The Journal of Physical Chemistry A最新文献

{"title":"Theoretical Studies on the Competing Mechanism and Origin of Diastereoselectivity of NHC-Catalyzed Intramolecular [3 + 2] Annulations of Ynals.","authors":"Chunhui Liu, Xusheng Zhang, Peilin Han, Yujiao Hou, Shixing Zhang, Suxiang Ge, Dapeng Li, Yubo Jiang, Yongyuan Li","doi":"10.1021/acs.jpca.4c08775","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08775","url":null,"abstract":"<p><p>Chiral tricyclic 6,5,5-fused rings exhibit structural diversity and possess important biological activities in the synthesis of natural products. However, predicting the possible mechanism and origin of stereoselectivity in these reactions remains a challenge. In this article, we conducted a theoretical investigation into the NHC-catalyzed intramolecular [3 + 2] annulations of ynals to generate tricyclic 6,5,5-fused rings. Our calculations revealed that NHC could nucleophilically attack the carbonyl group of the ynal reactant, leading to the formation of a Breslow intermediate via a 1,2-proton transfer. Subsequently, an intramolecular Michael addition takes place, resulting in a 6-5 bicyclic intermediate. We then compared the competitive processes involving proton transfer and the Mannich reaction. The more energetically favorable process involves an HOAc-assisted proton transfer process, followed by the Mannich reaction. To ascertain the origin of the diastereoselectivity, we performed noncovalent interaction (NCI) and atom-in-molecule (AIM) analyses. This work is useful for understanding the general principles and detailed mechanisms of the synthesis of chiral 6,5,5-fused tricyclic scaffolds with unique diastereoselectivity.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanism and Origins of Regio- and Stereoselectivities of NHC-Catalyzed Dearomative Annulation of Benzoazoles and Cinnamaldehydes from DFT","authors":"Yan Li*,&nbsp;Yanlong Kang,&nbsp;Junjie Xiao and Zhiqiang Zhang*,&nbsp;","doi":"10.1021/acs.jpca.4c0837310.1021/acs.jpca.4c08373","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08373https://doi.org/10.1021/acs.jpca.4c08373","url":null,"abstract":"<p >A theoretical study on the mechanism, regioselectivity, and enantioselectivity of NHC-catalyzed dearomatizing annulation of benzoxazoles with enals has been conducted using density functional theory calculations. Our calculated results indicate that the favored mechanism occurs through eight reaction steps: initial binding of the NHC to enals, followed by formation of the Breslow intermediate via proton transfer. Subsequent oxidation generates the α,β-unsaturated acylazolium intermediate, which can undergo Michael addition with benzoxazoles. Sequential protonation/deprotonation/cyclization produces the six-membered cyclic intermediate that undergoes catalyst elimination, leading to the final product. DABCO·H⁺ was found to play important roles in proton transfer and cyclization. Without DABCO·H⁺, the energy barrier up to 44.2 kcal/mol for step 2 is too high to be accessible. With DABCO·H⁺, the corresponding value is lowered to 18.6 kcal/mol. The energy barrier for cyclization can be lowered by 7.4 kcal/mol by using DABCO·H⁺. The Michael addition step determines both the enantioselectivity and the regioselectivity. According to NCI analysis, the enantioselectivity is controlled by the strong interactions (such as C–H···O, C–H···N, and π···π) between the α,β-unsaturated acylazolium intermediate and benzoxazoles. We also discuss the solvent and substituent effects on the enantioselectivity and the role of the NHC. The mechanistic insights obtained in the present study would help improving current reaction systems or designing new synthetic routes.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2482–2492 2482–2492"},"PeriodicalIF":2.7,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600453","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Automated Multireference Vertical Excitations for Transition-Metal Compounds","authors":"Jacob J. Wardzala,&nbsp;Daniel S. King and Laura Gagliardi*,&nbsp;","doi":"10.1021/acs.jpca.4c0859710.1021/acs.jpca.4c08597","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08597https://doi.org/10.1021/acs.jpca.4c08597","url":null,"abstract":"<p >Excited states of transition metal complexes are generally strongly correlated due to the near-degeneracy of the metal d orbitals. Consequently, electronic structure calculations of such species often necessitate multireference approaches. However, widespread use of multireference methods is hindered due to the active space selection problem, which has historically required system-specific chemical knowledge and a trial-and-error approach. Here, we address this issue with an automated method combining the approximate pair coefficient (APC) scheme for estimating orbital entropies with the discrete variational selection (DVS) approach for evaluating active space quality. We apply DVS-APC to the calculation of 67 vertical excitations in transition metal diatomics as well as to two larger complexes. We show DVS-APC generated active spaces yield NEVPT2 mean absolute errors of 0.18 eV, in line with previous accuracies obtained for organic systems, but larger than errors achieved with hand-selected active spaces (0.14 eV). If instead of using DVS we identify the best results from our trial wave functions, we