David van der Spoel 2. October 18, 2011

Transcription

1 Force Field Benchmark of Organic Liquids: Density, Enthalpy of Vaporization, Heat Capacities, Surface Tension, Compressibility, Expansion Coefficient and Dielectric Constant Carl Caleman 1 Paul J. van Maaren 2 Minyan Hong 2 Jochen S. Hub 2 Luciano T. da Costa 3 October 18, 2011 David van der Spoel 2 1 : Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron Notkestraße 85, DE Hamburg, Germany 2 : Department of Cell and Molecular Biology, Uppsala University Husargatan 3, Box 596, SE Uppsala, Sweden 3 : Departamento de Ciências Exatas, Federal University of Alfenas - MG Rua Gabriel Monteiro da Silva, 700 Alfenas - MG CEP: , Brazil : corresponding author, spoel@xray.bmc.uu.se 1

2 Contents 1 Derivation of equations of the two-phase thermodynamics method 7 2 Liquidity Test 10 3 Simulation Results per Property 11 4 Polynomial s to Experimental Data 80 List of Figures S1 S2 S2 S2 S2 S2 S2 S3 S4 S4 Liquidity test. The change in MSD, D as defined in the main text. On the x-axis all the simulated molecules are listed in alphabetic order. For all simulations with D 0.5the trajectories and MSD for the entire simulation was further investigated to ensure that the system was liquid during the whole simulation (part 1) Polynomial curves fitted to dielectric constant measurements for different molecules. For parameters see Table 4 in the main text (part 2) Polynomial curves fitted to dielectric constant measurements for different molecules. For parameters see Table 4 in the main text (part 3) Polynomial curves fitted to dielectric constant measurements for different molecules. For parameters see Table 4 in the main text (part 4) Polynomial curves fitted to dielectric constant measurements for different molecules. For parameters see Table 4 in the main text (part 5) Polynomial curves fitted to dielectric constant measurements for different molecules. For parameters see Table 4 in the main text (part 6) Polynomial curves fitted to dielectric constant measurements for different molecules. For parameters see Table 4 in the main text (part 1) Polynomial curves fitted to heat capacity at constant pressure measurements for different molecules. For parameters see Table 5 in the main text (part 1) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text (part 2) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text

3 S4 S4 S4 S4 S4 S4 S4 (part 3) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text (part 4) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text (part 5) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text (part 6) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text (part 7) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text (part 8) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text (part 9) Polynomial curves fitted to isothermal compressibility measurements for different molecules. For parameters see Table 6 in the main text List of Tables S1 Name, formula, molecular weight (g/cm 3 ), CAS number and ChemSpider ID for all molecules in the test set S1 Name, formula, molecular weight, CAS number, ChemSpider ID - continued S1 Name, formula, molecular weight, CAS number, ChemSpider ID - continued S1 Name, formula, molecular weight, CAS number, ChemSpider ID - continued S1 Name, formula, molecular weight, CAS number, ChemSpider ID - continued S2 Liquid density ρ (g/l) calculated and experimental. Blue font indicates that the calculated value differs more than 5% from the experimental ones, a red font indicates that it differs by more than 10%. The temperature in the calculations is noted in case it deviates from the one used in experiments S2 Liquid density - continued S2 Liquid density - continued S2 Liquid density - continued S2 Liquid density - continued S2 Liquid density - continued S2 Liquid density - continued S2 Liquid density - continued

