Dispersion Forces Research Articles

Adhesion Energy for Nonideal Cantilever and Its Relation to Casimir–Lifshitz Forces

The method of the adhered cantilever, borrowed from microtechnology, can help in gaining fundamental knowledge about dispersion forces acting at distances of about 10 nm, which are problematic to access in the usual Casimir-type experiments. A recently presented setup measures the shape of cantilevers with high precision, which is needed for analyzing the involved forces. The first measurements reveal several nonidealities crucial for the data analysis. In this paper, a generalized formula is deduced that relates the parameters of a cantilever to the adhesion energy. The application of the formula is demonstrated using the first test result from the setup, where a silicon cantilever adhered to a substrate sputters with ruthenium. Detailed information of the roughness of interacting surfaces, which deviates significantly from the normal distribution, is emphasized. Although not crucial, the electrostatic contribution can be significant due to the slight twisting of the cantilever. The theoretical prediction of the adhesion energy is based on Lifshitz theory. Comparing theory and experiment yields a contact distance of 45 nm and an adhesion energy of 1.3 µJ/m2, resulting from the Casimir–Lifshitz forces. Significant uncertainties arise from the uncontrolled electrostatic contribution. Factors that need to be addressed to measure weak adhesion between rough surfaces are highlighted.

Determination of surface free energy and acido-basicity of MXene materials measured by inverse gas chromatography at infinite dilution

Since the seminal report of Ti3C2Tx in 2011, MXene has emerged as a subject of considerable interest among researchers, finding diverse applications spanning energy storage, catalysis, and coatings. Despite extensive studies on the physicochemical properties of MXene, a comprehensive understanding of its surface energetics, free from environmental influences or external substitutes, remains lacking. This study aims to fill this gap by employing the inverse gas chromatography (IGC) technique at infinite dilution to delineate the London dispersive and specific components, alongside the Lewis acid-base characters, of surface free energy in MXene materials, including MAX phase and MXene. Our findings reveal that the London dispersive surface energy values of MAX phase and MXene range from 59.3 to 80.2 mJ m−2 and 107.8–119.9 mJ m−2, respectively, across temperature ranges of 303–333 K and 393–423 K. The observed augmentation in surface energy for MXene is attributed to a higher density of non-polar surface groups and an enlarged interlayer spacing. Additionally, our analysis indicates significantly higher acceptor (KA) and donor (KD) parameters for MXene (0.97 and 1.97, respectively) compared to MAX phase (0.41 and 0.63, respectively), suggesting a preference for the Lewis acid-base character in both materials, with MXene exhibiting a more pronounced tendency. These findings offer crucial insights into the fundamental surface energetic characteristics underlying multiple physicochemical properties of MXene. This understanding facilitates the informed design of interface engineering strategies, advancing the exploration and advancement of MXene-based technologies across a broad spectrum of applications.

Spatial Equilibria: The Case of Two Regions

In this paper we characterize the set of equilibria in a generalized version of the canonical two-region economic geography model that nests the class of models in Allen and Arkolakis (2014) as well as Krugman (1991) and features an input–output loop. We provide sufficient conditions for uniqueness of equilibria that — in contrast to the well-know result in Allen and Arkolakis (2014) — allow for positive agglomeration externalities, which concentrate economic activity, even in the absence of congestion effects, which disperse it, and highlight the key role played by three additional parameters: the trade elasticity, which regulates the strength of the dispersion force associated with the decline in the terms of trade caused by migration into a region; trade costs, which weaken this dispersion force by limiting trade across regions; and the importance of the agricultural sector, which pushes against agglomeration forces in manufacturing.

Smoother Semiclassical Dispersion for Density Functional Theory via D3S: Understanding and Addressing Unphysical Minima in the D3 Dispersion Correction Model.

