Efficiency Conceptualization Model: A Theoretical Method for Predicting the Turnover of Catalysts.

In recent times, the theoretical prediction of catalytic efficiency is of utmost urgency. With the advent of density functional theory (DFT), reliable computations can delineate a quantitative aspect of the study. To this state-of-the-art approach, valuable incorporation would be a tool that can acknowledge the efficiency of a catalyst. In the current work, we developed the efficiency conceptualization model (ECM) that utilizes the quantum mechanical tool to achieve efficiency in terms of turnover frequency (TOF). Twenty-six experimentally designed transition metal (TM) water oxidation catalysts were chosen under similar experimental conditions of temperature, pressure, and pH to execute the same. The computations conclude that the Fe-based [Fe(OTf)2(Me2Pytacn)] (MWOC-17) is a highly active catalyst and, therefore, can endure for more time in the catalytic cycle. Our results conclude that the Ir-based catalysts [Cp*Ir(κ2-N,O)X] with MWOC-23: X=Cl; and MWOC-24: X=NO3 report the highest computed turnover numbers (TONs), τ c o m p u t e d T O N 0 ${\tau _{computed\;TON}^0 }$ of 406 and 490 against the highest experimental TONs, τ e x p e r i m e n t a l T O N ${\tau _{experimental\;TON} }$ of 1200 and 2000 respectively, whereas the Co-based [Co(12-TMC)]2+ (MWOC-19) has the lowest TONs ( τ c o m p u t e d T O N 0 ${\tau _{computed\;TON}^0 }$ =19, τexperimental TON=16) among the chosen catalysts and thereby successful in corroborating the previous experimental results.

Dissociative electron attachment to halogenated nucleotides: a quest for better radiosensitizers.

Tumor hypoxia hampers radiotherapy efficacy, necessitating radiosensitizers. Substituted nucleobases offer advantages as radiosensitizers. They can be incorporated into DNA with minimal gene-expression alteration, selectively targeting tumor cells and having lower toxicity to normal tissues. They possess higher electron affinity than native DNA, facilitating rapid electron attachment for cancer-cell damage. Despite advancements, exploration beyond uracil nucleobases remains limited. Herein, we investigated electron attachment to potential radiosensitizers, specifically 5-halo-2'-deoxycytidine-3'-monophosphates (5X-3'-dCMPH). Our findings indicate that 5X-3'-dCMPH nucleotides possess higher electron affinity than unsubstituted 3'-dCMPH, suggesting halogenated nucleotides are better electron acceptors. Moreover, the high vertical detachment energy (VDE) implies minimal auto-detachment, and the dissociative electron attachment (DEA) pathways suggest that dehalogenation is the favored process for halogenated systems, supported by low dissociation barriers. Notably, 5Br-3'-dCMPH and 5I-3'-dCMPH exhibit nearly barrier-free dissociation after electron attachment, and thus, they may preferentially act as superior radiosensitizers.

Realization of efficient and selective NO and NO2 detection via surface functionalized h-B2S2 monolayer.

In the ever-growing field of two-dimensional (2D) materials, the boron-sulfide (B2S2) monolayer is a promising new addition to MoS2-like 2D materials, with the boron (a lighter element) pair (B2 pair) having similar valence electrons to Mo. Herein, we have functionalized the h-phase boron sulfide monolayer by introducing oxygen atoms (Oh-B2S2) to widen its application scope as a gas sensor. The charge carrier mobilities of this system were found to be 790 × 102 cm2 V-1 s-1 and 32 × 102 cm2 V-1 s-1 for electrons and holes, respectively, which are much higher than the mobilities of the MoS2 monolayer. The potential application of the 2D Oh-B2S2 monolayer in the realm of gas sensing was evaluated using a combination of density functional theory (DFT), ab initio molecular dynamics (AIMD), and non-equilibrium Green's function (NEGF) based simulations. Our results imply that the Oh-B2S2 monolayer outperforms graphene and MoS2 in NO and NO2 selective sensing with higher adsorption energies (-0.56 and -0.16 eV) and charge transfer values (0.34 and 0.13e). Furthermore, the current-voltage characteristics show that the Oh-B2S2 monolayer may selectively detect NO and NO2 gases after bias 1.4 V, providing a greater possibility for the development of boron-based gas-sensing devices for future nanoelectronics.

Atmospheric oxidation pathways of CF3CH2CFCl2 (HCFC-234fb) with OH-radicals and Cl-atoms: insights into the mechanism, thermodynamics, and kinetics.

