibit strong charge separation that lies at the root of the remarkable photocatalytic activity. We further investigate this system through multi‐pump experiments. We find that the system response to prior excitation changes over the period of nanoseconds, consistent with the charge reorganization in the system, well after the initial electron transfer. The results of these experiments are summarized in terms of a coulomb‐well interpretation.

Effects of solvent polarity on excited state behaviors for the two intramolecular proton-transfer-site 4,4’-(hydrazine-1,2-diylidene-bis(methanylylidene))-bis(3-hydroxybenzoic acid) compound

Excited state proton transfer (ESPT) behavior of organic fluorophores has been drawing continuously considerable interests, since it owns enormous potential in wide of application fields. Given the paramount importance of excited state relaxations, in this work, we focus on deciphering excited state behaviors for the novel two proton-transfer-site 4,4’-(hydrazine-1,2-diylidene-bis(methanylylidene))-bis(3-hydroxybenzoic acid) (HDBB) system. In aprotic solvents with different polarities, we confirm the dual hydrogen bonds of HDBB should be enhanced in S1 state. It is a remarkable fact that nonpolar solvents play a more vital role in enhancing dual hydrogen bonds in S1 state. Probing into photo-induced excitation, we verify charge reorganization around proton acceptor and donor triggers ESPT tendency. Comparing energy gaps of frontier molecular orbitals (MOs), we further predict the ESPT process of HDBB could be facilitated by nonpolar solvents. To clarify the specific excited state behaviors, potential energy surfaces (PESs) in different solvents are constructed along with dual hydrogen bonds to present the overall ESPT processes. Searching transition state (TS) along reaction path, we confirm the excited state intramolecular single proton transfer (ESISPT) mechanism for HDBB. Further, we successfully present the excited state regulation mechanism via solvent polarity, namely, nonpolar solvents contribute to ESISPT reaction for HDBB compound.

Long-Range Charge Reorganization as an Allosteric Control Signal in Proteins.

A new mechanism of allostery in proteins, based on charge rather than structure, is reported. We demonstrate that dynamic redistribution of charge within a protein can control its function and affect its interaction with a binding partner. In particular, the association of an antibody with its target protein antigen is studied. Dynamic charge shifting within the antibody during its interaction with the antigen is enabled by its binding to a metallic surface that serves as a source for electrons. The kinetics of antibody–antigen association are enhanced when charge redistribution is allowed, even though charge injection happens at a position far from the antigen binding site. This observation points to charge-reorganization allostery, which should be operative in addition or parallel to other mechanisms of allostery, and may explain some current observations on protein interactions.

Optical spectroscopy of cryogenic metalated flavins: The O2(+) isomers of M+lumiflavin (M=Li–Cs)