find improved performance (mean absolute error of 0.1 eV) over the manually selected results. We highlight this deviation between DVS and hand selected active spaces as a possible measure of bias introduced when hand selecting active spaces. However, we find that multiconfiguration pair-density functional theory (MC-PDFT) using the tPBE and tPBE0 functionals is roughly 0.15 eV less accurate than NEVPT2 across this class of diatomic systems, potentially accounting for the decreased performance of DVS-APC, which uses MC-PDFT energies to select between active spaces. We also showcase an ability to “down-sample” the DVS-APC wave functions using natural orbital occupancies to achieve smaller minimal active spaces which retain the accuracy of the larger starting active spaces. Finally, DVS-APC and tPBE0 are proven to be effective when applied to modeling excited states in two larger transition metal complexes, suggesting that the transition metal diatomics may be a particular outstanding challenge for DVS-APC and MC-PDFT approaches.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2683–2691 2683–2691"},"PeriodicalIF":2.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Parametrization of Linear Vibronic Coupling Models for Degenerate Electronic States","authors":"Dilara Farkhutdinova,&nbsp;Severin Polonius,&nbsp;Paul Karrer,&nbsp;Sebastian Mai* and Leticia González*,&nbsp;","doi":"10.1021/acs.jpca.4c0747210.1021/acs.jpca.4c07472","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07472https://doi.org/10.1021/acs.jpca.4c07472","url":null,"abstract":"<p >Linear vibronic coupling (LVC) models have proven to be effective in describing coupled excited-state potential energy surfaces of rigid molecules. However, obtaining the LVC parameters in molecules with many degrees of freedom and a large number of, possibly (near-)degenerate, electronic states can be challenging. In this paper, we discuss how the linear intra- and interstate couplings can be computed correctly using a numerical differentiation scheme, requiring a phase correction and sufficient numerical precision in the involved electronic structure calculations. The numerical scheme is applied to three test systems with symmetry-induced state degeneracies: SO₃, [PtBr₆]^2–, and [Ru(bpy)₃]²⁺. The first two systems are employed to validate the performance of the parametrization scheme. LVC potentials for SO₃ are shown to reproduce the trigonal symmetry of the potential energy surfaces. The integration of the LVC potentials for [PtBr₆]^2– with the surface-hopping trajectory method illustrates how spurious parameters lead to erroneous trajectory behavior. In the transition metal complex [Ru(bpy)₃]²⁺, extensive nonadiabatic simulations using LVC potentials are compared to those conducted with direct on-the-fly potentials. The simulations with LVC potentials demonstrate excellent agreement with the on-the-fly results while incurring costs that are 5 orders of magnitude lower. Further, the simulations evidence that intersystem crossing in [Ru(bpy)₃]²⁺ occurs at a slightly slower rate than luminescence decay, underscoring the importance of simulating the actual experimental observable when comparing computed time constants with experimental time constants. Lastly, the initial nuclear response to excitation involves a rapid, short-lived, and small elongation of the Ru–N bonds, with no charge localization occurring on a sub-ps time scale.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2655–2666 2655–2666"},"PeriodicalIF":2.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c07472","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Parahydrogen-Induced Methylated Amino Acid Hyperpolarization and Regression-Based Hyperpolarization Enhancement Factor Prediction","authors":"Sarah Kim,&nbsp;Hye Jin Jeong,&nbsp;Sein Min,&nbsp;Heelim Chae,&nbsp;Ung H. Yoon,&nbsp;Juhee Baek,&nbsp;Jisu Kim,&nbsp;Sung K. Namgoong,&nbsp;Jean Chung and Keunhong Jeong*,&nbsp;","doi":"10.1021/acs.jpca.5c0037310.1021/acs.jpca.5c00373","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00373https://doi.org/10.1021/acs.jpca.5c00373","url":null,"abstract":"<p >Nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) are powerful analytical tools with diverse applications in research and medicine. However, the inherently poor signal-to-noise ratios induce technical limitations, which suppress their widespread use. Hyperpolarization enhances the NMR signals by inducing highly nonequilibrated population distributions among the nuclear spin states. We demonstrated real-time amino acid hyperpolarization using signal amplification by reversible exchange (SABRE). We aimed to hydrolyze hyperpolarized methyl esters to induce amino acid hyperpolarization. We successfully hyperpolarized 19 methylated amino acids via SABRE. This groundwork enabled the development of a predictive model for the hyperpolarization enhancement factors of methylated amino acids. The model accurately predicted the hyperpolarization of three synthetic methylated amino acids, paving the way for advanced bio-NMR and MRI applications requiring the immediate hyperpolarization of other amino acids. This research underlines the potential of hyperpolarization in overcoming the current limitations of NMR spectroscopy and MRI.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2692–2699 2692–2699"},"PeriodicalIF":2.