The atmospheric oxidation of 1,1-dichloro-1,3,3,3-tetrafluoropropane, HCFC-234fb (DTP), leads to the formation of harmful radicals, contributing to stratospheric ozone depletion. Thus, a detailed study of the gas-phase oxidation of the first-generation chlorofluorocarbon alternative HCFC-234fb by a reaction with hydroxyl radicals and chlorine atoms is important to understand its harmful effects on the environment. In this work, we have performed quantum chemical calculations to investigate the thermodynamic and kinetic aspects of the titled reaction. The potential energy profile calculated at the CCSD(T)/aug-cc-pVTZ//MP2/cc-pVTZ level of theory shows that the major reaction pathway involves the abstraction of the H-atom from the central carbon atom, C2, giving rise to the product radical CF3C˙HCCl2F. The calculated rate-coefficients for the reaction with ˙OH and Cl-atoms are 3.89 × 10-15 and 2.54 × 10-17 cm3 molecule-1 s-1, respectively, at 298 K and are in accordance with the experimental rate coefficients. The results suggest that the rate-coefficient for the reaction of DTP with ˙OH is two orders of magnitude higher than that with Cl-atoms, indicating greater significance of the former reaction in the atmosphere. With the rate-coefficient values, the lifetime and the radiative efficiency were calculated to be 8.2 years and 0.246 W m-2 ppb-1, respectively. A 100-year global warming potential (GWP) of 712 was also estimated using the lifetime corrected radiative efficiency value.

Unraveling the Stability and Magnetic Properties of Bis-Hydrated Mn(II) Complexes via Tailored Ligand Design.

Exploring the electronic structure and dynamic behavior of Mn(II) complexes reveals fascinating magnetic properties and prospective biomedical applications. In this study, we investigate the solvent phase dynamics of heptacoordinated Mn(II) complexes through ab initio molecular dynamics simulations and density functional theory (DFT) calculations with effectively varying temperatures. We observed that the complex with high stability ([Mn(pmpa)(H2O)2]) remains relatively rigid as the temperature increases to 90 °C, with only a minor change in its radial distribution functions (RDFs), compared to the RDF peaks at 25 °C. To elucidate the impact of halogens on the magnetic anisotropy of seven-coordinated Mn(II) complexes, we performed both DFT and multireference calculations. This shows that the zero-field splitting (ZFS) parameter D follows the order D(I)> D(Br)> D(Cl). We observed a significant increase in the D-value following the substitution of soft Se-donors in the equatorial position and heavier halogens in the axial position. The D-value of halogen derivatives of Se-analogues varies in the order of D(Cl) < D(I) < D(Br), deviating from the regular spectrochemical series with the discrepancy between the covalency of the Mn(II)-Se bond and the ligand field strength. We anticipate that this study will enhance our understanding of the solvent phase dynamics and structural aspects of ZFS in various Mn(II) complexes with different electronic environments.

Deciphering the Internal Conversion Processes Involved in the Photochemical Ring-Opening of 1,3-Cyclohexadiene by Symmetric sp2-Carbon Substitutions.

Chemical substituents hold the potential to markedly influence the photochemical behavior in molecular systems and assist in gaining a comprehensive understanding of nonadiabatic phenomena. In this study, we have conducted a comparative analysis of the influence of chemical substituents on the photochemical ring-opening of 1,3-cyclohexadiene (CHD), considering four systems: CHD, 2,3-dimethylcyclohexadiene (CHD-Me2-1), 1,4-dimethylcyclohexadiene (CHD-Me2-2), and 1,2,3,4-tetramethylcyclohexadiene (CHD-Me4), using electronic structure theory calculations and nonadiabatic molecular dynamics simulations. Employing extended multistate complete active space second-order perturbation (XMS-CASPT2) theory, we optimized reactants, S1 states, conical intersections (CIns), and products, revealing structural and energetic variations consistent with prior research. Nonadiabatic molecular dynamics simulation was used to gain insights into photochemical dynamics at state-averaged complete active space self-consistent field (SA-CASSCF) theory. CHD-Me4 exhibited reduced carbon-carbon single bond rupture rates, responsible for ring-opening, due to substituent proximity. Further, CHD-Me2-2 and CHD-Me4 displayed prolonged excited-state relaxation times, highlighting notable substituents' impact. Analysis of kinetic energy profiles of specific carbon atoms also revealed restrained atomic displacements, particularly in CHD-Me2-2 and CHD-Me4. These findings advance our understanding of how substituents modulate photochemical reactions in cyclohexadiene derivatives, guiding new molecular design and future research.

