{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,11]],"date-time":"2026-10-11T13:15:37Z","timestamp":1791724537111,"version":"4.3.4"},"reference-count":77,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2020,7,24]],"date-time":"2020-07-24T00:00:00Z","timestamp":1595548800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Intense electric fields applied on H-bonded systems are able to induce molecular dissociations, proton transfers, and complex chemical reactions. Nevertheless, the effects induced in heterogeneous molecular systems such as methanol-water mixtures are still elusive. Here we report on a series of state-of-the-art ab initio molecular dynamics simulations of liquid methanol-water mixtures at different molar ratios exposed to static electric fields. If, on the one hand, the presence of water increases the proton conductivity of methanol-water mixtures, on the other, it hinders the typical enhancement of the chemical reactivity induced by electric fields. In particular, a sudden increase of the protonic conductivity is recorded when the amount of water exceeds that of methanol in the mixtures, suggesting that important structural changes of the H-bond network occur. By contrast, the field-induced multifaceted chemistry leading to the synthesis of e.g., hydrogen, dimethyl ether, formaldehyde, and methane observed in neat methanol, in 75:25, and equimolar methanol-water mixtures, completely disappears in samples containing an excess of water and in pure water. The presence of water strongly inhibits the chemical reactivity of methanol.<\/jats:p>","DOI":"10.3390\/molecules25153371","type":"journal-article","created":{"date-parts":[[2020,7,24]],"date-time":"2020-07-24T11:16:35Z","timestamp":1595589395000},"page":"3371","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["Ab Initio Molecular Dynamics Study of Methanol-Water Mixtures under External Electric Fields"],"prefix":"10.3390","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1895-2950","authenticated-orcid":false,"given":"Giuseppe","family":"Cassone","sequence":"first","affiliation":[{"name":"CNR-IPCF, Viale F. Stagno d\u2019Alcontres 37, 98158 Messina, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Adriano","family":"Sofia","sequence":"additional","affiliation":[{"name":"Dipartimento di Matematica \u201cG. Peano\u201d, Universit\u00e0 degli Studi di Torino, Via Carlo Alberto 10, 10123 Torino, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiri","family":"Sponer","sequence":"additional","affiliation":[{"name":"Institute of Biophysics of the Czech Academy of Sciences, Kr\u00e1lovopolsk\u00e1 135, 61265 Brno, Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"A. Marco","family":"Saitta","sequence":"additional","affiliation":[{"name":"Sorbonne Universit\u00e9, Msu\u00e9um National d\u2019Histoire Naturelle, UMR CNRS 7590, IMPMC, F-075005 Paris, France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5970-9001","authenticated-orcid":false,"given":"Franz","family":"Saija","sequence":"additional","affiliation":[{"name":"CNR-IPCF, Viale F. Stagno d\u2019Alcontres 37, 98158 Messina, Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,7,24]]},"reference":[{"key":"ref_1","unstructured":"Franks, F. (1973). Water-A Comprehensive Treatise, Plenum. Chapter 5."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1980","DOI":"10.1063\/1.440541","article-title":"Effects of solute\u2013solvent attractive forces on hydrophobic correlations","volume":"73","author":"Pratt","year":"1980","journal-title":"J. Chem. Phys."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"214309","DOI":"10.1063\/1.4921380","article-title":"CH3OH (H2O)n [n = 1\u20134] clusters in external electric fields","volume":"142","author":"Gurav","year":"2015","journal-title":"J. Chem. Phys."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"429","DOI":"10.1038\/416829a","article-title":"Molecular segregation observed in a concentrated alcohol\u2013water solution","volume":"416","author":"Dixit","year":"2002","journal-title":"Nature"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"157401","DOI":"10.1103\/PhysRevLett.91.157401","article-title":"Molecular Structure of Alcohol-Water Mixtures","volume":"91","author":"Guo","year":"2003","journal-title":"Phys. Rev. Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"6456","DOI":"10.1063\/1.1789951","article-title":"Methanol-water solutions: A bi-percolating liquid mixture","volume":"121","author":"Dougan","year":"2004","journal-title":"J. Chem. Phys."