{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,5]],"date-time":"2026-09-05T01:49:57Z","timestamp":1788572997112,"version":"build-2803163510"},"reference-count":47,"publisher":"MDPI AG","issue":"22","license":[{"start":{"date-parts":[[2023,11,9]],"date-time":"2023-11-09T00:00:00Z","timestamp":1699488000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Ministerio de Ciencia e Innovaci\u00f3n (MICINN) of Spain","award":["PID2021-125207NB-C31"],"award-info":[{"award-number":["PID2021-125207NB-C31"]}]},{"name":"Ministerio de Ciencia e Innovaci\u00f3n (MICINN) of Spain","award":["PID2021-125207NB-C32"],"award-info":[{"award-number":["PID2021-125207NB-C32"]}]},{"name":"Ministerio de Ciencia e Innovaci\u00f3n (MICINN) of Spain","award":["PID2019-110091GB-I00"],"award-info":[{"award-number":["PID2019-110091GB-I00"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>In the search for common bonding patterns in pure and mixed clusters of beryllium and magnesium derivatives, the most stable dimers and trimers involving BeX2 and MgX2 (X = H, F, Cl) have been studied in the gas phase using B3LYP and M06-2X DFT methods and the G4 ab initio composite procedure. To obtain some insight into their structure, stability, and bonding characteristics, we have used two different energy decomposition formalisms, namely MBIE and LMO-EDA, in parallel with the analysis of the electron density with the help of QTAIM, ELF, NCIPLOT, and AdNDP approaches. Some interesting differences are already observed in the dimers, where the stability sequence observed for the hydrides differs entirely from that of the fluorides and chlorides. Trimers also show some peculiarities associated with the presence of compact trigonal cyclic structures that compete in stability with the more conventional hexagonal and linear forms. As observed for dimers, the stability of the trimers changes significantly from hydrides to fluorides or chlorides. Although some of these clusters were previously explored in the literature, the novelty of this work is to provide a holistic approach to the entire series of compounds by using chemical bonding tools, allowing us to understand the stability trends in detail and providing insights for a significant number of new, unexplored structures.<\/jats:p>","DOI":"10.3390\/molecules28227507","type":"journal-article","created":{"date-parts":[[2023,11,9]],"date-time":"2023-11-09T10:19:27Z","timestamp":1699525167000},"page":"7507","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["A Holistic View of the Interactions between Electron-Deficient Systems: Clustering of Beryllium and Magnesium Hydrides and Halides"],"prefix":"10.3390","volume":"28","author":[{"given":"Otilia","family":"M\u00f3","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica, M\u00f3dulo 13, Facultad de Ciencias, and Institute of Advanced Chemical Sciences (IAdChem), Universidad Aut\u00f3noma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049 Madrid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9499-0900","authenticated-orcid":false,"given":"M. Merced","family":"Montero-Campillo","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, M\u00f3dulo 13, Facultad de Ciencias, and Institute of Advanced Chemical Sciences (IAdChem), Universidad Aut\u00f3noma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049 Madrid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0854-585X","authenticated-orcid":false,"given":"Manuel","family":"Y\u00e1\u00f1ez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, M\u00f3dulo 13, Facultad de Ciencias, and Institute of Advanced Chemical Sciences (IAdChem), Universidad Aut\u00f3noma de Madrid, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049 Madrid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6876-6211","authenticated-orcid":false,"given":"Ibon","family":"Alkorta","sequence":"additional","affiliation":[{"name":"Instituto de Qu\u00edmica M\u00e9dica, IQM-CSIC, Juan de la Cierva, 3, 28006 Madrid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jos\u00e9","family":"Elguero","sequence":"additional","affiliation":[{"name":"Instituto de Qu\u00edmica M\u00e9dica, IQM-CSIC, Juan de la Cierva, 3, 28006 Madrid, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,11,9]]},"reference":[{"key":"ref_1","unstructured":"Muetterties, E.L. (1975). Boron Hydride Chemistry, Academic Press."