Investigating the Atmospheric Fate and Kinetics of OH Radical-Initiated Oxidation Reactions for Epoxybutane Isomers: Theoretical Insight.

Epoxides, which belong to the category of oxygenated volatile organic compounds (OVOCs), are emitted into the atmosphere by an array of sources and can impact both human and environmental well-being significantly. This study involves comprehensive computational analyses aimed at investigating the mechanism, thermodynamic aspects, and reaction kinetics associated with hydrogen abstraction reactions of cis-2,3-epoxybutane, trans-2,3-epoxybutane, and 1,2-epoxybutane by OH radicals. The potential energy diagrams involving all of the species for each specific pathway were constructed at the CCSD(T)/aug-cc-pVTZ//M06-2X/cc-pVTZ level of theory. The rate coefficients for all possible pathways were calculated using the Rice-Ramsperger-Kassel-Marcus master equation (RRKM-ME) corrected by Eckart tunneling within the 200-350 K temperature range and 1 atm pressure. The overall rate coefficients of the reaction of cis-2,3-epoxybutane, trans-2,3-epoxybutane, and 1,2-epoxybutane with OH radicals at 298.15 K were found to be 0.32 × 10-12, 0.33 × 10-12, and 0.66 × 10-12 cm3 molecule-1 s-1, respectively. We also studied the atmospheric lifetime and photochemical ozone creation potential (POCP) of all three compounds. In addition, we have provided extensive degradation pathways for the product radicals formed from the initial reaction with OH radicals in the presence of O2 and NO. The study showed that the product radicals can result in various harmful end products, including grade 1 and grade 2 carcinogens, as listed by the World Health Organization (WHO).

Revisiting fulgide photochromism: Mechanistic decoding and electron transport from computational exploration.

The photochromic behavior of the fulgide molecule relies on ring-closure and ring-opening processes involving conical intersections during excited state transformation between isomers. The precise location and topography of these conical intersections significantly shape the decay process and fluorescence phenomena inherent to the molecule. This work combines electronic structure theory calculations using the density functional theory and wavefunction methods, as well as surface hopping simulation to analyze the photochemical behavior of an experimentally synthesized fulgide molecule, (E)-p-methylacetophenylisopropylidenesuccinic anhydride (1E). Our study reveals the conical intersection between the first excited state (S1) and the ground electronic state (S0), which emerges beyond the S1 minimum of 1E to the ring-closing side. The distinctive topography of this conical intersection appears to be sloped. These findings suggest a reduced quantum yield for the formation of the closed isomer, indicating a higher likelihood of reformation of the open isomer(s). The surface hopping simulation further supports this observation, revealing a mere ∼8% quantum yield for the formation of the closed isomer. In addition, the photoisomerization of the fulgide molecule initiates a cascade of conduction switching and holds great potential for applications in molecular electronics. Delving into the realm of molecular electronics, we have further examined the electron transport properties, disclosing the higher conductivity of the closed isomer.

Torsional Rotation in Ditopic Receptor Host and its Complex Formation with Resorcinol Guest: A Computational Study.

Noncovalent interactions due to the presence of heteroatoms in supramolecular compounds have gained a lot of attention. These different heteroatom-based supramolecular compounds have inspired us to examine the noncovalent interaction in the isolated host and host-guest complexes. In view of this, in the current manuscript, we investigated the stability and torsional energy barrier of different conformers of the ditopic receptor host 1,6-bis(2,6-bis(benzothiazol-2-yl) pyridine-4-yloxy) hexane (bbh). The conformer that is accompanied by intramolecular C-H⋯N and C-H⋯S interactions is relatively more stable than the others. Due to torsional angle rotation within the host, the C-H⋯N and C-H⋯S interactions get disrupted and exhibit different binding sites for capturing guest molecules. In addition, we have extended the investigation to understand the interaction energy and nature of interaction in host-guest (1 : 1 and 1 : 2) complexes formed between the host (bbh) and guest (resorcinol) by using different DFT functionals. Extended transition state-natural orbital chemical valence (ETS-NOCV) analysis of complexes revealed that the electrostatic interaction significantly contributes to the host-guest interaction energy. The noncovalent (NCI) analysis provides the existence of intermolecular hydrogen bonding and other weak interactions within the complexes.

