Prof. Jose M. Mercero

@article{Berti2025,

title = {Ultra-Low Atomic Diffusion Barrier on Two-Dimensional Materials: The Case of Pt on Epitaxial Graphene},

author = {Andrea Berti and Ramón M. Bergua and Jose M. Mercero and Deborah Perco and Paolo Lacovig and Silvano Lizzit and Elisa Jimenez-Izal and Alessandro Baraldi},

doi = {10.1021/acsnano.5c13305},

issn = {1936-086X},

year  = {2025},

date = {2025-10-14},

urldate = {2025-10-14},

journal = {ACS Nano},

volume = {19},

number = {40},

pages = {35921--35932},

publisher = {American Chemical Society (ACS)},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2025,

title = {Enhancing the computational efficiency of the DoNOF program through a new orbital sorting scheme},

author = {Élodie Boutou and Juan Felipe Huan Lew-Yee and Jose M. Mercero and Mario Piris},

doi = {10.1016/bs.aiq.2025.03.001},

isbn = {9780443343575},

year  = {2025},

date = {2025-02-04},

urldate = {2025-02-04},

booktitle = {Advances in Quantum Chemistry},

journal = {Advances in Quantum Chemistry},

volume = {91},

pages = {169--189},

publisher = {Elsevier},

abstract = {This work presents a novel approach to distribute orbitals into subspaces within electron-pairing-based natural orbital functionals (NOFs). This approach modifies the coupling between weakly and strongly occupied orbitals by applying an alternating orbital sorting strategy. In contrast to the previous orbital sorting that enforced electron pairing within subspaces of contiguous orbitals, the new approach provides greater flexibility, enabling a calculation scheme where the size of the subspaces can be gradually expanded. As a consequence, one can start using subspaces of only one weakly occupied orbital (perfect pairing) and progressively enlarge their size by incorporating more weakly occupied orbitals (extended pairing) up to the maximum size allowed by the basis set. In this way, the alternate orbital sorting allows solving first a simpler problem with small subspaces and leverage its orbital solution for the more intensive problem with larger subspaces, thereby reducing the overall computational cost and improving convergence, as we observed in the DoNOF program. The efficiency provided by the new sorting approach has been validated through benchmark calculations in H2O, H2O2, and NH3. In particular, we compared three strategies: (i) solving directly the calculation with the largest subspaces (one-shot strategy), as was usually done before this work, (ii) starting with perfect pairing and stepwise increasing the number of orbitals in the subspaces one by one until reaching the maximum size (incremental strategy), and (iii) starting with perfect pairing and transitioning directly to the maximum subspace size (two-step strategy). Our results show that the two-step approach emerges as the most effective strategy, achieving the lowest computational cost while maintaining high accuracy. These results confirm that the alternating orbital sorting scheme provides a robust and scalable framework for improving NOF calculations and could be particularly advantageous for extending these methods to larger and strongly correlated systems.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Grande‐Aztazi2024,

title = {The Aromaticity of Osmapentalenes Derivatives – An Analysis Based on Electron‐Delocalization Indices},

author = {Rafael Grande‐Aztazi and Eduard Matito and Jesus M. Ugalde and Jose M. Mercero},

doi = {10.1002/cphc.202400713},

issn = {1439-7641},

year  = {2025},

date = {2025-02-01},

journal = {ChemPhysChem},

volume = {26},

number = {3},

publisher = {Wiley},

abstract = {<jats:title>Abstract</jats:title><jats:p>A systematic investigation of the aromatic features of the electronic structures of a family of recently synthesized osmapentalene derivatives has been carried by means of indices derived from the calculated one‐electron density matrix of the corresponding geometry optimized compounds, and complemented by the analysis of the valence molecular orbitals and the delocalized bonding units emerging from the adaptive natural density partitioning method. The calculated delocalization indices between consecutive atom pairs, and normalized multicenter indices are very suggestive of the aromatic character of the equatorial fused carbon rings (except triangular ones) for all the members of the family. Since the electron‐delocalization based indices allow precise quantification of the aromaticity, differences of the aromatic character among the various members have also been highlighted, and have been found to be consistent with the magnetic based criteria indices reported earlier. Finally, the valence molecular orbitals along with the delocalized bonding units of the adaptive natural density partitioning indicate that the aromaticity of these compounds is sustained by either 10 or 14 <jats:italic>π</jats:italic> electrons, which satisfy the Hückel aromatic electron counting rule.</jats:p>},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Ugartemendia2024c,