4 S3 Heat of vaporization H vap (kj/mol) calculated and experimental. Blue font indicates that the calculated value differs more than 10% from the experimental ones, a red font indicates that it differs by more than 25%. The temperature in the calculations is noted in case it deviates from the one used in experiments S3 Heat of vaporization - continued S3 Heat of vaporization - continued S3 Heat of vaporization - continued S3 Heat of vaporization - continued S3 Heat of vaporization - continued S3 Heat of vaporization - continued S3 Heat of vaporization - continued S4 Surface tension γ (10 3 Nm 1 ) calculated and experimental. Blue font indicates that the calculated value differs more than 10% from the experimental ones, a red font indicates that it differs by more than 25%. The temperature in the calculations is noted in case it deviates from the one used in experiments S4 Surface tension - continued S4 Surface tension - continued S4 Surface tension - continued S4 Surface tension - continued S4 Surface tension - continued S5 Dielectric constant ε(0) calculated and experimental. Missing simulated ε(0) due to simulations not having converged, see main text. Blue font indicates that the calculated value differs more than 25% from the experimental ones, a red font indicates that it differs by more than 50%. The temperature in the calculations is noted in case it deviates from the one used in experiments S5 Dielectric constant - continued S5 Dielectric constant - continued S5 Dielectric constant - continued S5 Dielectric constant - continued S5 Dielectric constant - continued S5 Dielectric constant - continued S6 Thermal expansion coefficient α P (10 3 /K), calculated and experimental. Blue font indicates that the calculated value differs more than 25% from the experimental ones, a red font indicates that it differs by more than 50%. The temperature in the calculations is noted in case it deviates from the one used in experiments S6 Thermal expansion coefficient - continued S6 Thermal expansion coefficient - continued S6 Thermal expansion coefficient - continued S6 Thermal expansion coefficient - continued S6 Thermal expansion coefficient - continued

5 S6 Thermal expansion coefficient - continued S6 Thermal expansion coefficient - continued S7 Isothermal compressibility κ T (1/GPa), calculated and experimental Blue font indicates that the calculated value differs more than 10% from the experimental ones, a red font indicates that it differs by more than 25%. The temperature in the calculations is noted in case it deviates from the one used in experiments S7 Isothermal compressibility - continued S7 Isothermal compressibility - continued S7 Isothermal compressibility - continued S7 Isothermal compressibility - continued S7 Isothermal compressibility - continued S7 Isothermal compressibility - continued S7 Isothermal compressibility - continued S8 Heat capacity at constant pressure c P (J/mol K) calculated (based on density of states) and experimental. Blue font indicates that the calculated value differs more than 25% from the experimental ones, a red font indicates that it differs by more than 50%. The temperature in the calculations is noted in case it deviates from the one used in experiments S8 Heat capacity at constant pressure c P based on DoS - continued 63 S8 Heat capacity at constant pressure c P based on DoS - continued 64 S8 Heat capacity at constant pressure c P based on DoS - continued 65 S8 Heat capacity at constant pressure c P based on DoS - continued 66 S9 Heat capacity at constant volume c V (J/mol K) calculated (based on density of states) compared to the experimental c P - c (J/mol K). Blue font indicates that the calculated value differs more than 25% from the experimental ones, a red font indicates that it differs by more than 50%. The temperature in the calculations is noted in case it deviates from the one used in experiments S9 Heat capacity at constant volume c V based on DoS - continued 68 S9 Heat capacity at constant volume c V based on DoS - continued 69 S9 Heat capacity at constant volume c V based on DoS - continued 70 S9 Heat capacity at constant volume c V based on DoS - continued 71 S10 Classical heat capacity at constant pressure c class P (J/mol K) calculated and experimental. Blue font indicates that the calculated value differs more than 25% from the experimental ones, a red font indicates that it differs by more than 50%. The temperature in the calculations is noted in case it deviates from the one used in experiments S10 Classical heat capacity at constant pressure - continued S10 Classical heat capacity at constant pressure - continued S10 Classical heat capacity at constant pressure - continued S10 Classical heat capacity at constant pressure - continued S10 Classical heat capacity at constant pressure - continued S10 Classical heat capacity at constant pressure - continued

6 S10 Classical heat capacity at constant pressure - continued S11 References used for deriving fits of dielectric constants as a function of temperature to experimental data S12 References used for deriving fits of isothermal compressibilities as a function of temperature to experimental data S13 References used for deriving fits of isothermal compressibilities as a function of temperature to experimental data S13 References used for deriving fits of isothermal compressibilities as a function of temperature to experimental data (continued)