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"7884","DOI":"10.1021\/acs.jpcb.8b03543","article-title":"Temperature-Dependent Segregation in Alcohol-Water Binary Mixtures Is Driven by Water Clustering","volume":"122","author":"Lenton","year":"2018","journal-title":"J. Phys. Chem. B"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"064506","DOI":"10.1063\/1.4941414","article-title":"Dynamical properties of water-methanol solutions","volume":"144","author":"Mallamace","year":"2016","journal-title":"J. Chem. Phys."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"4388","DOI":"10.1021\/jp4091602","article-title":"Local Structures of Methanol-Water Binary Solutions Studied by Soft X-ray Absorption Spectroscopy","volume":"118","author":"Nakasaga","year":"2014","journal-title":"J. Phys. Chem. B"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"586","DOI":"10.1016\/j.molliq.2015.06.045","article-title":"Microscopic structure of methanol\u2013water mixtures: Synchrotron X-ray diffraction experiments and molecular dynamics simulations over the entire composition range","volume":"209","author":"Pusztai","year":"2015","journal-title":"J. Mol. Liq."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"2924","DOI":"10.1063\/1.480865","article-title":"Hydrophobic hydration and molecular association in methanol-water mixtures studied by microwave dielectric analysis","volume":"112","author":"Sato","year":"2000","journal-title":"J. Chem. Phys."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"H549","DOI":"10.1149\/2.0491809jes","article-title":"Reorientational Relaxation and Hydrogen Bonding in Mixtures of Water and Methanol","volume":"165","author":"Negro","year":"2018","journal-title":"J. Electrochem. Soc."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"5156","DOI":"10.1063\/1.458652","article-title":"Molecular-dynamics simulation of aqueous mixtures: Methanol, acetone, and ammonia","volume":"93","author":"Ferrario","year":"1990","journal-title":"J. Chem. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2626","DOI":"10.1063\/1.463051","article-title":"Structure and thermodynamic properties of water-methanol mixtures: Role of the water-water interaction","volume":"97","author":"Tanaka","year":"1998","journal-title":"J. Chem. Phys."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"5910","DOI":"10.1021\/jp970673c","article-title":"Three-Dimensional Structure in Water-Methanol Mixtures","volume":"101","author":"Laaksonen","year":"1997","journal-title":"J. Phys. Chem. A"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"7308","DOI":"10.1063\/1.1607918","article-title":"Dynamic properties of water-alcohol mixtures studied by computer simulation","volume":"119","author":"Wensink","year":"2003","journal-title":"J. Chem. Phys."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"5004","DOI":"10.1039\/b808326f","article-title":"Water-methanol mixtures: Topology of hydrogen bonded network","volume":"10","author":"Bako","year":"2008","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_18","first-page":"90","article-title":"Effect of hydrogen bonding on self-diffusion in methanol\/water liquid mixtures: A molecular dynamics simulation study","volume":"203","author":"Zhang","year":"2015","journal-title":"J. Mol. Phys."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"43602","DOI":"10.5488\/CMP.18.43602","article-title":"On the composition dependence of thermodynamic, dynamic and dielectric properties of water-methanol model mixtures. Molecular dynamics simulation results","volume":"18","author":"Dominguez","year":"2015","journal-title":"Condens. Matter. Phys."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"8593","DOI":"10.1021\/acs.jpcb.5b03344","article-title":"Water-Methanol Mixtures: Simulations of Mixing Properties over the Entire Range of Mole Fractions","volume":"119","author":"Soetens","year":"2015","journal-title":"J. Phys. Chem. B"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"16765","DOI":"10.1039\/C7CP02919E","article-title":"Methanol\u2013methanol and methanol-water systems: The intermolecular interactions controlling the transition from small clusters to the liquid phase","volume":"19","author":"Alberti","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_22","first-page":"112581","article-title":"Parametrizing hydrogen bond interactions in dissipative particle dynamics simulations: The case of water, methanol and their binary mixtures","volume":"302","author":"Kacar","year":"2020","journal-title":"J. Mol. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"290","DOI":"10.1016\/S0009-2614(00)01387-7","article-title":"Hydration of methanol in water. A DFT-based molecular dynamics study","volume":"333","author":"Meijer","year":"2001","journal-title":"Chem. Phys. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"10728","DOI":"10.1021\/jp9044447","article-title":"Are There Immobilized Water Molecules around Hydrophobic Groups? Aqueous Solvation of Methanol from First Principles","volume":"113","author":"Silvestrelli","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"134703","DOI":"10.1063\/1.4896233","article-title":"Hydrogen bonded structure, polarity, molecular motion and frequency fluctuations at liquid-vapor interface of a water-methanol mixture: An ab initio molecular dynamics study","volume":"141","author":"Chouduri","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"3712","DOI":"10.1021\/jp0554036","article-title":"Ab Initio Molecular Dynamics Simulation of the Structure and Proton Transport Dynamics of Methanol-Water Solutions","volume":"110","author":"Morrone","year":"2006","journal-title":"J. Phys. Chem. B"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"134502","DOI":"10.1063\/1.2647105","article-title":"Influence of electric field on the hydrogen bond network of methanol","volume":"126","author":"Suresh","year":"2007","journal-title":"J. Chem. Phys."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"054502","DOI":"10.1063\/1.4907010","article-title":"Liquid methanol under a static electric field","volume":"142","author":"Cassone","year":"2015","journal-title":"J. Chem. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"207801","DOI":"10.1103\/PhysRevLett.108.207801","article-title":"Ab Initio Molecular Dynamics Study of Dissociation of Water under an Electric Field","volume":"108","author":"Saitta","year":"2012","journal-title":"Phys. Rev. Lett."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"4419","DOI":"10.1021\/jp5021356","article-title":"Proton Conduction in Water Ices under an Electric Field","volume":"118","author":"Cassone","year":"2014","journal-title":"J. Phys. Chem. B"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"074505","DOI":"10.1063\/1.5079393","article-title":"Anisotropic structure and dynamics of water under static electric fields","volume":"150","author":"Shafiei","year":"2019","journal-title":"J. Chem. Phys."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"21205","DOI":"10.1039\/C9CP03101D","article-title":"Ab initio spectroscopy of water under electric fields","volume":"21","author":"Cassone","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"88","DOI":"10.1038\/nature16989","article-title":"Electrostatic catalysis of a Diels-Alder reaction","volume":"531","author":"Aragones","year":"2016","journal-title":"Nature"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1091","DOI":"10.1038\/nchem.2651","article-title":"Oriented electric fields as future smart reagents in chemistry","volume":"8","author":"Shaik","year":"2016","journal-title":"Nat. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"5153","DOI":"10.1021\/acscatal.7b02899","article-title":"Elucidating the Roles of Electric Fields in Catalysis: A Perspective","volume":"8","author":"Che","year":"2018","journal-title":"ACS Catal."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"2329","DOI":"10.1039\/C6SC04269D","article-title":"One-step electric-field driven methane and formaldehyde synthesis from liquid methanol","volume":"8","author":"Cassone","year":"2017","journal-title":"Chem. Sci."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"6901","DOI":"10.1038\/s41598-017-07187-8","article-title":"Novel electrochemical route to cleaner fuel dimethyl ether","volume":"7","author":"Cassone","year":"2017","journal-title":"Sci. Rep."},{"key":"ref_38","unstructured":"Kaila, K., and Ransom, B.R. (1998). pH and Brain Function, Wiley."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"99","DOI":"10.1016\/j.cplett.2015.06.049","article-title":"The structure of water-methanol mixtures under an electric field: Ab initio molecular dynamics simulations","volume":"635","author":"He","year":"2015","journal-title":"Chem. Phys. Lett."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"15","DOI":"10.1002\/wcms.1159","article-title":"CP2K: Atomistic simulations of condensed matter systems","volume":"4","author":"Hutter","year":"2014","journal-title":"Wiley Interdiscip. Rev.-Comput. Mol. Sci."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"103","DOI":"10.1016\/j.cpc.2004.12.014","article-title":"QUICKSTEP: Fast and accurate Density Functional calculations using a mixed gaussian and plane waves approach","volume":"167","author":"Vandevondele","year":"2005","journal-title":"Comput. Phys. Commun."