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A molecular dynamics investigation on thermo-physical properties and hydrogen-bonding of 1-ethyl-3-methylimidazolium dimethylphosphate-
water working fluids
Tianyu Lia,b, Zongchang Zhaoa,b,1, Xiaodong Zhangc,a State Key Laboratory of Fine Chemicals, Dalian University of Technology, P.R. China
bResearch Institute of Chemical Engineering, Dalian University of Technology, P.R. China
c Research Institute of Chemical Machinery, Dalian University of Technology, No.2 Linggong
Road, Dalian, 116024, P.R. China
1 Corresponding author: Zongchang ZhaoEmail address: [email protected]
Figure.S1. (a) Mean-square displacement (MSD) of geometrical center and linear fit of all particles of pure [Emim][Dmp] at 293.15 K; (b) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.200 at 293.15 K; (c) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.400 at 293.15 K; (d) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.600 at 293.15 K; (e) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.800 at 293.15 K.
Figure.S2. (a) Mean-square displacement (MSD) of geometrical center and linear fit of all particles of pure [Emim][Dmp] at 313.15 K; (b) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.200 at 313.15 K; (c) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.400 at 313.15 K; (d) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.600 at 313.15 K; (e) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.800 at 313.15 K.
Figure.S3. (a) Mean-square displacement (MSD) of geometrical center and linear fit of all particles of pure [Emim][Dmp] at 333.15 K; (b) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.200 at 333.15 K; (c) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.400 at 333.15 K; (d) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.600 at 333.15 K; (e) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.800 at 333.15 K.
Figure.S4. (a) Mean-square displacement (MSD) of geometrical center and linear fit of all particles of pure [Emim][Dmp] at 353.15 K; (b) MSD and linear fit of all particles of geometrical center of [Emim][Dmp] with H2O mole fraction of 0.200 at 353.15 K; (c) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.400 at 353.15 K; (d) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.600 at 373.15 K; (e) MSD of geometrical center and linear fit of all particles of [Emim][Dmp] with H2O mole fraction of 0.800 at 373.15 K.
Table S1The results of self-diffusion coefficients of each system at different temperature (293.15 K-
373.15 K).[Emim][Dmp]
T/K DIL
/(10-11m2/s)D+
/(10-11m2/s)D-
/(10-11m2/s)293.15 1.0759 1.4055 0.5857313.15 2.8871 3.9257 1.3743333.15 5.7865 6.9004 3.5316353.15 11.2029 14.3694 7.3783373.15 20.2820 26.1154 11.7849
[Emim][Dmp] with H2O(xH2O=0.2)
T/K DAll
/(10-11m2/s)DIl
/(10-11m2/s)D+
/(10-11m2/s)D-
/(10-11m2/s)DH20
/(10-11m2/s)293.15 1.0766 1.0623 1.2712 0.7710 1.3047313.15 2.4445 2.4314 3.1756 1.3169 2.9873333.15 6.0026 5.9885 7.5792 3.6525 6.6495353.15 10.0768 10.0429 12.2206 6.3300 20.6212373.15 20.1436 19.3215 23.0402 14.6464 38.7207
[Emim][Dmp] with H2O(xH2O=0.4)
T/K DAll
/(10-11m2/s)DIl
/(10-11m2/s)D+
/(10-11m2/s)D-
/(10-11m2/s)DH20
/(10-11m2/s)293.15 0.956 0.932 1.160 0.592 1.487
313.15 2.841 2.724 3.469 1.638 4.669333.15 6.725 6.529 8.263 4.035 10.006353.15 9.617 9.119 11.072 6.312 19.408373.15 20.053 19.065 23.615 12.400 35.922
[Emim][Dmp] with H2O(xH2O=0.6)
T/K DAll
/(10-11m2/s)DIl
/(10-11m2/s)D+
/(10-11m2/s)D-
/(10-11m2/s)DH20
/(10-11m2/s)293.15 0.945 0.839 0.971 0.649 1.680313.15 2.747 2.415 2.989 1.577 5.125333.15 6.985 6.070 7.632 3.781 13.479353.15 13.429 11.691 13.371 9.251 25.616373.15 28.250 24.432 29.972 16.350 55.378
[Emim][Dmp] with H2O(xH2O=0.8)
T/K DAll
/(10-11m2/s)DIL
/(10-11m2/s)D+
/(10-11m2/s)D-
/(10-11m2/s)DH20
/(10-11m2/s)293.15 3.296 2.293 2.673 1.735 5.976313.15 8.936 5.839 6.742 4.495 17.278333.15 17.502 11.990 14.350 8.538 32.250353.15 36.526 24.902 27.663 20.834 67.516373.15 64.296 41.204 46.084 34.064 109.371
Figure S5. Radial distribution functions of [Emim] [Dmp] with H2O (xH2O=0.000). (a) RDFs of ion-ion at 293.15 K; (b) RDFs of H2 at 293.15 K; (c) RDFs of P20-1 at 293.15 K; (d) RDFs of P20-2 at 293.15 K; (e) RDFs of H19 at 293.15 K.