One of the most widely used and computationally efficient models that accounts for London dispersion interactions within density functional theory (DFT) is the D3 dispersion correction model. In this work, we demonstrate that this model can induce the appearance of unphysical minima on the potential energy surface (PES) when the coordination number of atoms changes. Optimizing to these artifactual structures can lead to significant errors in determining the interaction energy between two molecules and in estimating the thermodynamic properties of the system. In several specific examples, such as Kuratowski-type H2-NiKur and H2-PdKur clusters, these local minima exhibited extremely high PES curvature, resulting in incorrect estimations of harmonic frequencies and significant overestimations of zero-point energy and enthalpy values. Although such erroneous behavior of the D3 model is relatively rare, it can occur across a wide range of chemical species, including molecules like the [Li(C6H6)]+ complex and the dispiro(acridan)-substituted pyracene (DSAP) molecule. Our analysis reveals that the root of the problem lies in the definition of the AB atomic-pair dependent C6AB coefficients in the D3 model. To address this issue, we propose a reparameterization of the D3 model by introducing a modified C6AB functional form that now depends on the specific pair of considered atoms. This new model, termed D3-Smooth (or D3S for short), is designed to smooth out the PES associated with the dispersion correction. By doing so, we demonstrate that D3S eliminates unphysical local minima while maintaining the quite satisfactory accuracy of the parent D3 method in interaction energy benchmark sets. For example, the RMS difference between using the D3(BJ) correction to B3LYP and the D3S(BJ) correction across the large MGCDB84 data set of nearly 5000 data points is only 0.12 kJ/mol. Similar results are obtained for every other D3-corrected functional tested. Consistent with this result, no significant improvement could be obtained for the B3LYP-D3S(0) correction by reoptimizing the damping function.

Exploring the Application of Advanced Chromatographic Methods to Characterize the Surface Physicochemical Properties and Transition Phenomena of Polystyrene-b-poly(4-vinylpyridine)

The linear diblock copolymer polystyrene-b-poly(4-vinylpyridine) (PS-P4VP) is an important copolymer recently used in many applications such as optoelectronics, sensors, catalysis, membranes, energy conversion, energy storage devices, photolithography, and biomedical applications. (1) Background: The surface thermodynamic properties of PS-P4VP copolymers are of great importance in many chemical and industrial processes. (2) Methods: The inverse gas chromatography (IGC) at infinite dilution was used for the experimental determination of the retention volumes of organic solvents adsorbed on copolymer surfaces as a function of temperature. This led to the variations in the free energy of interaction necessary to the evaluation of the London dispersive and polar acid–base surface energies, the polar enthalpy and entropy, the Lewis acid–base constants, and the transition temperatures of the PS-P4VP copolymer. (3) Results: The application of the thermal Hamieh model led to an accurate determination of the London dispersive surface energy of the copolymer that showed non-linear variations versus the temperature, highlighting the presence of two transition temperatures. It was observed that the Lewis acid–base parameters of the copolymer strongly depend on the temperature, and the Lewis base constant of the solid surface was shown to be higher than its acid constant. (4) Conclusions: An important effect of the temperature on the surface thermodynamic properties of PS-P4VP was proven and new surface correlations were determined.

Eliminating the Deadwood: A Machine Learning Model for CCS Knowledge-Based Conformational Focusing for Lipids.

Accurate elucidation of gas-phase chemical structures using collision cross section (CCS) values obtained from ion-mobility mass spectrometry benefits from a synergism between experimental and in silico results. We have shown in recent work that for a molecule of modest size with a proscribed conformational space we can successfully capture a conformation(s) that can match experimental CCS values. However, for flexible systems such as fatty acids that have many rotatable bonds and multiple intramolecular London dispersion interactions, it becomes necessary to sample a much greater conformational space. Sampling more conformers, however, accrues significant computational cost downstream in optimization steps involving quantum mechanics. To reduce this computational expense for lipids, we have developed a novel machine learning (ML) model to facilitate conformer filtering according to the estimated gas-phase CCS values. Herein we report that the implementation of our CCS knowledge-based approach for conformational sampling resulted in improved structure prediction agreement with experiment by achieving favorable average CCS prediction errors of ∼2% for lipid systems in both the validation set and the test set. Moreover, most of the gas-phase candidate conformations obtained by using CCS focusing achieved lower energy-minimum geometries than the candidate conformations without focusing. Altogether, the implementation of this ML model into our modeling workflow has proven to be beneficial for both the quality of the results and the turnaround time. Finally, while our approach is limited to lipids, it can be readily extended to other molecules of interest.

Electrostatically embedded symmetry-adapted perturbation theory.

