Specific Ion Solvtion in Ethylene Carbonate and Propylene Carbonate

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Specific Ion Solvtion in Ethylene Carbonate and Propylene Carbonate A. Arslanargin, A. Powers, S. Rick, T. Pollard, T. Beck Univ Cincinnati Chemistry Support: NSF, OSC TSRC 2016 November 2, 2016 A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 1 / 26

Outline 1. Introduction 2. Force fields 3. Energies 4. Classical structure 5. Thermodynamics 6. Cavity potentials 7. Quantum studies A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 2 / 26

EC and PC (a) (b) Figure: Images of the EC (a) and PC (b) molecules. Modeled with AMBER-GAFF force field. LJ and Buckingham models for ions. Fixed charges, enhanced molecular dipoles relative to gas phase. Cations bind on top (hard), anions on bottom (soft). J. Phys. Chem. B 120, 1497 (2016) A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 3 / 26

EC and PC EC: dipole 4.61 D, ε 89.8, BP 515 K, MP 36.4 K, α 6.8 Å 3 PC: dipole 4.81 D, ε 64.9, BP 515 K, MP -49 K, α 8.7 Å 3 EC AMBER GAFF dipole 6.2 D PC AMBER GAFF dipole 6.4 D AMBER GAFF good for density, ε, surf tension, not so good for enthalpy of vaporization (20 % too large) 20 % charge reduction fixes above error, but other consequences? Water polarizability is only α 1.47 Å 3 A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 4 / 26

Force field and QM interactions: Li + /EC Binding energies (kcal/mol) 40 20 0 20 40 Lennard Jones MP2 Buckingham (a) 0 1 2 3 4 Ion displacement (Å) Figure: Li + -EC (a) binding energy curves with Lennard-Jones and modified Buckingham potentials, and MP2 calculations. A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 5 / 26

Force field and QM interactions: Cl /EC Binding energies (kcal/mol) 0 10 20 Lennard Jones MP2 Buckingham (b) 0 1 2 3 4 Ion displacement (Å) Figure: Cl -EC (b) binding energy curves with Lennard-Jones and modified Buckingham potentials, and MP2 calculations. A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 6 / 26

MD simulations and FE calcs AMBER GAFF FF for EC and PC LJ models taken from Horinek et al. params for ion-water Derived modified Buckingham model from MP2 calcs above PBC and Ewald Free energies using our LMFT-type approach; separates electrostatics into local and far field contributions Experimental thermodynamic data from Pierandrea Lo Nostro group s papers cited in our paper. Ion pair solubility measurements. A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 7 / 26

SAPT energy partitioning Table: SAPT2/aug-cc-phwCVDZ interaction energies for ion-solvent dimers; all energies are given in kcal/mol. Solvent Ion E elst E exch E ind E disp E SAPT E MP2 EC Li + -41.63 13.55-21.52-0.57-50.17-49.57 K + -28.04 10.08-8.43-1.73-28.12-27.42 F - -40.83 30.97-17.05-5.25-32.17-30.62 Cl - -28.23 19.02-8.21-5.43-22.85-22.12 Br - -26.43 18.05-7.01-5.57-20.97-20.24 PC Li + -43.50 13.81-21.09-0.50-51.27-51.20 K + -29.01 10.41-8.78-1.77-29.14-28.45 F - -39.81 31.70-19.03-5.79-32.93-30.84 Cl - -26.90 19.27-9.20-6.02-22.85-21.82 Br - -25.08 18.31-7.85-6.21-20.84-19.88 A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 8 / 26

Ion specificity Dispersion differs between cations and anions as expected, but weak contribution to ion specificity between anions. Electrostatics, exchange, and induction make larger contributions. A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 9 / 26

RDF Li + /EC 50 10 g(r) 40 30 20 10 (a) Buckingham Lennard Jones 8 6 4 2 Coordination number 0 1 2 3 4 5 6 0 r (Å) Figure: RDFs A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 10 / 26

Experiment/Theory Experiment (neutron, Xray absorption) suggest coordination of 4-4.5. Ab initio simulation puts first maximum at about 2 Å, and 4-coordinated (see below). A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 11 / 26

RDF Cl /EC 3 60 g(r) 2 1 (b) Buckingham Lennard Jones 0 2 4 6 8 10 12 14 0 r (Å) 40 20 Coordination number Figure: RDFs A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 12 / 26

Ion FEs Table: Single-ion free energies and enthalpies are calculated for the two models at T = 313 K for EC and PC. U SR is solvent reorganization energy. Marcus values for K + and Cl in PC are -73.2 and -76.7. Solvent Ion µ ex LJ h ex LJ µ ex Buck h ex Buck s ex Buck U SR EC K + -84.0-93.7-87.8-97.6-31.3 60.8 F - -67.0-77.7-82.4-90.3-25.2 45.2 Cl - -57.8-71.2-68.2-75.4-23.0 41.9 Br - -50.5-65.8-61.1-70.3-29.4 38.8 PC K + -87.1-100.9-87.9-99.1-35.8 58.0 F - -64.0-77.1-83.5-91.9-26.8 45.1 Cl - -51.3-65.5-63.7-71.6-25.2 41.0 Br - -47.1-63.6-59.5-70.9-36.4 39.6 A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 13 / 26