7 1 Derivation of equations of the two-phase thermodynamics method Here we derive the equations needed to implement the two-phase thermodynamic (2PT) model introduced by the Goddard group [1, 2, 3, 4]. This model treats a liquid as something in between a solid and an ideal gas, the rationale for this being that there is existing analytical theory for treating the thermodynamic properties of ideal gases and solids, but no such theory exists for liquids. The reason to summarize the equations here rather than to refer to the original publications, is first and foremost that in the three papers mentioned [1, 2, 3] there is no single complete derivation of the method, and second that the equations below serve as a blueprint for a new GROMACS [5] analysis tool, g dos, that computes properties based on the density of states using the 2PT method. It is important to give credit to one of the first papers in this field by Berens et al. [6], that attempted to treat a fluid just like a solid, and which derived most of the equations that the 2PT method is based upon. Another contributing theory is the Carnahan-Starling model of fluids of rigid spheres [7]. Since the equations published by Berens are internally consistent and can be derived from statistical mechanics textbooks (e.g. McQuarrie [8]) we use this as the foundation for deriving the equations below, however, we note as far as possible from which source the equations below were taken. We derive equations in the context of molecular dynamics simulations, i.e. using finite sampling and simulation lengths. We start from the mass-weighted velocity autocorrelation function: C(t) = N 3 m j vj k (t)vj k (t + τ) τ j=1 k=1 (S1) where vj k (t) is the velocity of atom j in the k direction at time t, N is the number of atoms, m j are the atomic masses and τ indicates averaging over time origins τ; C(t) has the units of energy. The Fourier transform of C(t) yields the density of states as a function of frequency ν (Equation 7, reference [1]): DoS(ν) = 2 +τ k B T lim C(t)e i2πνt dt 4 K 1 C(k t)e i2πνkt/k τ τ k B T k=0 (S2) where t is the time between saving velocities in the MD trajectory (4 fs in our simulations), k B is Boltzmann s constant and K is the number of data points, and the extra factor two in the summation comes from the lower limit being 0 instead of - in the integral (cf. Equation 22 in reference [1]). Note that the Density of States (DoS) in this definition is a dimensionless quantity. The density of states at zero frequency, DoS(0), is associated with the diffusion constant D through (Equation 3.16, reference [6]): D = DoS(0)k BT 12Mm (S3) 7

8 where M is the number of equivalent particles and m is their mass. The 2PT method approximates DoS liquid (ν) = DoS gas (ν)+dos solid (ν) (S4) and if we would have an analytical expression for DoS gas (ν) note that Pascal et al. [3] use the subscript diff rather than gas as we do for consistency here we could subtract this from the DoS(ν) obtained from the simulation (Eq. S2). Indeed, the gaseous (diffusive) component of the density of states DoS(ν) gas, described as a gas of hard spheres (Equation 24, reference [1]) can be written as: ( [ ] DoS(0)πν 2 ) 1 DoS gas (ν) = DoS(0) 1+ (S5) 6fN where f is the fluidicity, the fraction of the 3N degrees of freedom that corresponds to the diffusional parts of the system, or in other words DoS gas (ν)dν =3fN, (S6) 0 independent of DoS(0). A derivation of the equation needed to solve for f can be found in reference [1], the final result being (Equation 12, reference [2]): 2(f 5 / 3 ) 3/2 6(f 5 / 3 ) (f 7 / 3 ) 1/2 + 6(f 5 / 3 ) 1/2 +2f = 2 (S7) where is the dimensionless diffusion constant defined by (Equation 13, reference [2]): = 2DoS(0) 9N ( ) πkb TN 1/2 ( ) N 1/3 ( ) 6 2/3 (S8) M V π with V is the volume of the system. Eq. S7 is monotonous between 0 and 1 (cf. Figure 2 in reference [1]) and hence a bisection algorithm can be used to solve for f given. Now we will try to comprehend the solid component of the density of states, DoS solid (ν). Here, each mode is considered to be harmonic and we use the partition function for a quantum harmonic oscillator as given by McQuarrie [8]: q q HO (ν) = e βhν/2 1 e βhν (S9) where h is Planck s constant, β = 1/k B T. Since the canonical partion function Q of a system is given by the product of the components (Equations , reference [6]): N Q = (S10) and therefore ln Q = 8 q i i=1 N ln q i i=1 (S11)