Symmetry-adapted perturbation theory (SAPT) is an abinitio approach that directly computes noncovalent interaction energies in terms of electrostatics, exchange repulsion, induction/polarization, and London dispersion components. Due to its high computational scaling, routine applications of even the lowest order of SAPT are typically limited to a few hundred atoms. To address this limitation, we report here the addition of electrostatic embedding to the SAPT (EE-SAPT) and ISAPT (EE-ISAPT) methods. We illustrate the embedding scheme using water trimer as a prototype example. Then, we show that EE-SAPT/EE-ISAPT can be applied for efficiently and accurately computing noncovalent interactions in large systems, including solvated dimers and protein-ligand systems. In the latter application, particular care must be taken to properly handle the quantum mechanics/molecular mechanics boundary when it cuts covalent bonds. We investigate various schemes for handling charges near this boundary and demonstrate which are most effective in the context of charge-embedded SAPT.

On the Role of the Interlayer Interactions in Atomistic Simulations of Kaolinite Clay

A systematic simulation study was performed to investigate the interlayer interactions in a 1:1 layered phyllosilicate clay, kaolinite. Atomistic simulations with classical realistic force fields (INTERFACE and ClayFF) were used to examine the influence of the individual non-bonded interactions on the interlayer binding in the kaolinite model system. By switching off selected pairwise interactions in the applied force fields (leaving the intralayer interactions intact), it was confirmed that the tetrahedral–octahedral-type pairwise interactions held the kaolinite plates together and that interlayer hydrogen bonding, modeled by Coulombic forces, played a dominant role in this. Furthermore, it was observed that the number of hydrogen bonds formed had a significant influence on the basal spacing, and thus there was a striking change in the layer–layer interaction strength when there were only two kaolinite plates in the system, rather than several plates, as in real kaolinite particles. Contrary to expectations, the dispersion forces of the studied force fields alone were found to be strong enough to hold the kaolinite plates together.

Multi-stage and multi-colour liquid crystal reflections using a chiral triptycene photoswitchable dopant.

The photomodulation of the helical pitch of cholesteric liquid crystals results in dynamic and coloured canvases that can potentially be used in applications ranging from energy-efficient displays to colour filters, anti-counterfeiting tags and liquid crystal (LC) lasers. Here we report on the analysis of a series of photoswitchable chiral dopants that combine the large geometrical change and bistability of hydrazone switches with the efficient helical pitch induction of the chiral motif, triptycene. We elucidate the effects that conformational flexibility, dispersion forces and π-π interactions have on the chirality transfer ability of the dopant. We then use the irradiation time with visible light (442 nm) combined with a simple digital light processing microscope projection set-up to draw numerous stable multi-coloured images on an LC canvas, showcasing the fine control this dopant yields over the LC assembly.

Analytical simulation of the simultaneous adsorption process of methane and water vapor in shales

ABSTRACT Investigations on the diffusion – adsorption of methane and water vapour in shale nanopores are essential for developing shale gas extraction. A kinetic model considering diffusion and different adsorption mechanisms was proposed. An analytical solution to the model was obtained through the integral transformation method and used to predict the distributions of methane and water within a shale particle. The results suggest that the reversible adsorption caused by the dispersion force is not the only adsorption mechanism; irreversible adsorption caused by hydrogen bonding or other types of intermolecular forces is more prominent, lengthening the delay to reach equilibrium. The presence of water strongly affects shale, considerably decreasing the diffusivity and adsorption capacity as well as the swelling of the shale matrix caused by the increase in the methane pressure. The diffusion and adsorption process expands to the shale particle surface after the pores near the particle centre are filled. The transport and storage of water vapour are more sensitive to the pore structure than those of methane. In the initial stage of the methane diffusion‒adsorption process, a large number of water molecules enter the particles, and the adsorbed water hinders methane molecules from contacting the shale surface.

An experimental and computational investigation of the cyclopentene-containing peptide-derived compounds: focus on pseudo-cyclic motifs via intramolecular interactions.