title = {Boosting synergistic effects between PtGe nanoalloys and 2D materials for PEMFC applications},

author = {Andoni Ugartemendia and Ramón M. Bergua and Jose M. Mercero and Elisa Jimenez-Izal},

doi = {10.1016/j.ijhydene.2024.09.279},

issn = {0360-3199},

year  = {2024},

date = {2024-11-01},

urldate = {2024-11-01},

journal = {International Journal of Hydrogen Energy},

volume = {89},

pages = {233--253},

publisher = {Elsevier BV},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Ugartemendia2024d,

title = {Doping Efects on Ethane/Ethylene Dehydrogenation Catalyzed by Pt_{2}X Nanoclusters},

author = {Andoni Ugartemendia and José M. Mercero and Elisa Jimenez‐Izal and Abel de Cózar},

doi = {10.1002/cphc.202400095},

issn = {1439-7641},

year  = {2024},

date = {2024-06-17},

urldate = {2024-06-17},

journal = {ChemPhysChem},

volume = {25},

number = {12},

publisher = {Wiley},

abstract = {<jats:title>Abstract</jats:title><jats:p>The catalytic dehydrogenation of light alkanes is key to transform low‐cost hydrocarbons to high value‐added chemicals. Although Pt is extremely efficient at catalyzing this reaction, it suffers from coke formation that deactivates the catalyst. Dopants such as Sn are widely used to increase the stability and lifetime of Pt. In this work, the dehydrogenation reaction of ethane catalyzed by Pt<jats:sub>3</jats:sub> and Pt<jats:sub>2</jats:sub>X (X=Si, Ge, Sn, P and Al) nanocatalysts has been studied computationally by means of density functional calculations. Our results show how the presence of dopants in the nanocluster structure affects its electronic properties and catalytic activity. Exploration of the potential energy surfaces show that non–doped catalyst Pt<jats:sub>3</jats:sub> present low selectivity towards ethylene formation, where acetylene resulting from double dehydrogenation reaction will be obtained as a side product (in agreement with the experimental evidence). On the contrary, the inclusion of Si, Ge, Sn, P or Al as dopant agents implies a selectivity enhancement, where acetylene formation is not energetically favoured. These results demonstrate the effectiveness of such dopant elements for the design of Pt–based catalysts on ethane dehydrogenation.</jats:p>},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Escayola2024,

title = {Unveiling the quantum secrets of triel metal triangles: a tale of stability, aromaticity, and relativistic effects},

author = {Sílvia Escayola and Elisa Jimenez-Izal and Eduard Matito and Jesus M. Ugalde and Rafael Grande-Aztatzi and Jose M. Mercero},

doi = {10.1039/d4cp00484a},

issn = {1463-9084},

year  = {2024},

date = {2024-04-24},

journal = {Phys. Chem. Chem. Phys.},

volume = {26},

number = {16},

pages = {12619--12627},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {MCSCF natural orbitals and the corresponding number of (α/β) electrons and its aromaticity (Hückel), Baird odd-symmetry anti-aromaticity and Baird odd-symmetry aromaticity after applying Mandados rules.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Ugartemendia2024,

title = {Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**},

author = {Andoni Ugartemendia and Jose M. Mercero and Abel de Cózar and Marko M. Melander and Jaakko Akola and Elisa Jimenez‐Izal},