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigating Carrier Dynamics Modulation in Nanoscale Multiple Quantum Wells through B+ Ion Implantation: Mechanisms and Performance Enhancement","authors":"Meng Wang,&nbsp;Rong Wang,&nbsp;Qingyu Liu,&nbsp;Nan Lin*,&nbsp;Yonggang Wang* and Sicong Liu*,&nbsp;","doi":"10.1021/acs.jpca.5c0054110.1021/acs.jpca.5c00541","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00541https://doi.org/10.1021/acs.jpca.5c00541","url":null,"abstract":"<p >This study investigates the modification of carrier dynamics in nanoscale multiple quantum wells (MQWs) through <i>B</i>⁺ ion implantation, combining experimental and theoretical approaches to provide a comprehensive understanding of the impact on ultrafast optoelectronic responses. Using femtosecond time-resolved transient absorption (TA) spectroscopy, we examine the changes in carrier dynamics in both pristine and <i>B</i>⁺-implanted In_0.25Ga_0.75As/GaAs_0.9P_0.1 MQWs. Our results reveal significant modifications in the transient absorption spectra, with ion implantation reducing the excited-state absorption cross section (σ_ES) and leading to faster carrier recovery times. To further analyze these changes, we introduce a novel cascade rate equation model that incorporates two effective relaxation times, allowing for more accurate simulations of the experimental data. The model captures the complex interactions between various carrier states and provides a deeper understanding of the ion implantation effects on carrier trapping, recombination, and recovery processes. The comparison of experimental results and theoretical simulations demonstrates that ion implantation enhances ultrafast recovery times and modulates the carrier dynamics, offering a pathway for tailoring the optoelectronic properties of semiconductor materials. This work provides both a theoretical framework and experimental evidence for the design of next-generation ultrafast photonic devices with optimized carrier dynamics.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2558–2567 2558–2567"},"PeriodicalIF":2.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Configuration Weights in Coupled-Cluster Theory","authors":"Håkon Emil Kristiansen*,&nbsp;Håkon Kvernmoen,&nbsp;Simen Kvaal and Thomas Bondo Pedersen*,&nbsp;","doi":"10.1021/acs.jpca.4c0744310.1021/acs.jpca.4c07443","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07443https://doi.org/10.1021/acs.jpca.4c07443","url":null,"abstract":"<p >We introduce a simple definition of the weight of any given Slater determinant in the coupled-cluster state, namely as the expectation value of the projection operator onto that determinant. The definition can be applied to any coupled-cluster formulation, including conventional coupled-cluster theory, perturbative coupled-cluster models, nonorthogonal orbital-optimized coupled-cluster theory, and extended coupled-cluster theory, allowing for wave function analyses on par with configuration-interaction-based wave functions. Numerical experiments show that for single-reference systems the coupled-cluster weights are in excellent agreement with those obtained from the full configuration-interaction wave function. Moreover, the well-known insensitivity of the total energy obtained from truncated coupled-cluster models to the choice of orbital basis is clearly exposed by weights computed in the <i></i><math><msub><mover><mi>T</mi><mo>^</mo></mover><mn>1</mn></msub></math>-transformed determinant basis. We demonstrate that the inseparability of the conventional linear parametrization of the bra (left state) for systems composed of noninteracting subsystems may lead to ill-behaved (negative or greater than unity) weights, an issue that can only be fully remedied by switching to extended coupled-cluster theory. The latter is corroborated by results obtained with quadratic coupled-cluster theory, which is shown numerically to yield a significant improvement.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2638–2654 2638–2654"},"PeriodicalIF":2.7,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c07443","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The “Bubblepole” (BUPO) Method for Linear-Scaling Coulomb Matrix Construction with or without Density Fitting","authors":"Frank Neese*,&nbsp;Pauline Colinet,&nbsp;Bernardo DeSouza,&nbsp;Benjamin Helmich-Paris,&nbsp;Frank Wennmohs and Ute Becker,&nbsp;","doi":"10.1021/acs.jpca.4c0741510.1021/acs.jpca.4c07415","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07415https://doi.org/10.1021/acs.jpca.4c07415","url":null,"abstract":"<p >In this work, we describe the development of a new algorithm for the computation of Coulomb-type matrices using the well-known resolution of the identity (RI) or density fitting (DF) approximation. The method is linear-scaling with respect to system size and computationally highly efficient. For small molecules, it performs almost as well as the Split-RI-J algorithm (which might be the most efficient RI-J implementation to date), while outperforming it for larger systems with about 300 or more atoms. The method achieves linear scaling through multipole approximations and a hierarchical treatment of multipoles. However, unlike in the fast multipole method (FMM), the algorithm does not use a hierarchical boxing algorithm. Rather, close-lying objects like auxiliary