Conformational flexibility is one of the main disadvantages of peptide-based compounds. We focus on their molecular 'chameleonicity' related to forming pseudo-cyclic motifs via modulation of weak intramolecular interactions. It is an appealing strategy for controlling equilibrium between the polar open and the nonpolar closed conformations. Within this context, we report here the crystal structure of the (R)-(2-tert-butoxycarbonyl)amino-1-oxo-3-phenyl)propyl)-1-cyclopentene (1), synthesis of which in high yield was achieved by a facile multi-step protocol. Our Cambridge Structural Database (CSD) overview for the peptide-based crystals revealed the exclusivity of this compound from the viewpoint of the unusual pseudo-bicyclic system via C-H…O and C-O…π interactions, in which cyclopentene shields the amide bond. Notably, cyclopentene as a bioisostere of proline is an appealing scaffold in medicinal chemistry. An extensive combined experimental and computational study provided more profound insight into the supramolecular landscape of 1 with respect to similar derivatives deposited in the CSD, including the tendency of cyclopentene for the generation of pseudo-cyclic motifs through weak H-bonding and π-based intramolecular interactions. These weak interactions have been examined by either the quantum theory of 'atoms-in-molecules' (QTAIM) or complex Hirshfeld surface methodology, including enrichment ratios, molecular electrostatic potential surfaces and energy frameworks. In all analysed crystals, all types of H-bonded motifs involving cyclopentene are formed at all levels of supramolecular architecture. A library of cyclopentene-based H-bonding synthons is provided. A molecular docking study depicted vital interactions of cyclopentene with key amino acid residues inside the active sites of two prominent protein kinases, uncovering the therapeutic potential of 1 against breast cancer. To a large extent, dispersion forces have significance in stabilizing the supramolecular structure of both ligand and bio-complex ligand-protein. Finally, the satisfactory in silico bio-pharmacokinetic profile of 1 related to drug-likeness and blood-brain barrier permeation was also revealed.

Investigations on adsorptive removal of PVC microplastics from aqueous solutions using Pinus roxburghii-derived biochar.

This study investigates the adsorption mechanisms of pine bark biochar (BC) and modified pine bark biochar (MBC) in the removal of polyvinyl chloride (PVC) microplastics from aqueous solutions, with a significant focus on resource recovery from pine residues which is one of the key Himalayan Forest byproducts. The research findings highlighted the optimal adsorption capacity of biochar at 131.5mg/g achieved after 6h of contact time, with a pH of 10 and a PVC microplastic concentration of 200mg/L. The primary mechanisms of PVC microplastic adsorption involved ion exchange and physical adsorption, driven by forces such as Vander-Waals, London forces, and electrostatic forces. Thermodynamic analysis showed the exothermic nature of the PVC and BC/MBC interaction, with spontaneous adsorption occurring within the temperature range of 10 to 40°C. Isotherm and kinetic models fit well with Temkin model and PSO kinetics, as indicated by R2 values exceeding 0.9. Particularly, MBC exhibited superior removal efficiency and adsorption capacity compared to its precursor, reaching an optimum adsorption capacity of 156.08mg/g with a removal efficiency of 78%, surpassing the performance of BC. This research contributes valuable insights into potential applications of BC for PVC removal and underscores the effectiveness of MBC in achieving enhanced adsorption outcomes.

Anisole-Water and Anisole-Ammonia Complexes in Ground and Excited (S1) States: A Multiconfigurational Symmetry-Adapted Perturbation Theory (SAPT) Study.

Binary complexes of anisole have long been considered paradigm systems for studying microsolvation in both the ground and electronically excited states. We report a symmetry-adapted perturbation theory (SAPT) analysis of intermolecular interactions in anisole-water and anisole-ammonia complexes within the framework of the multireference SAPT(CAS) method. Upon the S1 ← S0 electronic transition, the hydrogen bond in the anisole-water dimer is weakened, which SAPT(CAS) shows to be determined by changes in the electrostatic energy. As a result, the water complex becomes less stable in the relaxed S1 state despite decreased Pauli repulsion. Stronger binding of the anisole-ammonia complex following electronic excitation is more nuanced and results from counteracting shifts in the repulsive (exchange) and attractive (electrostatic, induction and dispersion) forces. In particular, we show that the formation of additional binding N-H···π contacts in the relaxed S1 geometry is possible due to reduced Pauli repulsion in the excited state. The SAPT(CAS) interaction energies have been validated against the coupled cluster (CC) results and experimentally determined shifts of the S1 ← S0 anisole band. While for the hydrogen-bonded anisole-water dimer SAPT(CAS) and CC shifts are in excellent agreement, for ammonia SAPT(CAS) is only qualitatively correct.