Flavin complexes are used by nature in many photobiological processes, because their photochemical response in the visible range can be strongly modulated by their environment. Herein, we report optical spectra of mass-selected metal complexes of lumiflavin (LF) with alkali metal ions (M=Li–Cs) recorded in the visible range by photodissociation (VISPD) at cryogenic temperatures (T<20 K). VISPD spectra are measured in a tandem mass spectrometer coupled to a cryogenic ion trap and an electrospray ionization source. The vibrationally-resolved VISPD spectra obtained in the 420–450 nm range are assigned to the S0←S1 (ππ*) transition of the O2(+) isomers of M+LF by comparison to time-dependent density functional theory calculations (PBE0/cc-pVDZ) coupled to multidimensional Franck–Condon (FC) simulations. The preferred binding motif and interaction strength strongly depend on the size of M+. The spectra of M+LF with the smaller M+ ions (M=Li and Na) are attributed to the most stable O2+ isomers characterized by a N1–M–O2 chelate binding motif in which M+ can interact with the lone pairs of both N1 and O2 of LF. Because of steric interaction with the CH3 group at N10, the tricyclic aromatic ring is slightly bent and the VISPD spectra feature low-frequency out-of-plane bending modes of LF. Such an O2+ structure is sterically repulsive for the larger M+ ions (M=Rb and Cs), which instead form planar O2 minima with nearly linear C2–O2–M bonds. Their VISPD spectra are characterized by low-frequency in-plane bending modes (β) describing the M+…LF interaction. The VISPD spectrum of K+LF with the intermediate-size K+ ion is more complex and features very low-frequency modes resulting from a very shallow potential along the O2↔O2+ isomerization coordinate, which cannot be described well by harmonic FC simulations. Electronic S1 excitation slightly weakens the M+…LF interaction (6–9%), as deduced from the small ΔS1 blueshifts upon metalation at the O2(+) binding site, consistent with the charge reorganization deduced from the molecular orbitals involved in ππ* excitation. Overall, the effects of O2(+) complexation of LF are drastically different from those of the previously studied O4+ isomers, which are characterized by large ΔS1 redshifts based on the strong increase in the M+…LF interaction (up to 20%) upon the same ππ* excitation of the LF chromophor. The drastic site-specific variation in the photophysical response of the O2(+) and O4+ isomers arises mainly from the different effect of electronic excitation on the M+…LF bond strength rather than from the metal-induced change of the electronic structure and molecular orbitals of LF responsible for ππ* excitation.

Block deformation analysis: Density matrix blocks as intramolecular deformation density.

Block deformation analysis as deformation density of atomic orbitals is introduced to analyze intramolecular interactions. In this respect, density matrix blocks in terms of natural atomic orbitals are employed to find interacting and noninteracting multicenter subsystem and extract the corresponding deformation density. Eigenanalysis of this deformation density is performed to result eigenvalues and eigenorbitals as displaced charge due to the intramolecular interaction and orbital space responsible for charge reorganization, respectively, that possesses advantages of other methods, simultaneously. It is applied to several small molecules, different types of carbon allotropes including zero-, one-, and two-dimensional nanostructures, and challenging systems such as ortho-hydrogen atoms in planar biphenyl. Results highly correlate with delocalization and Wiberg bond indices and show that eigenvalues of block deformation analysis deserved to be considered as bonding index.

Applying Marcus theory to describe the carrier transports in organic semiconductors: Limitations and beyond.

Marcus theory has been successfully applied to molecular design for organic semiconductors with the aid of quantum chemistry calculations for the molecular parameters: the intermolecular electronic coupling V and the intramolecular charge reorganization energy λ. The assumption behind this is the localized nature of the electronic state for representing the charge carriers, being holes or electrons. As far as the quantitative description of carrier mobility is concerned, the direct application of Marcus semiclassical theory usually led to underestimation of the experimental data. A number of effects going beyond such a semiclassical description will be introduced here, including the quantum nuclear effect, dynamic disorder, and delocalization effects. The recently developed quantum dynamics simulation at the time-dependent density matrix renormalization group theory is briefly discussed. The latter was shown to be a quickly emerging efficient quantum dynamics method for the complex system.

Uncovering photo-excited intramolecular charge transfer and ESIPT mechanism for 5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis(2-benzo[d]thiazol-2-yl) phenol compound

In view of their facile synthetic routes and remarkable photo-induced stabilities, excited state intramolecular proton-transfer (ESIPT)-vibrant luminous materials have drawn more and more attention. In this work, we mainly focus on the photo-induced excitation behaviours, including excited state hydrogen bonding interactions and ESIPT reaction of a new 5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl)-bis(2-benzo[d]thiazol-2-yl) phenol molecule theoretically. To be consistent with the previous experiment, we name this molecule as IIa. Using molecular electrostatic potential (MEP), we explored the dual intramolecular hydrogen bonding interactions in IIa form. Then on the level of chemical geometries and infrared (IR) spectra, we confirmed that the double hydrogen bonds should be enhanced upon photoexcitation. Probing into charge reorganisation, we found that hydrogen proton does prefer to be attracted by enhanced electronic densities around N3 and N6. Combining potential energy surfaces (PESs) and electronic spectra, the excited state intramolecular single proton-transfer (ESISPT) behaviour could be verified for IIa although it owns two hydrogen bonds.