Unveiling the Noncovalent Interaction of Thiazol-2-ylidene and Its Derivatives as N-heterocyclic Carbene with Different Proton Donor Molecules.

The importance of noncovalent interaction has gained attention in various domains covering drug and novel catalyst design. The present study mainly characterizes the role of hydrogen bond (H-bond) and other intermolecular interactions in different (1 : 1) complex analogues formed between the N-aryl-thiazol-2-ylidene (YR) and five proton donor (HX) molecules. The analysis of the singlet-triplet energy gap ( Δ E S - T ${{\rm{\Delta }}E_{\left( {S - T} \right)} }$ ) confirmed the stability of the singlet state for this class of N-aryl-thiazol-2-ylidenes than the triplet state. The interaction energy values of the YR-HX complexes follow the order: YR-NH3

Perturbing π-clouds with Substituents to Study the Effects on Reaction Dynamics of gauche-1,3-Butadiene to Bicyclobutane Electrocyclization.

The conical intersection (CI) governs the ultra-fast relaxation of excited states in a radiationless manner and are observed mainly in photochemical processes. In the current work, we investigated the effects of substituents on the reaction dynamics for the conversion of gauche-1,3-butadiene to bicyclobutane via photochemical electrocyclization. We incorporated both electron withdrawing (-F) and donating (-CH3 ) groups in the conjugated system. In our study, we optimized the minimum energy conical intersection (MECI) geometries using the multi-configurational state-averaged CASSCF approach, whereas, to study the ground state reaction pathways for the substituted derivatives, dispersion corrected, B3LYP-D3 functional was used. The non-adiabatic surface hopping molecular dynamics simulations were performed to observe the behaviour of electronic states involved throughout the photoconversion process. The results obtained from the multi-reference second-order perturbation correction of energy at the XMS-CASPT2 level of theory, topography analysis, and non-adiabatic dynamics suggest that the -CH3 substituted derivatives can undergo faster thermal conversion to the product in the ground state with a smaller activation energy barrier compared to -F substituted derivative. Our study also reveals that the GBUT to BIBUT conversion follows both conrotatory and disrotatory pathways, whereas, on substitution with -F or -CH3 , the conversion proceeds via the conrotatory pathway.

Probing the dynamic behaviour and magnetic identification of seven coordinated Mn(II) complexes: a combined AIMD and multi-reference approach.

We present an in-depth solution phase dynamics of rare seven coordinated pentagonal bipyramidal Mn(II) complexes, together with their binding affinity anticipated using ab initio molecular dynamics (AIMD) simulations and density functional theory (DFT). Moreover, the simulations at different temperatures (25 °C and 90 °C) interpret the rigidity and stability of the ligands with Mn(II) ions. An intuitive approach for modulating the easy plane magnetic anisotropy of the mononuclear Mn(II) complex has been revealed by this work. In this regard, we have performed an extensive theoretical study based on the ab initio CASSCF/NEVPT2 method, exhibiting the presence of an easy plane magnetic anisotropy with a positive value of axial zero-field splitting (ZFS) parameter D. The complex's magnetic properties and electronic relaxation reveal that the rhombic ZFS term (E) can be modulated as the symmetry around the Mn(II) ion varies. The magnitude of the D-value increased with a more symmetrical equatorial ligand as found in the order of [Mn(pydpa)(H2O)] > [Mn(cbda)(H2O)]- > [Mn(dpaaa)(H2O)]- > [Mn(dpasam)(H2O)]-. Furthermore, we found that substituting the equatorial oxygen atom with heavier S and Se-donor atoms switches the sign of magnetic anisotropy for the Mn(II) complexes. The magnitude of the D-value increased when the energy levels of the ground state (GS) and the first excited state (ES) decreased. The observed magneto-structural correlation reveals that shortening the distance of the axial water molecule (Mn-O(w)) increases the D-value by an order of magnitude for the symmetrical [Mn(pydpa)(H2O)] complex. Overall, the combined analysis of solution phase dynamics of Mn(II) complexes and their magnetic characterization opens up new avenues in coordination chemistry, molecular magnetism, spin-crossover materials, and catalysis.

Exploring π-π interactions and electron transport in complexes involving a hexacationic host and PAH guest: a promising avenue for molecular devices.