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1651","DOI":"10.1103\/PhysRevB.47.1651","article-title":"Theory of polarization of crystalline solids","volume":"47","author":"Vanderbilt","year":"1993","journal-title":"Phys. Rev. B."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"899","DOI":"10.1103\/RevModPhys.66.899","article-title":"Macroscopic polarization in crystalline dielectrics: The geometric phase approach","volume":"66","author":"Resta","year":"1994","journal-title":"Rev. Mod. Phys."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1098\/rspa.1984.0023","article-title":"Quantal phase factors accompanying adiabatic changes","volume":"392","author":"Berry","year":"1984","journal-title":"Proc. R. Soc. Lond. A"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"157602","DOI":"10.1103\/PhysRevLett.89.157602","article-title":"Ab initio molecular dynamics in a finite homogeneous electric field","volume":"89","author":"Umari","year":"2002","journal-title":"Phys. Rev. Lett."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"12407","DOI":"10.1039\/C5CP00629E","article-title":"Perspectives on external electric fields in molecular simulation: Progress, prospects and challenges","volume":"17","author":"English","year":"2015","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"145","DOI":"10.1007\/s00214-005-0655-y","article-title":"Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals","volume":"114","author":"Krack","year":"2005","journal-title":"Theor. Chem. Acc."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density-Functional exchange-energy approximation with correct asymptotic behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A consistent and accurate ab initio parametrization of Density Functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_51","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_52","doi-asserted-by":"crossref","first-page":"3902","DOI":"10.1021\/ct3001848","article-title":"Structure and dynamics of liquid water from ab initio molecular dynamics\u2014comparison of BLYP, PBE, and revPBE Density Functionals with and without van der Waals corrections","volume":"8","author":"Lin","year":"2012","journal-title":"J. Chem. Theory Comput."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"29401","DOI":"10.1021\/jp506120t","article-title":"Structure, dynamics, and spectral diffusion of water from first-principles molecular dynamics","volume":"118","author":"Bankura","year":"2014","journal-title":"J. Phys. Chem. C"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"130901","DOI":"10.1063\/1.4944633","article-title":"Perspective: How good is DFT for water?","volume":"144","author":"Gillan","year":"2016","journal-title":"J. Chem. Phys."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"014101","DOI":"10.1063\/1.2408420","article-title":"Canonical sampling through velocity rescaling","volume":"126","author":"Bussi","year":"2007","journal-title":"J. Chem. Phys."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"2471","DOI":"10.1103\/PhysRevLett.55.2471","article-title":"Unified approach for molecular dynamics and Density-Functional Theory","volume":"55","author":"Car","year":"1985","journal-title":"Phys. Rev. Lett."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"1159","DOI":"10.1080\/00268979909483060","article-title":"The structure of liquid methanol revisited: A neutron diffraction experiment at \u221280 \u00b0C and +25 \u00b0C","volume":"96","author":"Yamaguchi","year":"1999","journal-title":"Mol. Phys."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"603","DOI":"10.1080\/00268979909482859","article-title":"The structure of liquid methanol revisited: A neutron diffraction experiment at \u221280 \u00b0C and +25 \u00b0C","volume":"97","author":"Yamaguchi","year":"1999","journal-title":"Mol. Phys."},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"9202","DOI":"10.1021\/acs.jpcc.9b01037","article-title":"Catalyst-Free Hydrogen Synthesis from Liquid Ethanol: An ab Initio Molecular Dynamics Study","volume":"123","author":"Cassone","year":"2019","journal-title":"J. Phys. Chem. C"},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"074710","DOI":"10.1063\/1.4865126","article-title":"Nanoconfined water under electric field at constant chemical potential undergoes electrostriction","volume":"140","author":"Vanzo","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.cplett.2011.09.040","article-title":"Ionization of water in interfacial electric fields: An electrochemical view","volume":"519\u2013520","author":"Stuve","year":"2012","journal-title":"Chem. Phys. Lett."