Abstract
Electric fields produce a range of effects by interacting with atoms, molecules, and complex matter modifying the activation barriers of chemical reactions, shaping their free-energy landscapes and reaction pathways, and hence holding a crucial place in catalysis. Owing to the development of novel theories and advanced computational approaches, nowadays supercomputing resources are routinely exploited to investigate the catalytic effects observed when intense electric fields are applied on condensed matter. Within this context, ab initio molecular dynamics simulations coupled with free-energy methods represent unique computational tools allowing for the fine characterization of the role played by static electric fields in activating chemical processes in liquids. Furthermore, the achievement of including crucial nuclear quantum effects in path-integral ab initio molecular dynamics simulations paves the way toward the systematic investigation of the field-induced catalytic effects on matter treated as a fully quantum object. In this review, a series of recent findings on the catalytic effects produced by applying strong electric fields on liquids, with implications not only in technological and industrial realms but also in investigating the “origins of life” enigma, are reported.
Similar content being viewed by others
References
Shaik S, de Visser SP, Kumar D (2004) External electric field will control the selectivity of enzymatic-like bond activations. J Am Chem Soc 126:11746–11749
Meir R, Chen H, Lai W, Shaik S (2010) Oriented electric fields accelerate Diels–Alder reactions and control the endo/exo selectivity. ChemPhysChem 11:301–310
English NJ, Waldron CJ (2015) Perspectives on external electric fields in molecular simulation: progress, prospects and challenges. Phys Chem Chem Phys 17:12407–12440
de Pomerai DI, Smith B, Dawe A et al (2003) Microwave radiation can alter protein conformation without bulk heating. FEBS Lett 543:93–97
Porcelli M, Cacciapuoti G, Fusco S et al (1998) Non-thermal effects of microwaves on proteins: thermophilic enzymes as model system. FEBS Lett 402:102–106
Futera CJ, English NJ (2017) Communication: Influence of external static and alternating electric fields on water from long-time non-equilibrium ab initio molecular dynamics. J Chem Phys 147:031102
Lamoreux G, Roux B (2003) Modeling induced polarization with classical Drude oscillators: theory and molecular dynamics simulation algorithm. J Chem Phys 119:3025
Schröder C, Steinhauser O (2010) Simulating polarizable molecular ionic liquids with Drude oscillators. J Chem Phys 133:154511
Heid E, Boresch S, Schröder C (2020) Polarizable molecular dynamics simulations of ionic liquids: influence of temperature control. J Chem Phys 152:094105
Lai W, Chen H, Cho K-B, Shaik S (2010) External electric field can control the catalytic cycle of cytochrome P450cam: a QM/MM study. J Phys Chem Lett 1:2082–2087
Stuyver T, Huang J, Mallick D, Danovich D, Shaik S (2019) TITAN: a code for modeling and generating electric fields-features and applications to enzymatic reactivity. J Comput Chem 41:74–82
Marx D, Hutter J (2009) Ab initio molecular dynamics—basic theory and advanced methods. Cambridge University Press, Cambridge
Umari P, Pasquarello A (2002) Ab initio molecular dynamics in a finite homogeneous electric field. Phys Rev Lett 89:157602
King-Smith RD, Vanderbilt D (1993) Theory of polarization of crystalline solids. Phys Rev B 47:1651
Resta R (1994) Macroscopic polarization in crystalline dielectrics: the geometric phase approach. Rev Mod Phys 66:899
Berry MV (1984) Quantal phase factors accompanying adiabatic changes. Proc R Soc Lond A 392:45
Ceriotti M, Bussi G, Parrinello M (2009) Nuclear quantum effects in solids using a colored-noise thermostat. Phys Rev Lett 103:030603
Ceriotti M, Manolopoulos DE, Parrinello M (2011) Accelerating the convergence of path integral dynamics with a generalized Langevin equation. J Chem Phys 134:084104
Ceriotti M, Manolopoulos DE (2012) Efficient first-principles calculation of the quantum kinetic energy and momentum distribution of nuclei. Phys Rev Lett 109:100604
Markland TE, Ceriotti M (2018) Nuclear quantum effects enter the mainstream. Nat Rev 2:0109