9 we can write for a system of quantum harmonic oscillators, assuming the frequencies are continuous, that: ln Q = 0 DoS solid (ν)ln q q HO (ν)dν. (S12) This equation is used for deriving the thermodynamic properties from the solid. We use the notation of Pascal et al. [3], but with corrections based on Berens et al. [6]: c Q V = 2k BT = k B 0 ( ln Q ) ( 2 ln Q T + k BT N,V T 2 )N,V DoS solid (ν)w c V solid (ν)dν where the weighting function is defined as: ( W c V W S solid (ν) = T solid (ν)) = T (2 lnqq HO (ν) T T + T 2 lnq q HO (ν) ) T 2 (S13) = (βhν)2 e βhν (1 e βhν ) 2 (S14) Now, finally, we can estimate the heat capacity of the liquids using: c V = k B 0 [ ] DoS gas (ν)w c V gas (ν)+dos solid (ν)w c V solid (ν) dν where the weighting factor for the diffusive part is: (S15) W c V gas = 1 2. (S16) Similar equations have been presented by the Goddard group for the Helmholtz energy, the entropy and the internal energy [1, 2, 3]. Finally, we can compare the heat capacity at constant volume c V to the one at constant presssure c P because they are related according to: c P = c V + VT α2 P κ T (S17) where α P is the volumetric thermal expansion coefficient and κ T the isothermal compressibility (see main text). 9

10 2 Liquidity Test ΔD GAFF OPLS/AA Molecule Figure S1: Liquidity test. The change in MSD, D as defined in the main text. On the x-axis all the simulated molecules are listed in alphabetic order. For all simulations with D 0.5 the trajectories and MSD for the entire simulation was further investigated to ensure that the system was liquid during the whole simulation. 10

11 3 Simulation Results per Property 11

12 Table S1: Name, formula, molecular weight (g/cm 3 ), CAS number and ChemSpider ID for all molecules in the test set. Name Formula MW CAS CSID 1. chloroform CHCl dichloro(fluoro)methane CHCl2F dibromomethane CH2Br dichloromethane CH2Cl methanal CH2O methanoic acid CH2O bromomethane CH3Br methanamide CH3NO nitromethane CH3NO methanol CH4O ,1,1,2,2-pentachloroethane C2HCl ,1,2,2-tetrachloroethane C2H2Cl ,1-dichloroethene C2H2Cl ,1,2-trichloroethane C2H3Cl acetonitrile C2H3N ,2-dibromoethane C2H4Br ,1-dichloroethane C2H4Cl ,2-dichloroethane C2H4Cl methyl formate C2H4O bromoethane C2H5Br chloroethane C2H5Cl chloroethanol C2H5ClO ethanamide C2H5NO N-methylformamide C2H5NO nitroethane C2H5NO methoxymethane C2H6O ethanol C2H6O ,2-ethanedithiol C2H6S methyldisulfanylmethane C2H6S methylsulfinylmethane C2H6OS methylsulfanylmethane C2H6S aminoethanol C2H7NO ethane-1,2-diamine C2H8N prop-2-enenitrile C3H3N

13 Table S1: Name, formula, molecular weight, CAS number, ChemSpider ID - continued. Name Formula MW CAS CSID 35. 1,3-dioxolan-2-one C3H4O propanenitrile C3H5N ,2-dibromopropane C3H6Br ,3-dichloropropane C3H6Cl (2R)-2-methyloxirane C3H6O propan-2-one C3H6O methyl acetate C3H6O ,3-dioxolane C3H6O iodopropane C3H7I bromopropane C3H7Br N,N-dimethylformamide C3H7NO N-methylacetamide C3H7NO nitropropane C3H7NO nitropropane C3H7NO dimethoxymethane C3H8O propane-1,2,3-triol C3H8O propan-1-amine C3H9N propan-2-amine C3H9N methylpropane C4H ethylsulfanylethane C4H10S butane-1-thiol C4H10S butan-1-ol C4H10O methylpropan-2-ol C4H10O butane-1,4-diol C4H10O (2-hydroxyethoxy)ethan-2-ol C4H10O N-ethylethanamine C4H11N butan-1-amine C4H11N methylpropan-2-amine C4H11N (2-hydroxyethylamino)ethanol C4H11NO pyrimidine C4H4N furan C4H4O thiophene C4H4S H-pyrrole C4H5N ethenyl acetate C4H6O