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1016\/0166-1280(89)87037-X","article-title":"Bond orders in 3-center bonds\u2014An analytical investigation into the electronic-structure of diborane and the 3-center 4-electron bonds of hypervalent sulfur","volume":"55","author":"Mayer","year":"1989","journal-title":"J. Mol. Struct. Theochem"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"393","DOI":"10.1016\/0009-2614(89)87506-2","article-title":"Infrared-spectra of the unknown dialane (Al2H6) and recently observed digallane (Ga2H6) molecules","volume":"159","author":"Liang","year":"1989","journal-title":"Chem. Phys. Lett."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2806","DOI":"10.1021\/j100370a016","article-title":"Ab initio study on dialane(6) and digallane(6)","volume":"94","author":"Lammertsma","year":"1990","journal-title":"J. Phys. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2049","DOI":"10.1126\/science.1082456","article-title":"The infrared spectrum of Al2H6 in solid hydrogen","volume":"299","author":"Andrews","year":"2003","journal-title":"Science"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2549","DOI":"10.1007\/s00894-013-1805-0","article-title":"Natural bond orbital, nuclear magnetic resonance analysis and hybrid-density functional theory study of sigma-aromaticity in Al2F6, Al2Cl6, Al2Br6 and Al2I6","volume":"19","author":"Yahyaei","year":"2013","journal-title":"J. Mol. Model."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"5860","DOI":"10.1021\/acs.jpca.3c02747","article-title":"Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides","volume":"127","author":"Alkorta","year":"2023","journal-title":"J. Phys. Chem. A"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"348","DOI":"10.1007\/BF00528570","article-title":"Ab initio Calculations on Small Hydrides Including Electron Correlation","volume":"17","author":"Ahlrichs","year":"1970","journal-title":"Theoret. Chim. Acta"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"134","DOI":"10.1007\/BF00735205","article-title":"An ab initio calculation of the structure and stability of the complex hydrides MgBeH- and Mg2H-","volume":"24","author":"Kirillov","year":"1983","journal-title":"J. Struct. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"9627","DOI":"10.1021\/jp051978r","article-title":"Theoretical study on the small clusters of LiH, NaH, BeH2, and MgH2","volume":"109","author":"Chen","year":"2005","journal-title":"J. Phys. Chem. A"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"371","DOI":"10.1016\/j.comptc.2010.10.050","article-title":"Quantum chemical studies on beryllium hydride oligomers","volume":"963","author":"Lingam","year":"2011","journal-title":"Comput. Theor. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"201","DOI":"10.1021\/jp1100544","article-title":"Dihydrogen Bonding vs. Metal-\u03c3 Interaction in Complexes between H2 and Metal Hydride","volume":"115","author":"Alkorta","year":"2011","journal-title":"J. Phys. Chem. A"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"124102","DOI":"10.1063\/5.0087359","article-title":"Efficient and automated quantum chemical calculation of rovibrational nonresonant Raman spectra","volume":"156","author":"Erfort","year":"2022","journal-title":"J. Chem. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"244104","DOI":"10.1063\/5.0011832","article-title":"Toward a fully automated calculation of rovibrational infrared intensities for semi-rigid polyatomic molecules","volume":"152","author":"Erfort","year":"2020","journal-title":"J. Chem. Phys."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"11511","DOI":"10.1021\/jp046410h","article-title":"Infrared spectra of magnesium hydride molecules, complexes, and solid magnesium dihydride","volume":"108","author":"Wang","year":"2004","journal-title":"J. Phys. Chem. A"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"11547","DOI":"10.1021\/jp035971q","article-title":"Ab initio studies of static dipole polarizability of the polymeric beryllium hydride chain","volume":"107","author":"Abdurahman","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"610","DOI":"10.1021\/ic048464b","article-title":"One-dimensional BeH2 polymers: Infrared spectra and theoretical calculations","volume":"44","author":"Wang","year":"2005","journal-title":"Inorg. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1016\/0166-1280(92)87139-Q","article-title":"Ab initio study on the Be2F4, Mg2F4 dimers, on the mixed dimers BeMgF4 and LiNaF2 and on the Li2BeF4, LiBCl4 and LiAlCl4 ion-pairs","volume":"96","author":"Ramondo","year":"1992","journal-title":"J. Mol. Struct. Theochem"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"5224","DOI":"10.1063\/1.459667","article-title":"On the structure of the alkaline earth dihalides dimers","volume":"93","author":"Gigli","year":"1990","journal-title":"J. Chem. Phys."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"855","DOI":"10.1016\/S1386-1425(98)00009-2","article-title":"Quantum chemical studies of molecular difluorides and dichlorides of beryllium and magnesium","volume":"54","author":"Ystenes","year":"1998","journal-title":"Spectrochim. Acta A Mol. Biomol. Spectrosc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"9062","DOI":"10.1021\/j100022a018","article-title":"Molecular-structures and force-fields of monomeric and dimeric magnesium dichloride from electron-diffraction and quantum-chemical calculations","volume":"99","author":"Molnar","year":"1995","journal-title":"J. Phys. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"175","DOI":"10.1016\/S0022-2860(96)09333-7","article-title":"Structural investigation of molecules in the vapour over beryllium dichloride using electron diffraction and mass spectrometric data","volume":"384","author":"Girichev","year":"1996","journal-title":"J. Mol. Struct."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"381","DOI":"10.1515\/znb-2022-0015","article-title":"Hydrolysis and oxidation products of phosphine adducts to beryllium chloride","volume":"77","author":"Buchner","year":"2022","journal-title":"Z. Naturforsch. B J. Chem. Sci."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"7557","DOI":"10.1063\/1.469087","article-title":"An ab-initio investigation of structure and energetics of clusters MgnCl2n","volume":"102","author":"Eichkorn","year":"1995","journal-title":"J. Chem. Phys."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3729","DOI":"10.1080\/00268976.2015.1059508","article-title":"Structure, electronic properties and vibrational spectra of (MgF2)n clusters through a combination of genetic algorithm and DFT-based approach","volume":"113","author":"Neogi","year":"2015","journal-title":"Mol. Phys."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"3989","DOI":"10.1021\/jp030464u","article-title":"Structural characteristics of small magnesium dichloride clusters: A systematic theoretical study","volume":"108","author":"Luhtanen","year":"2004","journal-title":"J. Phys. Chem. B"},{"key":"ref_27","unstructured":"Values calculated at the M06-2X\/aug-cc-pVTZ level of theory (this work)."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1083","DOI":"10.1016\/0040-4020(68)88057-3","article-title":"Application of pople-santry-segal cndo method to cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane","volume":"24","author":"Wiberg","year":"1968","journal-title":"Tetrahedron"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"084108","DOI":"10.1063\/1.2436888","article-title":"Gaussian-4 theory","volume":"126","author":"Curtiss","year":"2007","journal-title":"J. Chem. Phys."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1456","DOI":"10.1002\/jcc.21759","article-title":"Effect of the Damping Function in Dispersion Corrected Density Functional Theory","volume":"32","author":"Grimme","year":"2011","journal-title":"J. Comp. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"5105","DOI":"10.1021\/acs.chemrev.5b00533","article-title":"Dispersion-Corrected Mean-Field Electronic Structure Methods","volume":"116","author":"Grimme","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"12590","DOI":"10.1021\/jp408166m","article-title":"Performance of M06, M06-2X, and M06-HF Density Functionals for Conformationally Flexible Anionic Clusters: M06 Functionals Perform Better than B3LYP for a Model System with Dispersion and Ionic Hydrogen-Bonding Interactions","volume":"117","author":"Walker","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"11977","DOI":"10.1021\/acs.joc.5b01814","article-title":"Importance of the Electron Correlation and Dispersion Corrections in Calculations Involving Enamines, Hemiaminals, and Aminals. Comparison of B3LYP, M06-2X, MP2, and CCSD Results with Experimental Data","volume":"80","author":"Cameros","year":"2015","journal-title":"J. Org. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"970","DOI":"10.1016\/j.molliq.2016.05.037","article-title":"Assessment of the performance of commonly used DFT functionals vs. MP2 in the study of IL-Water, IL-Ethanol and IL-(H2O)(3) clusters","volume":"220","author":"Ayala","year":"2016","journal-title":"J. Mol. Liq."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"24134","DOI":"10.1039\/C9RA03524A","article-title":"Exhaustive exploration of the conformational landscape of mono- and disubstituted five-membered rings by DFT and MP2 calculations","volume":"9","author":"Stortz","year":"2019","journal-title":"RSC Adv."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"4544","DOI":"10.1063\/1.1673986","article-title":"Water molecule interactions","volume":"53","author":"Hankins","year":"1970","journal-title":"J. Chem. Phys."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"7523","DOI":"10.1063\/1.466846","article-title":"Ab-initio studies of cyclic water clusters (H2O)n, n=1-6. 2. Analysis of many-body interactions","volume":"100","author":"Xantheas","year":"1994","journal-title":"J. Chem. Phys."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"2531","DOI":"10.1021\/jp500405s","article-title":"Energy Decomposition Scheme Based on the Generalized Kohn-Sham Scheme","volume":"118","author":"Su","year":"2014","journal-title":"J. Phys. Chem. A"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"1347","DOI":"10.1002\/jcc.540141112","article-title":"General atomic and molecular electronic-structure system","volume":"14","author":"Schmidt","year":"1993","journal-title":"J. Comp. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Bader, R.F.W. (1990). Atoms in Molecules. A Quantum Theory, Clarendon Press.","DOI":"10.1093\/oso\/9780198551683.001.0001"},{"key":"ref_41","unstructured":"Keith, T.A. (2023, January 01). Available online: aim.tkgristmill.com."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1736","DOI":"10.1063\/1.449360","article-title":"Natural localized molecular-orbitals","volume":"83","author":"Reed","year":"1985","journal-title":"J. Chem. Phys."},{"key":"ref_43","unstructured":"Glendening, E.D., Badenhoop, J.K., Reed, A.E., Carpenter, J.E., Bohmann, J.A., Morales, C.M., and Weinhold, F. (2004). NBO 5.G, Theoretical Chemistry Institute, University of Wisconsin."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"9590","DOI":"10.1039\/C9CP00379G","article-title":"Chemical bonding analysis of excited states using the adaptive natural density partitioning method","volume":"21","author":"Tkachenko","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"4150","DOI":"10.1021\/acs.jctc.0c00063","article-title":"NCIPLOT4: Fast, robust and quantitative analysis of non-covalent interactions","volume":"16","author":"Boto","year":"2020","journal-title":"J. Chem. Theory Comp."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"1809","DOI":"10.1002\/anie.199718081","article-title":"ELF: The electron localization function","volume":"36","author":"Savin","year":"1997","journal-title":"Angew. Chem. Int. Edit."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"e202203791","DOI":"10.1002\/chem.202203791","article-title":"Intermolecular Covalent Interactions: Nature and Directionality","volume":"29","author":"Santos","year":"2023","journal-title":"Chem. Eur. J."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/22\/7507\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T21:20:18Z","timestamp":1760131218000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/22\/7507"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,11,9]]},"references-count":47,"journal-issue":{"issue":"22","published-online":{"date-parts":[[2023,11]]}},"alternative-id":["molecules28227507"],"URL":"https:\/\/doi.org\/10.3390\/molecules28227507","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,11,9]]}}}