Cassone G (2020) Nuclear quantum effects largely influence molecular dissociation and proton transfer in liquid water under an electric field. J Phys Chem Lett 11:8983–8988
Ceriotti M, Cuny J, Parrinello M, Manolopoulos DE (2013) Nuclear quantum effects and hydrogen bond fluctuations in water. Proc Natl Acad Sci USA 110:15591–15596
Marsalek O, Markland TE (2017) Quantum dynamics and spectroscopy of ab initio liquid water: the interplay of nuclear and electronic quantum effects. J Phys Chem Lett 8:1545–1551
Lan J, Ribkyn VV, Iannuzzi M (2020) Ionization of water as an effect of quantum delocalization at aqueous electrode interfaces. J Phys Chem Lett 11:3724–3730
Laio A, Parrinello M (2002) Escaping free energy minima. Proc Natl Acad Sci USA 99:12562–12566
Bussi G, Laio A (2020) Using metadynamics to explore complex free-energy landscapes. Nat Rev Phys 2:200–212
Aragones AC, Haworth NL, Darwish N et al (2016) Electrostatic catalysis of a Diels–Alder reaction. Nature 531:88–91
Che F, Gray JT, Ha S et al (2018) Elucidating the roles of electric fields in catalysis: a perspective. ACS Catal 8:5153–5174
Cassone G, Pietrucci F, Saija F et al (2017) One-step electric-field driven methane and formaldehyde synthesis from liquid methanol. Chem Sci 8:2329–2336
Shaik S, Mandal D, Ramanan R (2016) Oriented electric fields as future smart reagents in chemistry. Nat Chem 8:1091–1098
Wang Z, Danovich D, Ramanan R, Shaik S (2018) Oriented-external electric fields create absolute enantioselectivity in Diels–Alder reactions: importance of the molecular dipole moment. J Am Chem Soc 140:13350–13359
Nunes RW, Vanderbilt D (1994) Real-space approach to calculation of electric polarization and dielectric constants. Phys Rev Lett 73:712
Nunes RW, Gonze X (2001) Berry-phase treatment of the homogeneous electric field perturbation in insulators. Phys Rev B 63:155107
Resta R (1998) Quantum-mechanical position operator in extended systems. Phys Rev Lett 80:1800
Wannier GH (1960) Wave functions and effective Hamiltonian for Bloch electrons in an electric field. Phys Rev 117:432
Nenciu G (1991) Dynamics of band electrons in electric and magnetic fields: rigorous justification of the effective Hamiltonians. Rev Mod Phys 63:91
Gonze X, Ghosez P, Godby RW (1995) Density-polarization functional theory of the response of a periodic insulating solid to an electric field. Phys Rev Lett 74:4035
Gonze X, Ghosez P, Godby RW (1997) Density-functional theory of polar insulators. Phys Rev Lett 78:294
Car R, Parrinello M (1985) Unified approach for molecular dynamics and density-functional theory. Phys Rev Lett 55:2471
Giannozzi P, Baroni S, Bonini N (2009) QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J Phys 21:395502
Hutter J, Iannuzzi M, Schiffmann F, VandeVondele J (2014) CP2K: Atomistic simulations of condensed matter systems. Wiley Interdiscip Rev 4:15–25
Vandevondele J, Krack M, Mohamed F et al (2005) QUICKSTEP: Fast and accurate Density Functional calculations using a mixed gaussian and plane waves approach. Comput Phys Commun 167:103–128
Saitta AM, Saija F, Giaquinta PV (2012) Ab initio molecular dynamics study of dissociation of water under an electric field. Phys Rev Lett 108:207801
Cassone G, Creazzo F, Giaquinta PV et al (2016) Ab initio molecular dynamics study of an aqueous NaCl solution under an electric field. Phys Chem Chem Phys 18:23164–23173
Cassone G, Creazzo F, Giaquinta PV et al (2017) Ionic diffusion and proton transfer in aqueous solutions of alkali metal salts. Phys Chem Chem Phys 19:20420–20429
Cassone G, Calogero G, Sponer J, Saija F (2018) Mobilities of iodide anions in aqueous solutions for applications in natural dye-sensitized solar cells. Phys Chem Chem Phys 20:13038–13046
Cassone G, Creazzo F, Saija F (2019) Ionic diffusion and proton transfer of MgCl\(_2\) and CaCl\(_2\) aqueous solutions: an ab initio study under electric field. Mol. Sim. 45:373–380
Cassone G, Giaquinta PV, Saija F, Saitta AM (2015) Liquid methanol under a static electric field. J Chem Phys 142:054502
Cassone G, Pietrucci F, Saija F et al (2017) Novel electrochemical route to cleaner fuel dimethyl ether. Sci Rep 7:6901
Cassone G, Sofia A, Sponer J et al (2020) Ab initio molecular dynamics study of methanol–water mixtures under external electric fields. Molecules 25:3371