Structural, electronic and catalytic properties of bimetallic PtnAgn (n=1–7) clusters

The geometrical, electronic and catalytic properties of PtnAgn (n = 1–7) clusters are investigated by means of density functional theory (DFT) computations. The ground state structures are obtained by a structure search procedure based in the simulated annealing method. In general, the PtnAgn clusters adopt structures with Pt cluster motifs at the central position surrounded by silver islands. We found that the Pt4Ag4 and Pt6Ag6 clusters have a closed shell geometric structure and are the most stable clusters in this series. The bimetallic cluster reactivity is investigated by using the ionization potential, electron affinity, the d-band center, and the adsorption energy descriptors, respectively. However, it turns out that the reactivity of these systems is more sensitive to the chemical element on the cluster surface exhibiting a local reactivity. The different reactive sites on the cluster surface can be explained by the molecular electrostatic potential surface. In the PtnAgn alloys, the Pt species perform similar interactions with a CO molecule in comparison to the unary Pt clusters, whereas the Ag species issue weaker interactions, increasing the catalyst resistance. In this context, the bimetallic clusters may serve as potential candidates for hydrogenation reactions. Furthermore, the distinct charge reorganization on the PtnAgn alloys is useful for incorporating a lower number of noble metals in order to achieve an increased catalytic and selectivity capabilities. Theoretical data on the infrared spectra of the clusters is also provided.

Interplay of charge transfer and disorder in optoelectronic response in Graphene/hBN/MoS2 van der Waals heterostructures

Strong optoelectronic response in the binary van der Waals heterostructures of graphene and transition metal dichalcogenides (TMDCs) is an emerging route towards high-sensitivity light sensing. While the high sensitivity is an effect of photogating of graphene due to inter-layer transfer of photo-excited carriers, the impact of intrinisic defects, such as traps and mid-gap states in the chalcogen layer remain largely unexplored. Here we employ graphene/hBN (hexagonal boron nitride)/MoS2 (molybdenum disulphide) trilayer heterostructures to explore the photogating mechanism, where the hBN layer acts as interfacial barrier to tune the charge transfer timescale. We find two new features in the photoresponse: First, an unexpected positive component in photoconductance upon illumination at short times that preceeds the conventional negative photoconductance due to charge transfer, and second, a strong negative photoresponse at infrared wavelengths (up to 1720 nm) well-below the band gap of single layer MoS2. Detailed time and gate voltage-dependence of the photoconductance indicates optically-driven charging of trap states as possible origin of these observations. The responsivity of the trilayer structure in the infrared regime was found to be extremely large (> 108 A/W at 1550 nm using 20 mV source drain bias at 180 K temperature and ≈ − 30 V back gate voltage). Our experiment demonstrates that interface engineering in the optically sensitive van der Waals heterostructures may cast crucial insight onto both inter- and intra-layer charge reorganization processes in graphene/TMDC heterostructures.

H-Bonding-mediated binding and charge reorganization of proteins on gold nanoparticles.