Single isolated molecules and supramolecular host-guest systems, which consist of π-π stacking interactions, are emerging as promising building blocks for creating molecular electronic devices. In this article, we have investigated the noncovalent π-π interaction and intermolecular electron charge transport involved in a series of host-guest complexes formed between a cage-like host (H6+) and polycyclic aromatic hydrocarbon (PAH) guests (G1-G7) using different quantum chemical approaches. The host (H6+) consists of two triscationic π-electron-deficient trispyridiniumtriazine (TPZ3+) units that are bridged face-to-face by three ethylene-triazole-ethylene. Our theoretical calculations show that the perylene and naphthalene inclusion complexes G7⊂H and G1⊂H have the highest and lowest interaction energies, respectively. In addition, energy decomposition analysis (EDA) indicated that the dispersion interaction term, ΔEdisp, significantly contributes to the host-guest interaction and is correlated with the existence of π-π van der Waals interaction. Using the nonequilibrium Greens function (NEGF) method in combination with density functional theory (DFT), the current-voltage (I-V) curves of the complexes were estimated. The conductance values increased when the guests were embedded inside the host cavity. Notably, the complex G7⊂H has the maximum conductance value. Overall, this study provided the electron transport of the PAH inclusion host-guest complex through π-π interaction and provided a direction for the fabrication of future supramolecular molecular devices.

The first HyDRA challenge for computational vibrational spectroscopy.

Vibrational spectroscopy in supersonic jet expansions is a powerful tool to assess molecular aggregates in close to ideal conditions for the benchmarking of quantum chemical approaches. The low temperatures achieved as well as the absence of environment effects allow for a direct comparison between computed and experimental spectra. This provides potential benchmarking data which can be revisited to hone different computational techniques, and it allows for the critical analysis of procedures under the setting of a blind challenge. In the latter case, the final result is unknown to modellers, providing an unbiased testing opportunity for quantum chemical models. In this work, we present the spectroscopic and computational results for the first HyDRA blind challenge. The latter deals with the prediction of water donor stretching vibrations in monohydrates of organic molecules. This edition features a test set of 10 systems. Experimental water donor OH vibrational wavenumbers for the vacuum-isolated monohydrates of formaldehyde, tetrahydrofuran, pyridine, tetrahydrothiophene, trifluoroethanol, methyl lactate, dimethylimidazolidinone, cyclooctanone, trifluoroacetophenone and 1-phenylcyclohexane-cis-1,2-diol are provided. The results of the challenge show promising predictive properties in both purely quantum mechanical approaches as well as regression and other machine learning strategies.

Pyridinic Dominance N-Doped Graphene: A Potential Material for SO2 Gas Detection.

The sensors based on graphene have shown great promise in the detection of toxic air pollutants that are detrimental to nature and create risks to human health. Many recent experimental and computational efforts have been dedicated to sensor concepts incorporating pure graphene, graphene oxide, and doped graphene. Herein, a combination of spin-polarized density functional theory (DFT) with van der Waals correction and ab initio molecular dynamics (AIMD) approaches are utilized to assess the gas sensing potential of pyridinic dominance N-doped graphene (PNG) toward SO2 detection. The potential of PNG systems as SO2 sensing can be explored through an in-depth analysis of adsorption energies, electronic parameters, charge transfer, selectivity, and thermal stability. It is further demonstrated that external strains and the modulation of external electric fields are two effective ways to modify the adsorption strength. In light of these findings, our studies suggest that PNG monolayers have the potential to be an essential substrate for the detection of SO2.

The role of the shape resonance state in low energy electron induced single strand break in 2'-deoxycytidine-5'-monophosphate.

Low energy electron (LEE) induced single strand break (SSB) has been studied for 2'-deoxycytidine-5'-monophosphate (5'-dCMPH) molecules in the gas phase by means of ab initio electronic structure methods and local complex potential based time-dependent wavepacket quantum mechanical calculations. We have found that the LEE attachment to this cytidine nucleotide results in the formation of a transient metastable anion. The results obtained here show that the electron attachment takes place at the cytosine nucleobase center and within 18-20 fs, the LEE transfers to the σ* orbital of the sugar-phosphate 5' C-O bond. The characteristic electron attachment cross section spectrum is found at ∼1 eV, which is in good agreement with the available experimental observations. Quantum mechanical tunneling of the 5' C-O bound vibrational energy levels may contribute to SSB only above 1.5 eV energy regimes.

Low-Energy Electron Interaction with the Phosphate Group in DNA Molecule and the Characteristics of Single-Strand Break Pathways.