Optical and electric properties of tin oxide (SnO2) with reduced graphene oxide nanocomposite thin films

Due to their superior properties, two-dimensional (2D) nanomaterial materials have become increasingly popular for enhancing SnO2 thin films. In the paper, a thermionic vacuum arc (TVA) deposition system was used to produce a thin film of SnO2 with a reduced graphene oxide (rGO) nanocomposite. SnO2 thin films have become widely used in sensor applications, and these sensors have been shown to work at relatively high temperatures compared to room-temperature semiconductors. As a result, working temperatures affect the material properties. The surface properties of the deposited and post-annealed samples were investigated using field emission scanning electron microscopy integrated with energy dispersive x-ray spectroscopy and atomic force microscopy. The weight ratios of carbon and tin were calculated as 35 % and 65 %, respectively. The mean Z-height of the nanoparticles was determined to be 9 nm, and the distribution of the surface grains is nearly homogeneous. Following the post-annealing process, the thin film's band gap energy decreased from 3.78 eV to 3.25 eV. According to the photoluminescence spectra, emission peaks at 393 nm, 406 nm, and 443 nm were measured. The transmittance spectra of the various post-annealed samples at 150 °C were recorded, and they remained nearly the same. This consistency is a beneficial property of the thin film because SnO2:rGO nanocomposite thin films are designed to operate at relatively high temperatures. The present study investigates the advantages and properties of the post-annealed (repeating annealing) SnO2: rGO thin film.

Kinetics and thermodynamics investigations of efficient and eco-friendly removal of alizarin red S from water via acid-activated Dalbergia sissoo leaf powder and its magnetic iron oxide nanocomposite.

The present work aimed to highlight an efficient, readily accessible, and cost-effective adsorbent derived from Dalbergia sissoo (DS) leaf powder for removing the environmentally hazardous dye "alizarin red S" (ARS) from hydrous medium. A variant of the adsorbent is activated via sulfuric acid and composited with magnetic iron oxide nanoparticles (DSMNC). Both adsorbents are thoroughly characterized using techniques such as Fourier transform infrared spectroscopy, point of zero charge, energy-dispersive X-ray spectroscopy, and scanning electron microscopy, which show that they have a porous structure rich in active sites. Different adsorption conditions are optimized with the maximum removal efficiency of 76.63% for DS and 97.89% for DSMNC. The study was highlighted via the application of various adsorption isotherms, including Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich, to adsorption data. Pseudo-first-order, pseudo-second-order, and intra-particle diffusion models were utilized to investigate the kinetics and mechanism of adsorption. The Freundlich model and pseudo-second-order kinetics exhibited the best fit, suggesting a combination of physical interactions, as confirmed by the D-R and Temkin models. The dominant adsorbate-adsorbent interactive interactions responsible for ARS removal were hydrogen bonding, dispersion forces, and noncovalent aromatic ring adsorbent pi-interactions. Thermodynamic parameters extracted from adsorption data indicated that the removal of the mutagenic dye "ARS" was exothermic and spontaneous on both DS and DSMNC, with DSMNC exhibiting higher removal efficiency.

Unveiling the competitive mechanism between SO2 and PCDD/Fs on activated carbon adsorption

In municipal solid waste incineration (MSWI) plants, activated carbon (AC) adsorption is the key technique for eliminating Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from flue gases. This research thoroughly investigates the potential competitive adsorption between SO2 and PCDD/Fs and examines how adsorption at the center and the edge of the AC layer impacts the adsorption process. The findings show a decline in the removal efficiency of PCDD/Fs from 86.8 % to 84.2 % and further to 74.4 % when using SO2 pre-treated (AC-A3) and H2SO4-impregnated (AC-B2) activated carbon, respectively. Multiple characterization methods reveal that sulfur elements occupy active sites within the inner pores of the activated carbon, reducing the availability of its pore structure, particularly affecting microporous more than mesoporous structures. DFT calculations suggest that the π-π EDA effect facilitates the adsorption of 2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), whereas dispersion force drive SO2 adsorption. Comparisons among various oxygenated functional groups show that the organic acid anhydride (CO-CO) has better adsorption selectivity toward TCDD and less adsorption to SO2. This study provides a novel perspective on the adsorption mechanisms of PCDD/Fs on AC and the competitive dynamics of sulfur in the flue gas.