doi = {10.1002/cctc.202301137},

issn = {1867-3899},

year  = {2024},

date = {2024-02-08},

urldate = {2024-02-08},

journal = {ChemCatChem},

volume = {16},

number = {3},

publisher = {Wiley},

abstract = {<jats:title>Abstract</jats:title><jats:p>Control of CO emissions raises serious environmental concerns in the current chemical industry, as well as in nascent technologies based on hydrogen such as electrolyzers and fuel cells. As for now, Pt remains one of the state‐of‐the‐art catalysts for the CO oxidation reaction, but unfortunately, it suffers from CO self‐poisoning. Recently, Pt−Ge alloys were proposed to be an excellent alternative to reduce CO poisoning. This work investigates the impact of Ge content on the CO oxidation kinetics of Pt<jats:sub>4</jats:sub>Ge<jats:sub>n</jats:sub> subnanoclusters supported on MgO. A Ge concentration dependence of the reaction kinetics is found due to a strong synergy between Pt and Ge. Pt−Ge nanoalloys act as a bifunctional catalyst by displaying dual adsorption sites; i. e., CO is adsorbed on Pt whereas oxygen binds to Ge, forming an alternative oxygen source GeO<jats:sub>x</jats:sub>. Besides, Ge alloying modifies the electronic structure of Pt (ligand effects) and reduces the affinity to CO. In this way, the competition between CO and O<jats:sub>2</jats:sub> adsorption and the overbinding of CO is alleviated, achieving a CO poisoning‐free kinetic regime. Our calculations suggest that Pt<jats:sub>4</jats:sub>Ge<jats:sub>3</jats:sub> is the optimal catalyst, evidencing that alloying composition is a parameter of extreme importance in nanocatalyst design. The work relies on global optimization search techniques to determine the accessibility of multiple structures at different conditions, mechanistic studies and microkinetic modeling.</jats:p>},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Aduriz-Arrizabalaga2023,

title = {Rules governing metal coordination in Aβ–Zn(ii) complex models from quantum mechanical calculations},

author = {Julen Aduriz-Arrizabalaga and Jose M. Mercero and David De Sancho and Xabier Lopez},

doi = {10.1039/d3cp02070c},

issn = {1463-9084},

year  = {2023},

date = {2023-10-18},

journal = {Phys. Chem. Chem. Phys.},

volume = {25},

number = {40},

pages = {27618--27627},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {QM cluster calculations explain the tendency found in the PDB of Aβ–Zn(ii) complexes to be arranged in tetrahedral coordination shells with Zn(ii) interacting with mixed His and Glu/Asp residues.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Mercero2023,

title = {Natural orbital functional theory studies of all-metal aromaticity: The Al3 anion},

author = {Jose M. Mercero and Rafael Grande-Aztatzi and Jesus M. Ugalde and Mario Piris},

doi = {10.1016/bs.aiq.2023.02.006},

isbn = {9780443186639},

year  = {2023},

date = {2023-10-01},

urldate = {2023-10-01},

booktitle = {Advances in Quantum Chemistry},

journal = {Adv. Quantum Chem.},

volume = {88},

pages = {229-248},

publisher = {Elsevier},

series = {Advances in Quantum Chemistry},

abstract = {In this chapter, the Al3− triangle singlet, triplet, and quintet states have been characterized. This study is developed from the point of view of an approximate natural orbital functional (NOF), for which the energy of the ground state is given as a functional of the natural orbitals and their occupation numbers. Specifically, the recently proposed global NOF (Piris, 2021 in Ref. 22) is used to address the electron delocalization features of an all-metal aromatic compound, the Al

 ring-like cluster anion in its lowest-lying electronic states of different spin. Its aromaticity is characterized by the multicenter index (MCI) and its π-fraction (MCIπ) by comparing them with paradigmatic cases of aromatic and antiaromatic organic compounds, namely benzene and cyclobutadiene. Our results have been compared with the highly accurate multiconfigurational self-consistent field (MCSCF) method complemented with quasidegenerate perturbation theory (MCQDPT) perturbative corrections, and with the available experimental data. GNOF was found to be able to give a satisfactorily quantitative agreement with the MCSCF/MCQDPT results and experiment, and also describing both the π- and σ-aromaticity of the 

, and the 3B2 states.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Villaescusa2023,

title = {Rigidified Bis(sulfonyl)ethylenes as Effective Michael Acceptors for Asymmetric Catalysis: Application to the Enantioselective Synthesis of Quaternary Hydantoins},

author = {Leire Villaescusa and Iker Hernández and Laura Azcune and Ainhoa Rudi and José M. Mercero and Aitor Landa and Mikel Oiarbide and Claudio Palomo},

doi = {10.1021/acs.joc.2c02403},

issn = {1520-6904},

year  = {2023},

date = {2023-01-20},

journal = {J. Org. Chem.},

volume = {88},

number = {2},

pages = {972--987},

publisher = {American Chemical Society (ACS)},

keywords = {},

pubstate = {published},

tppubtype = {article}

}