Cassone G, Sofia A, Rinaldi G, Sponer J (2019) Catalyst-free hydrogen synthesis from liquid ethanol: an ab initio molecular dynamics study. J Phys Chem C 123:9202–9208
Saitta AM, Saija F (2014) Miller experiments in atomistic computer simulations. Proc Natl Acad Sci USA 111:13768–13773
Cassone G, Sponer J, Sponer JE et al (2018) Synthesis of (d)-erythrose from glycolaldehyde aqueous solutions under electric field. Chem Commun 54:3211–3214
Ferus M, Laitl V, Knizek A et al (2018) HNCO-based synthesis of formamide in planetary atmospheres. Astron Astrophys 616:A150
Bussi G, Donadio D, Parrinello M (2007) Canonical sampling through velocity rescaling. J Chem Phys 126:014101
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865
Perdew JP, Burke K, Ernzerhof M (1997) ibidem. Phys Rev Lett 78:1396
Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098
Lee C, Yang W, Parr RG (1988) Development of the Colle–Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785
Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of Density Functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104
Grimme S, Ehrlich S, Goerigk L (2011) Effect of the damping function in dispersion corrected Density Functional Theory. J Comput Chem 32:1456–1465
Krack M (2005) Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals. Theor Chem Acc 114:145–152
Branduardi D, Gervasio FL, Parrinello M (2007) From A to B in free energy space. J Chem Phys 126:054103
Pietrucci F, Saitta AM (2015) Formamide reaction network in gas phase and solution via a unified theoretical approach: toward a reconciliation of different prebiotic scenarios. Proc Natl Acad Sci USA 112:15030–15035
Pietrucci F (2017) Strategies for the exploration of free energy landscapes: unity in diversity and challenges ahead. Rev Phys 2:32–45
Bonomi M, Branduardi D, Bussi G et al (2009) PLUMED: a portable plugin for free energy calculations with molecular dynamics. Comput Phys Commun 180:1961–1972
Tribello GA, Bonomi M, Branduardi D, Camilloni C, Bussi G (2014) PLUMED2: new feathers for an old bird. Comput Phys Commun 185:604–613
Bolhuis PG, Chandler D, Dellago C, Geissler PL (2002) TRANSITION PATH SAMPLING: throwing ropes over rough mountain passes, in the dark. Annu Rev Phys Chem 53:291–318
Chen M, Zheng L, Santra B et al (2018) Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer. Nat Chem 10:413–419
Rozsa V, Pan D, Giberti F, Galli G (2018) Ab initio spectroscopy and ionic conductivity of water under Earth mantle conditions. Proc Natl Acad Sci USA 115:6952–6957
Hassanali A, Giberti F, Cuny J et al (2013) Proton transfer through the water gossamer. Proc Natl Acad Sci USA 110:13723–13728
Futera Z, Tse JS, English NJ (2020) Possibility of realizing superionic ice VII in external electric fields of planetary bodies. Sci Adv 21:eaaz2915
Geissler PL, Dellago C, Chandler D et al (2001) Autoionization in liquid water. Science 291:2121–2124
Dellago C, Bolhuis PG, Geissler PL (2002) Transition path sampling. Adv Chem Phys 123:1–78
Cassone G, Giaquinta PV, Saija F, Saitta AM (2014) Proton conduction in water ices under an electric field. J Phys Chem B 118:4419–4424
Cassone G, Giaquinta PV, Saija F, Saitta AM (2014) Effect of electric field orientation on the mechanical and electrical properties of water ices: an ab-initio study. J Phys Chem B 118:12717–12724
Stuve EM (2012) Ionization of water in interfacial electric fields: an electrochemical view. Chem Phys Lett 519–520:1–17
Lee WK, Tsoi S, Whitener KE et al (2013) Robust reduction of graphene fluoride using an electrostatically biased scanning probe. Nano Res 6:767–774
Hammadi Z, Descoins M, Salançon E, Morin R (2012) Proton and light ion nanobeams from field ionization of water. Appl Phys Lett 101:243110
Martinez RJ, Farrell J (2019) Quantifying electric field enhancement of water dissociation rates in bipolar membranes. Ind Eng Chem Res 58:782–789
Rothfuss CJ, Medvedev VK, Stuve EM (2003) The influence of the surface electric field on water ionization: a two step dissociative ionization and desorption mechanism for water ion cluster emission from a platinum field emitter tip. J Electroanal Chem 554–555:133–143