},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"767","DOI":"10.1007\/s12274-013-0355-1","article-title":"Robust reduction of graphene fluoride using an electrostatically biased scanning probe","volume":"6","author":"Lee","year":"2013","journal-title":"Nano Res."},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"243110","DOI":"10.1063\/1.4770516","article-title":"Proton and light ion nanobeams from field ionization of water","volume":"101","author":"Hammadi","year":"2012","journal-title":"Appl. Phys. Lett."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"15591","DOI":"10.1073\/pnas.1308560110","article-title":"Nuclear quantum effects and hydrogen bond fluctuations in water","volume":"110","author":"Ceriotti","year":"2013","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"1545","DOI":"10.1021\/acs.jpclett.7b00391","article-title":"Quantum dynamics and spectroscopy of ab initio liquid water: The interplay of nuclear and electronic quantum effects","volume":"8","author":"Marsalek","year":"2017","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"2902","DOI":"10.1021\/acs.jpclett.5b00901","article-title":"Density and compressibility of liquid water and ice from first-principles simulations with hybrid functionals","volume":"6","author":"Gaiduk","year":"2015","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"034501","DOI":"10.1063\/1.4905333","article-title":"Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions","volume":"142","author":"Miceli","year":"2015","journal-title":"J. Chem. Phys."},{"key":"ref_68","doi-asserted-by":"crossref","first-page":"413","DOI":"10.1038\/s41557-018-0010-2","article-title":"Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer","volume":"10","author":"Chen","year":"2018","journal-title":"Nat. Chem."},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"387","DOI":"10.1146\/annurev-biochem-061516-044432","article-title":"Electric Fields and Enzyme Catalysis","volume":"86","author":"Fried","year":"2017","journal-title":"Annu. Rev. Biochem."},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"854","DOI":"10.1021\/ar0400443","article-title":"Electron-Transfer Processes of Cytochrome c at Interfaces. New Insights by Surface-Enhanced Resonance Raman Spectroscopy","volume":"37","author":"Murgida","year":"2004","journal-title":"Acc. Chem. Res."},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"13768","DOI":"10.1073\/pnas.1402894111","article-title":"Miller experiments in atomistic computer simulations","volume":"111","author":"Saitta","year":"2014","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"144101","DOI":"10.1063\/1.4820487","article-title":"The chemical bond in external electric fields: Energies, geometries, and vibrational Stark shifts of diatomic molecules","volume":"139","author":"Matta","year":"2013","journal-title":"J. Chem. Phys."},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"213","DOI":"10.1007\/s00214-009-0650-9","article-title":"Investigating sigma bonds in an electric field from the Pauling\u2019s perspective: The behavior of Cl-X and H-X (X = C,Si) bonds","volume":"126","author":"Papanikolaou","year":"2010","journal-title":"Theor. Chem. Acc."},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chemphys.2016.08.008","article-title":"On the activation of \u03c3-bonds by electric fields: A Valence Bond perspective","volume":"477","author":"Rincon","year":"2016","journal-title":"Chem. Phys."},{"key":"ref_75","doi-asserted-by":"crossref","first-page":"401","DOI":"10.1038\/092401b0","article-title":"Observation of the Separation of Spectral Lines by an Electric Field","volume":"92","author":"Stark","year":"1913","journal-title":"Nature"},{"key":"ref_76","doi-asserted-by":"crossref","first-page":"3179","DOI":"10.1063\/1.464090","article-title":"The vibrational Stark effect","volume":"98","author":"Bishop","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"1449","DOI":"10.1021\/ja00109a038","article-title":"Vibrational Stark Effect Spectroscopy","volume":"117","author":"Chattopadhyay","year":"1995","journal-title":"J. Am. Chem. Soc."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/15\/3371\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:51:33Z","timestamp":1760176293000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/15\/3371"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,7,24]]},"references-count":77,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2020,8]]}},"alternative-id":["molecules25153371"],"URL":"https:\/\/doi.org\/10.3390\/molecules25153371","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,7,24]]}}}