Figure S6. Radial distribution functions of [Emim] [Dmp] with H2O (xH2O=0.000). (a) RDFs of ion-ion at 313.15 K; (b) RDFs of H2 at 313.15 K; (c) RDFs of P20-1 at 313.15 K; (d) RDFs of P20-2 at 313.15 K; (e) RDFs of H19 at 313.15 K.
Figure S7. Radial distribution functions of [Emim] [Dmp] with H2O (xH2O=0.000). (a) RDFs of ion-ion at 373.15 K; (b) RDFs of H2 at 373.15 K; (c) RDFs of P20-1 at 373.15 K; (d) RDFs of P20-2 at 373.15 K; (e) RDFs of H19 at 373.15 K.
Figure S8. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.200). (a) RDFs of cation at 293.15 K; (b) RDFs of anion at 293.15 K (c) RDFs of H2 at 293.15 K; (d) RDFs of O33 at 293.15 K; (e) RDFs of P20 at 293.15 K.
Figure S9. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.200). (a) RDFs of cation at 353.15 K; (b) RDFs of anion at 353.15 K; (c) RDFs of H2 at 353.15 K; (d) RDFs of O33 at 353.15 K; (e) RDFs of P20 at 353.15 K.
Figure S10. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.200). (a) RDFs of cation at 373.15 K; (b) RDFs of anion at 373.15 K; (c) RDFs of H2 at 373.15 K; (d) RDFs of O33 at 373.15 K; (e) RDFs of P20 at 373.15 K.
Figure S11. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.400). (a) RDFs of cation at 293.15 K; (b) RDFs of anion at 293.15 K; (c) RDFs of H2 at 293.15 K; (d) RDFs of O21 at 293.15 K; (e) RDFs of O33 at 293.15 K.
Figure S12. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.400). (a) RDFs of cation at 353.15 K; (b) RDFs of anion at 353.15 K; (c) RDFs of H2 at 353.15 K; (d) RDFs of O21 at 353.15 K; (e) RDFs of O33 at 353.15 K.
Figure S13. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.400). (a) RDFs of cation at 373.15 K; (b) RDFs of anion at 373.15 K; (c) RDFs of H2 at 373.15 K; (d) RDFs of O21 at 373.15 K; (e) RDFs of O33 at 373.15 K.
Figure S14. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.600). (a) RDFs of cation at 313.15 K; (b) RDFs of anion at 313.15 K; (c) RDFs of H2 at 313.15 K; (d) RDFs of O21 at 313.15 K; (e) RDFs of O33 at 313.15 K.
Figure S15. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.600). (a) RDFs of cation at 353.15 K; (b) RDFs of anion at 353.15 K; (c) RDFs of H2 at 353.15 K; (d) RDFs of O21 at 353.15 K; (e) RDFs of O33 at 353.15 K.
Figure S16. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.600). (a) RDFs of cation at 373.15 K; (b) RDFs of anion at 373.15 K; (c) RDFs of H2 at 373.15 K; (d) RDFs of O21 at 373.15 K; (e) RDFs of H34 at 373.15 K.