14 Table S1: Name, formula, molecular weight, CAS number, ChemSpider ID - continued. Name Formula MW CAS CSID 69. oxolan-2-one C4H6O acetyl acetate C4H6O ,4-dichlorobutane C4H8Cl oxolane C4H8O ethoxyethene C4H8O ethyl acetate C4H8O tetrahydrothiophene 1,1-dioxide C4H8O2S thiolane C4H8S bromobutane C4H9Br chlorobutane C4H9Cl pyrrolidine C4H9N N,N-dimethylacetamide C4H9NO morpholine C4H9NO pyridine C5H5N cyclopentanone C5H8O cyclopropylethanone C5H8O pentane-2,4-dione C5H8O methyl 2-methylprop-2-enoate C5H8O pentanenitrile C5H9N ethyl propanoate C5H10O diethyl carbonate C5H10O pentan-1-ol C5H12O pentan-3-ol C5H12O methylbutan-2-ol C5H12O pentane-1,5-diol C5H12O pentan-3-amine C5H13N ,2,3,4-tetrafluorobenzene C6H2F ,2,3,5-tetrafluorobenzene C6H2F ,3-difluorobenzene C6H4F ,2-difluorobenzene C6H4F fluorobenzene C6H5F nitrobenzene C6H5NO chloroaniline C6H6ClN phenol C6H6O

15 Table S1: Name, formula, molecular weight, CAS number, ChemSpider ID - continued. Name Formula MW CAS CSID 103. benzenethiol C6H6S methylpyridine C6H7N methylpyridine C6H7N methylpyridine C6H7N cyclohexanone C6H10O (E)-hex-2-ene C6H hexan-2-one C6H12O ,4,6-trimethyl-1,3,5-trioxane C6H12O cyclohexanamine C6H13N propan-2-yloxypropane C6H14O methoxy-2-(2-methoxyethoxy)ethane C6H14O triethyl phosphate C6H15O4P N,N-diethylethanamine C6H15N N-propan-2-ylpropan-2-amine C6H15N trifluoromethylbenzene C7H5F benzonitrile C7H5N benzaldehyde C7H6O toluene C7H methoxybenzene C7H8O phenylmethanol C7H8O methylphenol C7H8O methylphenol C7H8O methylphenol C7H8O diethyl propanedioate C7H12O ,4-dimethylpentan-3-one C7H14O heptan-2-one C7H14O ethenylbenzene C8H phenylethanone C8H8O methyl benzoate C8H8O methyl 2-hydroxybenzoate C8H8O ethylbenzene C8H ,2-dimethylbenzene C8H ,2-dimethoxybenzene C8H10O ,4,6-trimethylpyridine C8H11N

16 Table S1: Name, formula, molecular weight, CAS number, ChemSpider ID - continued. Name Formula MW CAS CSID 137. octan-1-ol C8H18O butoxybutane C8H18O N-butylbutan-1-amine C8H19N isoquinoline C9H7N quinoline C9H7N (1-methylethyl)benzene C9H ,2,4-trimethylbenzene C9H ,6-dimethylheptan-4-one C9H18O chloronaphthalene C10H7Cl phenoxybenzene C12H10O

17 Table S2: Liquid density ρ (g/l) calculated and experimental. Blue font indicates that the calculated value differs more than 5% from the experimental ones, a red font indicates that it differs by more than 10%. The temperature in the calculations is noted in case it deviates from the one used in experiments. Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 1. chloroform [9] ± ± dichloro(fluoro)methane [10] ± ± dibromomethane [11] ± ± [9] ± ± dichloromethane [11] ± ± [9] ± ± methanal [11] ± ± [12] ± ± methanoic acid [11] ± ± [9] ± ± bromomethane [10] ± ± methanamide [9] ± ± nitromethane [11] ± ± [9] ± ± methanol [11] ± ± [9] ± ± ,1,1,2,2-pentachloroethane [11] ± ± ,1,2,2-tetrachloroethane [11] ± ± [9] ± ± ,1-dichloroethene [10] ± ± [10] ± ± ,1,2-trichloroethane [11] ± ± [9] ± ± acetonitrile [11] ± ± [9] ± ± ,2-dibromoethane [9] ± ± ,1-dichloroethane [11] ± ± [9] ± ± ,2-dichloroethane [9] ± ± methyl formate [11] ± ± [9] ± ±