We modeled the low-energy electron attachment to the sugar-phosphate-sugar (SPS) molecule for investigating the single-strand break (3' C-O and 5' C-O) at the DNA backbone. In particular, we predicted the electron capture at the phosphate center. We found that 0.6 eV electron can attach to the phosphate group, and the lifetime (∼40-55 fs) of the resulting temporary negative ion state is more than what we found for the lifetime of the metastable species (∼18-20 fs) formed at the cytosine base center. We treated the two competing dissociation channels in SPS molecule, that is, both the 3' C-O and 5' C-O lesions, separately. The activation energy barrier calculated for 5' C-O bond rupture is found to be less than that for 3' C-O bond dissociation. The overall low-energy electron transfer process is found to be mediated through a "shape resonance state" formed at the phosphate center.

Low energy electron induced cytosine base release in 2'-deoxycytidine-3'-monophosphate via glycosidic bond cleavage: a time-dependent wavepacket study.

Low energy electron (LEE) induced cytosine base release in a selected pyrimidine nucleotide, viz., 2'-deoxycytidine-3'-monophosphate is investigated using ab initio electronic structure methods and time dependent quantum mechanical calculations. It has been noted that the cytosine base scission is comparatively difficult process than the 3' C-O bond cleavage from the lowest π* shape resonance in energy region <1 eV. This is mainly due to the high activation energy barrier associated with the electron transfer from the π* orbital of the base to the σ* orbital of the glycosidic N-C bond. In addition, the metastable state formed after impinging LEE (0-1 eV) has very short lifetime (10 fs) which may decay in either of the two competing auto-detachment or dissociation process simultaneously. On the other hand, the selected N-C mode may cleave to form the cytosine base anion at higher energy regions (>2 eV) via tunneling of the glycosidic bond. Resonance states generated within this energy regime will exist for a duration of ~35-55 fs. Comparison of salient features of the two dissociation events, i.e., 3' C-O single strand break and glycosidic N-C bond cleavage in 3'-dCMPH molecule are also provided.

Ultrafast Hot Exciton Nonadiabatic Excited-State Dynamics in Green Fluorescent Protein Chromophore Analogue.

The ultrafast high-energy nonadiabatic excited-state dynamics of the benzylidenedimethylimidazolinone chromophore dimer has been investigated using an electronic structure method coupled with on-the-fly quantitative wave function analysis to gain insight into the photophysics of hot excitons in biological systems. The dynamical simulation provides a rationalization of the behavior of the exciton in a dimer after the photoabsorption of light to higher-energy states. The results suggest that hot exciton localization within the manifold of excited states is caused by the hindrance of torsional rotation due to imidazolinone (I) or phenolate (P) bonds i.e., ΦI- or ΦP-dihedral rotation, in the monomeric units of a dimer. This hindrance arises due to weak π-π stacking interaction in the dimer, resulting in an energetically uphill excited-state barrier for ΦI- and ΦP-twisted rotation, impeding the isomerization process in the chromophore. Thus, this study highlights the potential impact of the weak π-π interaction in regulating the photodynamics of the green fluorescent protein chromophore derivatives.

MaxKinEff: A Collision Theory-Based Approach for Analyzing Turnover Frequency and Turnover Number in Catalytic Processes.

The efficiency of catalysts relies on comprehending the underlying kinetics that govern their performance. Under the steady-state regime, the "rate" is referred to as the turnover frequency, where the reaction rate is first order with respect to catalysts. Here, we introduce the Maximum Kinetic Efficiency (MaxKinEff ) model, grounded in collision theory, to predict efficiency based on maximum turnover frequency, 𝛤max TOF0 and maximum turnover number, 𝜏max TON0. The model was applied to molecular water oxidation using twenty-six transition metal catalysts from the first (3d), second (4d), and third (5d) rows. A thorough investigation reveals that [Ru(pda)(Br-py)2] (pda = 1,10-phenanthroline-2,9-dicarboxylate; Py = pyridinophane) exhibits a notable 𝛤max TOF0 of 1176.87 × 10-5 s-1 due to its larger collision diameter (σ𝑅𝐶) and lower activation energy (E𝑎). Importantly, the trend in the computed 𝜏max TON0 values aligns with experimental TON, 𝜏experimental TON validating the model's accuracy. For instance, [Cp∗Ir(κ2-N,O)NO3] is identified by MaxKinEff as a standout performer, with the normalized maximum computed TON, 𝜏max TON0 resembling the experimental TON, 𝜏experimental TON = 2000.