Figure S17. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.800). (a) RDFs of cation at 293.15 K; (b) RDFs of anion at 293.15 K; (c) RDFs of H2 at 293.15 K; (d) RDFs of O21 at 293.15 K; (e) RDFs of O33 at 293.15 K.
Figure S18. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.800). (a) RDFs of cation at 313.15 K; (b) RDFs of anion at 313.15 K; (c) RDFs of H2 at 313.15 K; (d) RDFs of O21 at 313.15 K; (e) RDFs of O33 at 313.15 K.
Figure S19. Radial distribution functions of [Emim][Dmp] with H2O (xH2O=0.800). (a) RDFs of cation at 373.15 K; (b) RDFs of anion at 373.15 K; (c) RDFs of H2 at 373.15 K; (d) RDFs of O21 at 373.15 K; (e) RDFs of O33 at 373.15 K.
Figure S20. Radial distribution functions of Emim at water mole fraction at 0.200 at 333.15 K.
Table S2. Force field for [Emim][Dmp]Atom ID Mass/amu q/e σ/Å ε/(KJ·mol)
Cation (Emim)C1 12.0110 0.0971 3.3997 0.3598H2 1.0080 0.1326 2.4215 0.0628N3 14.0067 0.0786 3.2500 0.7113N4 14.0067 0.0053 3.2500 0.7113C5 12.0110 -0.1526 3.3997 0.3598H6 1.0080 0.1664 2.5106 0.0628C7 12.0110 -0.1697 3.3997 0.3598H8 1.0080 0.1861 2.5106 0.0628C9 12.0110 0.1982 3.3997 0.4577
H10 1.0080 -0.0092 2.4714 0.0657H11 1.0080 0.0524 2.4714 0.0657C12 12.0110 -0.0543 3.3997 0.4577H13 1.0080 0.0375 2.4714 0.0657H14 1.0080 0.0029 2.4714 0.0657H15 1.0080 0.0321 2.4714 0.0657C16 12.0110 -0.0456 3.3997 0.4577H17 1.0080 0.0710 2.4714 0.0657H18 1.0080 0.0560 2.4714 0.0657H19 1.0080 0.0950 2.4714 0.0657
Anion (Dmp)P20 30.9738 1.3244 3.7400 0.8364O21 15.9994 -0.7787 3.1500 0.8782O22 15.9994 -0.7399 3.1500 0.8782O23 15.9994 -0.5331 2.9000 0.5858O24 15.9994 -0.4492 2.9000 0.5858C25 12.0110 0.2122 3.5000 0.2761H26 1.0080 0.0265 2.5000 0.1255H27 1.0080 -0.0118 2.5000 0.1255H28 1.0080 -0.0067 2.5000 0.1255C29 12.0110 0.1266 3.5000 0.2761H30 1.0080 0.0048 2.5000 0.1255H31 1.0080 0.0396 2.5000 0.1255H32 1.0080 0.0055 2.5000 0.1255
Bonds kb/(KJ·mol-1·Å-2) r0/Å Angles kθ/(KJ·mol-1·rad-2) θ0
Cation (Emim)C1-H2 767.7648 1.0800 H2-C1-N3 146.4400 125.5000C1-N3 997.8848 1.3430 H2-C1-N4 146.4400 125.5400C1-N4 997.8848 1.3430 N3-C1-N4 146.4400 108.9900N3-C5 893.2848 1.3810 C1-N3-N5 146.4400 108.3600
N3-C16 705.0048 1.4750 C1-N3-C16 146.4400 125.9200N4-C7 893.2848 1.3810 C5-N3-C16 146.4400 125.7100N4-C9 705.0048 1.4750 C1-N4-C7 146.4400 108.3300C5-H6 767.7648 1.0800 C1-N4-C9 146.4400 125.7600C5-C7 1070.5923 1.3750 C7-N4-C9 146.4400 125.8000C7-H8 767.3971 1.0800 N3-C5-H6 73.2200 122.2200C9-10 710.9403 1.0900 N3-C5-C7 146.4400 107.0900