18 Table S2: Liquid density - continued Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 20. bromoethane [11] ± ± [13] ± ± chloroethane [11] ± ± [13] ± ± chloroethanol [11] ± ± ethanamide [11] ± ± N-methylformamide [11] ± ± [9] ± ± nitroethane [9] ± ± methoxymethane [13] ± ± ethanol [11] ± ± [9] ± ± ,2-ethanedithiol [11] ± ± [13] ± ± methyldisulfanylmethane [11] ± ± [13] ± ± methylsulfinylmethane [9] ± ± methylsulfanylmethane [11] ± ± [9] ± ± aminoethanol [11] ± ± [13] ± ± ethane-1,2-diamine [11] ± ± [9] ± ± prop-2-enenitrile [9] ± ± [13] ± ± ,3-dioxolan-2-one [11] ± ± propanenitrile [11] ± ± [9] ± ± ,2-dibromopropane [11] ± ± [10] ± ± ,3-dichloropropane [11] ± ± (2R)-2-methyloxirane [11] ± ±

19 Table S2: Liquid density - continued Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 40. propan-2-one [9] ± ± methyl acetate [11] ± ± [9] ± ± ,3-dioxolane [11] ± ± [9] ± ± iodopropane [11] ± ± [10] ± ± bromopropane [11] ± ± [10] ± ± N,N-dimethylformamide [9] ± ± N-methylacetamide [12] ± ± nitropropane [9] ± ± nitropropane [9] ± ± dimethoxymethane [11] ± ± [10] ± ± propane-1,2,3-triol [11] ± ± [10] ± ± propan-1-amine [11] ± ± [10] ± ± propan-2-amine [11] ± ± [10] ± ± methylpropane [10] ± ± ethylsulfanylethane [11] ± ± [9] ± ± butane-1-thiol [11] ± ± [12] ± ± butan-1-ol [11] ± ± [9] ± ± methylpropan-2-ol [10] ± ± butane-1,4-diol [11] ± ± [9] ± ± [13] ± ±

20 Table S2: Liquid density - continued Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 59. (2-hydroxyethoxy)ethan-2-ol [11] ± ± N-ethylethanamine [11] ± ± [9] ± ± butan-1-amine [11] ± ± [9] ± ± methylpropan-2-amine [11] ± ± [10] ± ± (2-hydroxyethylamino)ethanol [12] ± ± pyrimidine [9] ± ± furan [11] ± ± [9] ± ± thiophene [11] ± ± [12] ± ± H-pyrrole [11] ± ± [9] ± ± ethenyl acetate [11] ± ± oxolan-2-one [11] ± ± acetyl acetate [11] ± ± ,4-dichlorobutane [11] ± ± oxolane [9] ± ± ethoxyethene [11] ± ± ethyl acetate [11] ± ± [9] ± ± tetrahydrothiophene 1,1-dioxide [12] ± ± thiolane [11] ± ± [9] ± ± bromobutane [11] ± ± [9] ± ± chlorobutane [11] ± ± [9] ± ± pyrrolidine [11] ± ± [9] ± ±

21 Table S2: Liquid density - continued Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 80. N,N-dimethylacetamide [9] ± ± morpholine [11] ± ± pyridine [11] ± ± [9] ± ± cyclopentanone [11] ± ± [9] ± ± cyclopropylethanone [11] ± ± [14] ± ± pentane-2,4-dione [9] ± ± methyl 2-methylprop-2-enoate [11] ± ± pentanenitrile [11] ± ± [9] ± ± ethyl propanoate [9] ± ± diethyl carbonate [9] ± ± pentan-1-ol [11] ± ± [9] ± ± [10] ± ± pentan-3-ol [11] ± ± [10] ± ± methylbutan-2-ol [11] ± ± [9] ± ± [10] ± ± pentane-1,5-diol [11] ± ± [9] ± ± pentan-3-amine [11] ± ± [12] ± ± ,2,3,4-tetrafluorobenzene [15] ± ± ,2,3,5-tetrafluorobenzene [16] ± ± ,3-difluorobenzene [11] ± ± [12] ± ± ,2-difluorobenzene [12] ± ± [12] ± ±

