The liquid-vapour interface of QDO water. Flaviu Cipcigan Andrew Jones Jason Crain Vlad Sokhan Glenn Martyna

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1 The liquid-vapour interface of QDO water Flaviu Cipcigan Andrew Jones Jason Crain Vlad Sokhan Glenn Martyna

2 The liquid-vapour interface of QDO water 1. Molecular models 2. The Quantum Drude Oscillator (QDO) 3. Introducing QDO water 4. Liquid-vapour interface of QDO water

3 Architecture: 1950

4 Architecture: now

5 The liquid-vapour interface of QDO water 1. Molecular models 2. The Quantum Drude Oscillator (QDO) 3. Introducing QDO water 4. Liquid-vapour interface of QDO water

6 Challenge efficiently model intermolecular interactions

7 Challenge efficiently model intermolecular interactions Solution begin with simple building blocks

8 Challenge efficiently model intermolecular interactions Solution begin with simple building blocks and assemble them into molecules

9 Molecular building blocks

10 Molecular building blocks Electrostatics Point charges

11 Molecular building blocks Electrostatics Point charges Constraints Translational Rotational

12 Molecular building blocks Electrostatics Point charges Constraints Translational Non-Coulomb forces van der Waals Rotational repulsion

13 Molecular building blocks Electrostatics Point charges Constraints Translational Non-Coulomb forces van der Waals Rotational repulsion Response (limited) Fluctuating dipole Charge transfer

14 The liquid-vapour interface of QDO water 1. Molecular models 2. The Quantum Drude Oscillator (QDO) 3. Introducing QDO water 4. Liquid-vapour interface of QDO water

15 Quantum Drude Oscillator (QDO) Light negative particle tethered harmonically to a heavy positive, oppositely charged nucleus

16 Quantum Drude Oscillator (QDO) Light negative particle tethered harmonically to a heavy positive, oppositely charged nucleus Free parameters reduced mass spring frequency charge

17 Quantum Drude Oscillator: Response Polarisation dipole

18 Quantum Drude Oscillator: Response Polarisation dipole Dispersion dipole-dipole dipole-quadrupole

19 Quantum Drude Oscillator: Invariants CH 4 H 2 O He Ne Ar Kr Xe H Li K Rb Cs Polarisation

20 Quantum Drude Oscillator: Invariants BH 3 CH 4 NH 3 H 2 O He Ne Ar Kr Xe H Li K Rb Cs Dispersion

21 Molecular building blocks Electrostatics Point charges Constraints Translational Non-Coulomb forces van der Waals Rotational repulsion Response Fluctuating dipole Quantum Drude Oscillator Charge transfer

22 The liquid-vapour interface of QDO water 1. Molecular models 2. The Quantum Drude Oscillator (QDO) 3. Introducing QDO water 4. Liquid-vapour interface of QDO water

23 The liquid-vapour interface of QDO water 1. Molecular models 2. The Quantum Drude Oscillator (QDO) 3. Introducing QDO water Frame QDO Repulsion Damping Sampling 4. Liquid-vapour interface of QDO water

24 1. Frame ground state moments A H O M e A e H

25 2. QDO molecular response = amu = = e

26 3. Repulsion Short range correction

27 4. Electrostatic Damping Short range correction Gaussian charges

28 4. Electrostatic Damping Short range correction Damped Coulomb

29 5. Efficient Sampling Path Integral Molecular Dynamics replace electron with chain of beads

30 5. Efficient Sampling Path Integral Molecular Dynamics no cross interactions between beads

31 The liquid-vapour interface of QDO water 1. Molecular models 2. The Quantum Drude Oscillator (QDO) 3. Introducing QDO water 4. Liquid-vapour interface of QDO water

32 1. Setup 300 QDO-water molecules Periodic boundaries Unit cell A 3

33 2. Density (g cm -3 ) Distance from centre (A)

34 3. Dipole moment (Debye) liquid gas Distance from centre (A)

35 3. Surface charge density (e A ) Distance from centre (A)

36 4. Electronic distribution (minus gas phase ground state charge density) 1.0 Slice: 1A Density (g cm -3 ) Distance from centre (A)

37 4. Electronic distribution (minus gas phase ground state charge density) 1.0 Slice: 13A Density (g cm -3 ) Distance from centre (A)

38 4. Electronic distribution (minus gas phase ground state charge density) 1.0 Slice: 15A Density (g cm -3 ) Distance from centre (A)

39 5. Nearest neighbour distribution 1.0 Slice: 1A Density (g cm -3 ) Distance from centre (A)

40 5. Nearest neighbour distribution Slice: 13A z Density (g cm -3 ) Distance from centre (A)

41 The liquid-vapour interface of QDO water 1. Molecular models 2. The Quantum Drude Oscillator (QDO) 3. Introducing QDO water 4. Liquid-vapour interface of QDO water

42 Conclusions QDOs are an accurate model for long range forces QDO water has a physical liquid-vapour interface Next steps Exploration of the interface's structure and the effects of dispersion and polarisation on physical properties References A. Jones, Quantum drude oscillators for accurate many-body intermolecular forces, PhD thesis, The University of Edinburgh A. Jones, F. Cipcigan, V. Sokhan, J. Crain, G. Martyna, Electronically coarse grained water, PRL (under review)

43

44 Liquid radial distribution function 3.0 g OO (r) Skinner et al. (exp). TIP4P_pol2 QDO latest r

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