basis shells and basis set shell pairs are grouped together in spheres that enclose the set of objects completely, which includes a new definition of the shell-pair extent that defines a real-space radius outside of which a given shell pair can be safely assumed to be negligible. We refer to these spheres as “bubbles” and therefore refer to the algorithm as the “Bubblepole” (BUPO) algorithm, with the acronym being RI-BUPO-J. The bubbles are constructed in a way to contain a nearly constant number of objects such that a very even workload arises. The hierarchical bubble structure adapts itself to the molecular topology and geometry. For any target object (shell pair or auxiliary shell), one might envision that the bubbles “carve” out what might be referred to as a “far-field surface”. Using the default settings determined in this work, we demonstrate that the algorithm reaches submicro-Eh and even nano-Eh accuracy in the total Coulomb energy for systems as large as 700 atoms and 7000 basis functions. The largest calculations performed (the crambin protein solvated by 500 explicit water molecules in a triple-ζ basis) featured more than 2000 atoms and more than 33,000 basis functions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2618–2637 2618–2637"},"PeriodicalIF":2.7,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c07415","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Evaluating Ground State Energies of Chemical Systems with Low-Depth Quantum Circuits and High Accuracy","authors":"Shuo Sun*,&nbsp;Chandan Kumar,&nbsp;Kevin Shen,&nbsp;Elvira Shishenina and Christian B. Mendl*,&nbsp;","doi":"10.1021/acs.jpca.4c0704510.1021/acs.jpca.4c07045","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07045https://doi.org/10.1021/acs.jpca.4c07045","url":null,"abstract":"<p >Quantum computers have the potential to efficiently solve the electronic structure problem but are currently limited by noise and shallow circuits. We present an enhanced Variational Quantum Eigensolver (VQE) ansatz based on the Qubit Coupled Cluster (QCC) approach that requires optimization of only <i>n</i> parameters, where <i>n</i> is the number of Pauli string generators, rather than the typical <i>n</i> + 2<i>m</i> parameters, where <i>m</i> is the number of qubits. We evaluate the ground state energies and molecular dissociation curves of strongly correlated molecules, namely O₃ and Li₄, using active spaces of varying sizes in conjunction with our enhanced QCC ansatz, Unitary Coupled Cluster Single–Double (UCCSD) ansatz, and the classical Coupled Cluster Singles and Doubles (CCSD) method. Compared to UCCSD, our approach significantly reduces the number of parameters while maintaining high accuracy. Numerical simulations demonstrate the effectiveness of our approach, and experiments on superconducting and trapped-ion quantum computers showcase its practicality on real hardware. By eliminating the need for symmetry-restoring gates and reducing the number of parameters, our enhanced QCC ansatz enables accurate quantum chemistry calculations on near-term quantum devices for strongly correlated systems.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2379–2386 2379–2386"},"PeriodicalIF":2.7,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c07045","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT-Assisted Microkinetic Study of Transfer Hydrogenation over Homogeneous and Immobilized Cp*Ir Complexes","authors":"Ivan Mitrichev*,&nbsp;A. John Blacker,&nbsp;Michael Chapman,&nbsp;Yuji Kawakami,&nbsp;Mikhail Vasilev,&nbsp;Gert Goltz,&nbsp;Anna Podobedova,&nbsp;Antonia Borissova and Eleonora Koltsova,&nbsp;","doi":"10.1021/acs.jpca.4c0871810.1021/acs.jpca.4c08718","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08718https://doi.org/10.1021/acs.jpca.4c08718","url":null,"abstract":"<p >DFT calculations were done to investigate the kinetic mechanism of benzaldehyde transfer hydrogenation using [Cp*IrCl₂]₂ complexes in isopropyl alcohol in the presence of potassium <i>tert-</i>butoxide. Predicted energy barriers provide evidence that the inner-sphere (IS) mechanism (effective barrier 53.0 kJ/mol) is favored over the outer-sphere (OS) and Meerwein–Pondorf–Verley (MPV) mechanisms. Reaction kinetics was studied using both homogeneous and immobilized Cp*Ir complexes as catalysts. A mathematical model was developed to simulate the transfer hydrogenation of benzaldehyde on these catalysts, accounting for possible mass transfer limitations for the immobilized catalyst. A microkinetic model was constructed using both our density functional theory calculations and fitting of the kinetic parameters of catalyst activation and deactivation reactions. The simulation results predict that only about a quarter of Ir immobilized complexes are involved in the reaction, and this is the main reason for the observed higher activity of the homogeneous catalyst. The activity of the immobilized catalyst was found to be related to the hydride species concentration, which is a function of the base concentration. The results suggest that the amount of base has a drastic effect on the immobilized catalyst activity.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 10","pages":"2548–2557 2548–2557"},"PeriodicalIF":2.7,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600252","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}