22 Table S2: Liquid density - continued Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 99. fluorobenzene [11] ± ± [9] ± ± nitrobenzene [11] ± ± [9] ± ± chloroaniline [11] ± ± phenol [11] ± ± benzenethiol [11] ± ± [12] ± ± methylpyridine [11] ± ± [9] ± ± methylpyridine [11] ± ± [9] ± ± methylpyridine [11] ± ± [9] ± ± cyclohexanone [11] ± ± [9] ± ± (E)-hex-2-ene [11] ± ± hexan-2-one [10] ± ± ,4,6-trimethyl-1,3,5-trioxane [11] ± ± cyclohexanamine [12] ± ± propan-2-yloxypropane [9] ± ± methoxy-2-(2-methoxyethoxy)ethane [11] ± ± [9] ± ± triethyl phosphate [11] ± ± [9] ± ± [12] ± ± N,N-diethylethanamine [11] ± ± [9] ± ± N-propan-2-ylpropan-2-amine [11] ± ± [10] ± ± trifluoromethylbenzene [11] ± ± [12] ± ±

23 Table S2: Liquid density - continued Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 118. benzonitrile [11] ± ± benzaldehyde [9] ± ± toluene [9] ± ± methoxybenzene [11] ± ± [9] ± ± phenylmethanol [11] ± ± methylphenol [11] ± ± methylphenol [10] ± ± methylphenol [11] ± ± [10] ± ± diethyl propanedioate [11] ± ± ,4-dimethylpentan-3-one [11] ± ± [10] ± ± heptan-2-one [11] ± ± [9] ± ± ethenylbenzene [9] ± ± phenylethanone [11] ± ± [9] ± ± methyl benzoate [9] ± ± methyl 2-hydroxybenzoate [11] ± ± [12] ± ± ethylbenzene [9] ± ± ,2-dimethylbenzene [10] ± ± [9] ± ± ,2-dimethoxybenzene [9] ± ± ,4,6-trimethylpyridine [11] ± ± [9] ± ± octan-1-ol [9] ± ± [10] ± ± butoxybutane [11] ± ± [9] ± ± N-butylbutan-1-amine [11] ± ± [9] ± ±

24 Table S2: Liquid density - continued Experiment GAFF OPLS/AA CGenFF Name T ρ Ref. ρ ρ ρ 140. isoquinoline [11] ± ± [12] ± ± quinoline [11] ± ± [9] ± ± (1-methylethyl)benzene [9] ± ± ,2,4-trimethylbenzene [12] ± ± [12] ± ± ,6-dimethylheptan-4-one [11] ± ± [10] ± ± chloronaphthalene [11] ± ± phenoxybenzene [11] ± ±

25 Table S3: Heat of vaporization Hvap (kj/mol) calculated and experimental. Blue font indicates that the calculated value differs more than 10% from the experimental ones, a red font indicates that it differs by more than 25%. The temperature in the calculations is noted in case it deviates from the one used in experiments. Experiment GAFF OPLS/AA CGenFF Name T Hvap Ref. Hvap Hvap Hvap 1. chloroform [9] ± ± dichloro(fluoro)methane [13] ± ± dibromomethane [13] ± ± [9] ± ± dichloromethane [13] ± ± [9] ± ± methanal [13] ± ± [13] ± ± methanoic acid [13] ± ± [9] ± ± methanamide [9] ± ± nitromethane [13] ± ± [9] ± ± methanol [13] ± ± [9] ± ± ,1,1,2,2-pentachloroethane [13] ± ± ,1,2,2-tetrachloroethane [13] ± ± [9] ± ± ,1-dichloroethene [13] ± ± [13] ± ± ,1,2-trichloroethane [13] ± ± [9] ± ± acetonitrile [13] ± ± [9] ± ± ,2-dibromoethane [9] ± ± ,1-dichloroethane [13] ± ± [9] ± ± ,2-dichloroethane [9] ± ± methyl formate [13] ± ± [9] ± ±