Ion‐Pairing Chromonic Liquid Crystals via Alternately Stacked Assembly of Amphiphilic Charged π‐Electronic Systems

In this study, a new assembly strategy for lyotropic chromonic liquid crystals (LCLCs) is proposed using iπ–iπ interactions, mainly comprising electrostatic and dispersion forces, between charged π‐electronic systems to form stacking structures supported by the hydration of triethylene glycol (TEG) units. Meso‐TEG‐aryl‐substituted porphyrin AuIII complex, an amphiphilic π‐electronic cation, showed diverse states and assembly modes in ion pairs depending on the coexisting counteranions. The PCCp– ion pair formed a hexagonal columnar (Colh) LC phase based on a charge‐by‐charge assembly, suggesting the formation of an ordered arrangement of charged p‐electronic systems through iπ–iπ interactions, with reduced interactions between the TEG chains. Furthermore, in the presence of water, LCLC behaviors in the Colh and nematic columnar phases according to the amount of water were observed for the PCCp– ion pair via iπ–iπ interactions. Magnetic‐field‐induced orientation of the charge‐by‐charge columnar structures upon dehydration was observed. Furthermore, single‐stranded charge‐by‐charge columnar structures, as components of the LCLCs, were observed using transmission electron microscopy (TEM).

Strength of London Dispersion Forces in Organic Structure Directing Agent-Zeolite Assemblies.

Herein, we study the London dispersion forces between organic structure directing agents (OSDAs)-here tetraalkyl-ammonium or -phosphonium molecules-and silica zeolite frameworks (FWs). We demonstrate that the interaction energy for these dispersion forces is correlated to the number of H atoms in OSDAs, irrespective of the structures of OSDAs or FWs, and of variations in charges and thermal motions. All calculations considered-DFT-D3 and BOMD undertaken by us, and molecular mechanics from an accessible database-led to the same trend. The mean energy of these dispersion forces is ca. -2 kcal.mol-1 per H for efficient H-O contacts.

Theoretical insights into the diverse stabilizing effects of fenchyl alcohol/thymol eutectic solvent on carotenoids

Carotenoids, a class of vital natural pigments, are known for their antioxidant properties and are integral to various industrial applications. However, their instability during processing and storage has limited their broader utilization. This study investigated the stabilizing effects of a fenchyl alcohol/thymol-based deep eutectic solvent (DES) on a spectrum of carotenoids, including lutein, zeaxanthin, astaxanthin, and β-carotene. Through a combination of ab initio molecular dynamics (AIMD) simulations and quantum chemical calculations, we elucidated the molecular interactions and stabilization mechanisms within the DES environment (methanol as the benchmark). Our findings reveal that the DES could exert varying degrees of influence on the stability of different types of carotenoids. The temperature-dependent behavior of carotenoids in the DES suggested a complex interplay between hydrogen bonding, dispersion forces, and the inherent structural properties of carotenoids. AIMD simulations provided a detailed picture of the structural organization and hydrogen bond network topology within the DES, highlighting the role of temperature on the stability and orientation of solvent molecules around carotenoids. Energy decomposition analysis (EDA), Hirshfeld surface analysis, and visual study of interactions further dissected the non-covalent interactions, emphasizing the significance of electrostatic and dispersion forces-driven non-covalent interactions (van der Waals dispersion interactions) in stabilizing carotenoids within the DES matrix. In comparison to methanol, the interactions between components of the eutectic system and the target molecules demonstrate enhanced dynamism, increased complementarity, and a greater variety of interaction patterns. This research presented a novel perspective on the use of DESs for the stabilization of carotenoids, offering potential solutions to enhance their industrial applicability and performance. The insights gained from this study are crucial for the development of sustainable and eco-friendly solvent systems, aligning with the growing demand for green chemistry in the pharmaceutical, cosmetic, and food industries.

Optical and supramolecular properties of cyclometalated palladium nanostructures with tumor targeting properties in living mice: a quantum mechanics interpretation.

The recent discovery that metallophilic interactions between cyclometalated palladium supramolecular nanostructures - with efficient tumour accumulation rate in a skin melanoma model - maintain excellent photodynamic properties even in a hypoxic microenvironment has inspired the present study focused on the theoretical predictions of optical properties of the bis-cyclometalated palladium compound in different contexts. More specifically, structural and UV/Vis absorption properties of both monomeric and dimeric forms of this anticancer drug are well reproduced with a Time-Dependent Density Functional Theoretical (TD-DFT) approach based on Exchange-Correlation (XC) hybrid functionals in conjunction with conductor-like and polarization solvation effects. A further novelty is represented by a fine investigation of the supramolecular interactions between the different subunits of the drug via dispersion force correction andQuantum Theory of Atoms in Molecules (QTAIM). This contribution while supporting the photoexcitation properties derived in laboratory following the self-assembly of monomeric units when passing from dimethyl sulfoxide (DMSO) to a H2O/DMSO mixture at 298K, shed some light on the nature of the chemical interactions modulating the formation of nano-size aggregates.