Model comparison Table: Free energy, enthalpy, and entropy changes of solvation. First 3 rows for EC, second 3 for PC. Potassium salts with F, Cl, Br. Second row adds U SR correction for induced dipoles. µ ex LJ hlj ex slj ex µ ex Buck hbuck ex sbuck ex µ ex exp hexp ex sexp ex -151.8(19.8) -172.1(-3.6) -64.9(-74.8) -170.4(1.2) -187.9(-19.4) -55.9(-65.8) -171.6-168.5 9.9-179.4(-10.9) -28.8(-38.7) -143.2(5.2) -166.3(-16.6) -73.8(-69.6) -156.4(-8.0) -173.3(-23.6) -54.0(-49.8) -148.4-149.7-4.2-164.8(-15.1) -26.8(-22.6) -135.9(7.1) -160.9(-11.0) -79.9(-57.9) -150.1(-7.1) -169.1(-19.2) -60.7(-38.7) -143.0-149.9-22.0-160.6(-10.7) -33.5(-11.5) -151.7-178.3-85.0-171.4-190.8-62.0-182.3-34.8-140.4(3.6) -168.7(-3.7) -90.4(-24.6) -152.4(-8.4) -173.2(-8.2) -66.5(0.7) -144.4-165.0-65.8-164.7(0.3) -39.3(26.5) -136.0(4.6) -166.3(-5.4) -96.8(-31.9) -148.0(-7.4) -171.1(-10.2) -73.8(-8.9) -140.6-160.9-64.9-162.6(-1.7) -46.7(18.2) A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 14 / 26

Solvent reorganization energy effect? U SR shows up in both enthalpy and entropy, but cancels in free energy. Seems like an extra repulsive contribution helps some compared with experiment. Where does this come from? We proposed it is repulsive interaction of induced dipoles (all pointing towards ion) in first solvation shell (see below). A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 15 / 26

Cycle Figure: Thermodynamic cycle shows the relationship between the free energies of solution and solvation and the lattice free energy. A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 16 / 26

Volcano plot 30 KF KF H soln (kcal/mol) 20 10 KCl KBr KCl 0 KBr 0 10 20 30 40 H solv (X - - K +, kcal/mol) Figure: Relationship between the enthalpy of solution and the difference between the single solvation enthalpies of K + and halide ions (F, Cl, and Br ) for both EC (circles) and PC (triangles). H solv is our calculated value. A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 17 / 26

ES mean potl at ion center vs. chg 200 m c (kcal/mol) 100 0 100 EC PC 200 1 0.5 0 0.5 1 q/e (a) A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 18 / 26

ES potl fluct vs. chg Quite different from water. Cations are more strongly solvated, and smooth transition as charge mutated. (Hummer, Pratt, Garcia, 1996) 200 180 (b) f c (kcal/mol) 160 140 120 EC PC 100 1 0.5 0 0.5 1 q/e A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 19 / 26

ES potl vs. cavity radius 2 m c (kcal/mol) 4 6 EC PC 2 4 6 8 r (Å) Figure: Electrostatic potential at the center of a vdw particle cavity in EC and PC as a function of the cavity radius. The dashed line shows the size of the particle (Cl size). A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 20 / 26

Introduction Force fields Energies Classical structure Thermodynamics Cavity potentials Quantum studies Li+ in EC; AIMD; PBE/D3BJ; 240 ps, 31 EC A. Arslanargin, A. Powers, S. Rick, T. Pollard,Specific T. Beck Ion(Univ Solvtion Cincinnati in Ethylene Chemistry Carbonate Support: and NSF, Propylene OSC November Carbonate TSRC 2016) 2, 2016 21 / 26

EC dipoles near and far from Li + A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 22 / 26

g(r) for Li + /EC 30 30 25 25 g(r) / arb. 20 15 10 20 15 10 n(r) 5 5 0 0 200 400 600 800 1000 0 r / pm A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 23 / 26

PC dipoles near and far from Li + A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 24 / 26

g(r) for Li + /PC 40 30 32 25 g(r) / arb. 24 16 20 15 10 n(r) 8 5 0 0 200 400 600 800 1000 0 r / pm A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 25 / 26

Conclusions Classical models can yield some insights into solvation But they struggle to reproduce solvation thermodynamic quantities Fixed charges can to some extent mimic polarization in pure solvent condensed phase, but can t reproduce ion solvation quantities Polarization is extreme near Li + ion that is likely important for solvation thermodynamics in EC especially it tends to disorder the solvation shell and creates repulsive solvent-solvent interactions A. Arslanargin, A. Powers, S. Rick, T. Pollard, Specific T. Beck Ion(Univ Solvtion Cincinnati Ethylene Chemistry Carbonate Support: and NSF, Propylene OSCNovember Carbonate TSRC 2016) 2, 2016 26 / 26

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