26 Table S3: Heat of vaporization - continued Experiment GAFF OPLS/AA CGenFF Name T Hvap Ref. Hvap Hvap Hvap 20. bromoethane [13] ± ± [13] ± ± chloroethane [13] ± ± [13] ± ± chloroethanol [13] ± ± ethanamide [13] ± ± N-methylformamide [13] ± ± [9] ± ± nitroethane [9] ± ± methoxymethane [13] ± ± ethanol [13] ± ± [9] ± ± ,2-ethanedithiol [13] ± ± [13] ± ± methyldisulfanylmethane [13] ± ± [13] ± ± methylsulfinylmethane [9] ± ± methylsulfanylmethane [13] ± ± [9] ± ± aminoethanol [13] ± ± [13] ± ± ethane-1,2-diamine [13] ± ± [9] ± ± prop-2-enenitrile [9] ± ± [13] ± ± ,3-dioxolan-2-one [13] ± ± propanenitrile [13] ± ± [9] ± ± ,2-dibromopropane [12] ± ± [17] ± ± ,3-dichloropropane [13] ± ± (2R)-2-methyloxirane [17] ± ±

27 Table S3: Heat of vaporization - continued Experiment GAFF OPLS/AA CGenFF Name T Hvap Ref. Hvap Hvap Hvap 40. propan-2-one [9] ± ± methyl acetate [13] ± ± [9] ± ± ,3-dioxolane [17] ± ± [9] ± ± iodopropane [13] ± ± [13] ± ± bromopropane [13] ± ± [13] ± ± N,N-dimethylformamide [9] ± ± N-methylacetamide [13] ± ± nitropropane [9] ± ± nitropropane [9] ± ± dimethoxymethane [13] ± ± [13] ± ± propane-1,2,3-triol [13] ± ± propan-1-amine [13] ± ± [13] ± ± propan-2-amine [13] ± ± [13] ± ± methylpropane [13] ± ± ethylsulfanylethane [13] ± ± [9] ± ± butane-1-thiol [12] ± ± [12] ± ± butan-1-ol [13] ± ± [9] ± ± methylpropan-2-ol [13] ± ± butane-1,4-diol [13] ± ± [9] ± ± [13] ± ± (2-hydroxyethoxy)ethan-2-ol [13] ± ±

28 Table S3: Heat of vaporization - continued Experiment GAFF OPLS/AA CGenFF Name T Hvap Ref. Hvap Hvap Hvap 60. N-ethylethanamine [13] ± ± [9] ± ± butan-1-amine [13] ± ± [9] ± ± methylpropan-2-amine [13] ± ± [13] ± ± (2-hydroxyethylamino)ethanol [13] ± ± pyrimidine [9] ± ± furan [13] ± ± [9] ± ± thiophene [13] ± ± [13] ± ± H-pyrrole [13] ± ± [9] ± ± ethenyl acetate [13] ± ± oxolan-2-one [12] ± ± acetyl acetate [13] ± ± ,4-dichlorobutane [13] ± ± oxolane [9] ± ± ethoxyethene [13] ± ± ethyl acetate [13] ± ± [9] ± ± tetrahydrothiophene 1,1-dioxide [13] ± ± thiolane [13] ± ± [9] ± ± bromobutane [13] ± ± [9] ± ± chlorobutane [12] ± ± [9] ± ± pyrrolidine [13] ± ± [9] ± ± N,N-dimethylacetamide [9] ± ±

29 Table S3: Heat of vaporization - continued Experiment GAFF OPLS/AA CGenFF Name T Hvap Ref. Hvap Hvap Hvap 81. morpholine [13] ± ± pyridine [13] ± ± [9] ± ± cyclopentanone [13] ± ± [9] ± ± cyclopropylethanone ± ± [17] ± ± pentane-2,4-dione [9] ± ± methyl 2-methylprop-2-enoate [13] ± ± pentanenitrile [13] ± ± [9] ± ± ethyl propanoate [9] ± ± diethyl carbonate [9] ± ± pentan-1-ol [13] ± ± [9] ± ± [13] ± ± pentan-3-ol [13] ± ± [13] ± ± methylbutan-2-ol [13] ± ± [9] ± ± [13] ± ± pentane-1,5-diol [13] ± ± [9] ± ± pentan-3-amine [12] ± ± [12] ± ± ,2,3,4-tetrafluorobenzene [18] ± ± ,2,3,5-tetrafluorobenzene [18] ± ± ,3-difluorobenzene [12] ± ± [12] ± ± ,2-difluorobenzene [12] ± ± [12] ± ± fluorobenzene [13] ± ± [9] ± ±