Once introduced into the human body, nanoparticles often interact with blood proteins, which in turn undergo structural changes upon adsorption. Although protein corona formation is a widely studied phenomenon, the structure of proteins adsorbed on nanoparticles is far less understood. We propose a model to describe the interaction between human serum albumin (HSA) and nanoparticles (NPs) with arbitrary coatings. Our model takes into account the competition between protonated and unprotonated polymer ends and the curvature of the NPs. To this end, we explored the effects of surface ligands (citrate, PEG-OMe, PEG-NH2, PEG-COOH, and glycan) on gold nanoparticles (AuNPs) and the pH of the medium on structural changes in the most abundant protein in blood plasma (HSA), as well as the impact of such changes on cytotoxicity and cellular uptake. We observed a counterintuitive effect on the ζ-potential upon binding of negatively charged HSA, while circular dichroism spectroscopy at various pH values showed an unexpected pattern in the reduction of α-helix content, as a function of surface chemistry and curvature. Our model qualitatively reproduces the decrease in α-helix content, thereby offering a rationale based on particle curvature. The simulations quantitatively reproduce the charge inversion measured experimentally through the ζ-potential of the AuNPs in the presence of HSA. Finally, we found that AuNPs with adsorbed HSA display lower toxicity and slower cell uptake rates, compared to functionalized systems in the absence of protein. Our study allows examining and explaining the conformational dynamics of blood proteins triggered by NPs and corona formation, thereby opening new avenues toward designing safer NPs for drug delivery and nanomedical applications.

Strong Headgroup Interactions Drive Highly Directional Growth and Unusual Phase Co-Existence in Self-Assembled Phenolic Films.

Self-assembled materials as surface coatings are used to confer functional properties to substrates, but such properties are highly dependent on molecular organization that can be controlled through tailoring the noncovalent interactions. For monomolecular films, it is well-known that strong, dipolar interactions can oppose line tension generating noncircular domain growth. While many surfactant films exhibit liquid crystalline arrangement of the alkyl chains, there are relatively few reports of crystalline headgroups. Here, we report the self-assembly of phenolic surfactants where the combination of hydrogen bonding and π-stacking leads to a herringbone arrangement of the headgroups, generating a molecular super-lattice that can be observed using grazing incidence X-ray diffraction; such an arrangement has been previously proposed for related phenolic systems but never experimentally observed. We also investigated using pH to modulate the intermolecular interactions and the response of the system in terms of molecular organization. The first hydroxyl deprotonation does not appear to impact the structure but has significant impact on the domain size and morphology. Higher pH generates both strong directional domain growth and a loss of the molecular lattice structure, attributed to a second deprotonation. In contrast, a shorter chain surfactant, lauryl gallate, forms a liquid expanded phase that can contract upon deprotonation. In the condensed phase, the deprotonation kinetics are unusually slow for which an internal charge re-organization is proposed. The slow kinetics leads to the co-existence of three distinct phases for a single component system over relatively long timescales and provides evidence of a liquid-mediated polymorphic transformation process in two-dimensional, soft-matter films. This work has implications for understanding the long-range ordering in aromatic self-assembled structures and the mechanisms underlying Langmuir monolayer polymorphism.

Toward enhanced CO2 adsorption on bimodal calcium-based materials with porous truncated architectures

To increase the mineralization capabilities for the adsorption of carbon dioxide, we prepared bimodal calcium-based materials such as calcium oxide and calcium hydroxide with porous structures using a precipitation method with various drying processes. The various drying methods on porous structure develop different composition ratio of CaO and Ca(OH)2 in bimodal materials, and in particular, formation of different morphology and structure, which leads different adsorption characteristics. Samples prepared with such methods attained porous structure and more active adsorption sites. It is worth noting that the freeze drying (FD) and aerogel drying (AD) methods created the truncated crystal phase of the adsorbents, exposing active facet sites in the place of the vertices. The results of CO2 temperature programmed desorption and dynamic flow experiments reveal that porous calcium-based materials, synthesized through a process combining FD and AD sequentially, show high CO2 adsorption capacity (up to 26.1 wt% at 650 °C) with enhanced adsorption kinetics. To gain insight into CO2 adsorptive configuration at the atomistic scale and the adsorption mechanism, the adsorption of multiple CO2 molecules on the CaO (1 0 0) surface is investigated using density functional theory calculation. The CO2 molecules are chemisorbed through active charge reorganization between the CaO surface and CO2 molecules while the adsorption energy is highly stabilized at –1.56 eV. The experimental and theoretical findings both suggest that CO2 mineralization is feasible on calcium-based bimodal structured materials.