Laage D, Elsaesser T, Hynes JT (2017) Perspective: Structure and ultrafast dynamics of biomolecular hydration shells. Struct Dyn 4:044018
Kundu A, Dahms F, Fingerhut BP et al (2019) Hydrated excess protons in acetonitrile/water mixtures: solvation species and ultrafast proton motions. J Phys Chem Lett 10:2287–2294
Sellner B, Valiev M, Kathmann SM (2013) Charge and electric field fluctuations in aqueous NaCl electrolytes. J Phys Chem B 117:10869–10882
Dougan L, Bates SP, Hargreaves R et al (2004) Methanol–water solutions: a bi-percolating liquid mixture. J Chem Phys 121:6456
Lenton S, Rhys NH, Towey JJ et al (2018) Temperature-dependent segregation in alcohol–water binary mixtures is driven by water clustering. J Phys Chem B 122:7884–7894
Olah GA, Goeppert A, Prakash GKS (2009) Chemical recycling of carbon dioxide to methanol and dimethyl ether: from greenhouse gas to renewable, environmentally carbon neutral fuels and synthetic hydrocarbons. J Org Chem 74:487–498
Miri MJ, Bailey AV, Takacs GA (2008) Introduction to hydrogen technology. Wiley, Hoboken
Häussinger P, Lohmüller R, Watson AM (2011) Ullman’s encyclopedia of industrial chemistry. Wiley, Hoboken
Erisman JW, Sutton MA, Galloway J et al (2008) How a century of ammonia synthesis changed the world. Nat Geo 1:636–639
Grochala W (2015) First was hydrogen. Nat Chem 7:264
Jacobson MZ, Colella WG, Golden DM (2005) Cleaning the air and improving health with hydrogen fuel-cell vehicles. Science 308:1901–1905
Haile SM, Boysen DA, Chisholm CRI, Merle RM (2001) Solid acids as fuel cell electrolytes. Nature 410:910–913
Marzari N, Mostofi AA, Yates JR et al (2012) Maximally localized Wannier functions: theory and applications. Rev Mod Phys 84:1419–1475
Miller SL (1953) A production of aminoacids under possible primitive Earth conditions. Science 117:528–529
Cassone G, Saija F, Sponer J et al (2018) Dust motions in magnetized turbulence: source of chemical complexity. Astrophys J Lett 866:L23
Saladino R, Carota E, Botta G et al (2016) First evidence on the role of heavy ion irradiation of meteorites and formamide in the origin of biomolecules. Orig Life Evol Biosph 46:515–521
Saladino R, Carota E, Botta G et al (2015) Meteorite-catalyzed syntheses of nucleosides and of other prebiotic compounds from formamide under proton irradiation. Proc Natl Acad Sci USA 112:E2746–E2755
Rotelli L, Trigo-Rodríguez JM, Moyano-Cambero CE et al (2016) The key role of meteorites in the formation of relevant prebiotic molecules in a formamide/water environment. Sci Rep 6:38888
Sponer JE, Mladek A, Sponer J et al (2012) Formamide-based prebiotic synthesis of nucleobases: a kinetically accessible reaction route. J Phys Chem A 116:720–726
Saitta AM, Saija F, Pietrucci F, Guyot F (2015) Reply to bada and cleaves: ab initio free-energy landscape of Miller-like prebiotic reactions. Proc Natl Acad Sci USA 112:E343–E344
Petroff CA, Cassone G, Sponer J, Hutchison GR (2021) Intrinsically polar piezoelectric self-assembled oligopeptide monolayers. Adv Math 33:2007486
Hammadi Z, Astier JP, Morin R, Veesler S (2007) Protein crystallization induced by a localized voltage. Cryst Growth Des 7:1472–1475
Miller SL, Urey HC (1959) Organic compound synthesis on the primitive Earth. Science 130:245
Miller SL (1957) The mechanism of synthesis of amino acids by electric discharges. Biochem Biophys Acta 23:480–489
Lazcano A, Bada JL (2003) The 1953 Stanley L. Miller experiment: fifty years of prebiotic organic chemistry. Orig Life Evol Biosph 33:235–242
Jalbout AF, Abrell L, Adamowicz L et al (2007) Sugar synthesis from a gas-phase formose reaction. Astrobiology 7:433–442
Steer AM, Bia N, Smith DK, Clarke PA (2017) Prebiotic synthesis of 2-deoxy-d-ribose from interstellar building blocks promoted by amino esters or amino nitriles. Chem Commun 53:10362–10365
Fukui K, Yonezawa T, Shingu H (1952) A molecular orbital theory of reactivity in aromatic hydrocarbons. J Chem Phys 20:722
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Cassone, G., Sponer, J. & Saija, F. Ab Initio Molecular Dynamics Studies of the Electric-Field-Induced Catalytic Effects on Liquids. Top Catal 65, 40–58 (2022). https://doi.org/10.1007/s11244-021-01487-0
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11244-021-01487-0