C9-H11 710.9403 1.0900 H6-C5-C7 73.2200 130.7500C9-C12 560.3882 1.5290 N4-C7-C5 146.4400 107.2300
C12-H13 710.9403 1.0900 N4-C7-H8 73.2200 122.2300C12-H14 710.9403 1.0900 C5-C7-H8 73.2200 130.5400C1-H15 710.9403 1.0900 N4-C9-H10 104.6000 106.7400C16-H17 710.9403 1.0900 N4-C9-H11 104.6000 106.5800C16-H18 710.9403 1.0900 N4-C9-C12 104.6000 112.4200C16-H19 710.9403 1.0900 H10-C9-H11 73.2200 107.5100
H10-C9-C12 104.6000 111.7500H11-C9-C12 104.6000 111.5100C9-C12-H13 104.6000 108.9400C9-C12-H14 104.6000 111.7200C9-C12-H15 104.6000 111.4100
H13-C12-H14 73.2200 107.8000H13-C12-H15 73.2200 108.1400H14-C12-H15 73.2200 108.7100N3 -C16-H17 73.2200 109.4400N3-C16-H18 73.2200 109.4500N3-C16-H19 73.2200 108.9600
H17-C16-H18 73.2200 110.1200H17-C16-H19 73.2200 109.4400H18-C16-H19 73.2200 109.4100
Anion (Dmp)P20-O21 2195.5507 1.4975 O21-P20-O22 585.4797 123.4450P20-O22 2195.5507 1.4975 O21-P20-O23 418.1992 107.1940P20-O23 961.8602 1.6797 O21-P20-O24 418.1992 109.7470P20-O24 961.8602 1.6797 O22-P20-O23 418.1992 109.7310O23-C25 1338.2403 1.4172 O22-P20-O24 418.1992 107.1680O24-C29 1338.2403 1.4172 O23-P20 -O24 188.1880 96.1410C25-H26 1421.8805 1.0951 P20-O23-C25 418.1992 118.4920C25-H27 1421.8805 1.0951 P20-O24-C29 418.1992 117.2300C25-H28 1421.8805 1.0951 O23-C25-H26 209.0996 107.2860C29-H30 1421.8805 1.0951 O23-C25 -H27 209.0996 111.1380C29-H31 1421.8805 1.0951 O23-C25-H28 209.0996 110.9930C29-H32 1421.8805 1.0951 H26-C25 -H27 146.3689 109.6400
H26-C25-H28 146.3689 109.0130H27-C25-H28 146.3689 108.7370O24-C29-H30 209.0996 111.5210O24-C29-H31 209.0996 107.5770O24-C29-H32 209.0996 111.2190H30-C29-H31 146.3689 108.4820H30-C29-H32 146.3689 108.5850H31-C29-H32 146.3689 109.4000
Dihedrals K1/(KJ·mol-1·Å-2) K2/(KJ·mol-1·Å-2) K3(KJ·mol-1·Å-2) K4(KJ·mol-1·Å-2) K5(KJ·mol-1·Å-2)Cation (Emim)
H2-C1-N3-C5 12.5520 0.0000 -12.5520 0.0000 0.0000 H2-C1-N3-C16 12.5520 0.0000 -12.5520 0.0000 0.0000
N4-C1-N3-C5 100.4202 0.0000 -100.4202 0.0000 0.0000 N4-C1-N3-C16 16.7360 0.0000 -16.7360 0.0000 0.0000 H2-C1-N4-C7 12.5520 0.0000 -12.5520 0.0000 0.0000 H2-C1-N4-C9 12.5520 0.0000 -12.5520 0.0000 0.0000 N3-C1-N4-C7 100.4202 0.0000 -100.4202 0.0000 0.0000 N3-C1-N4-C9 16.7360 0.0000 -16.7360 0.0000 0.0000 C1-N3-C5-H6 16.7360 0.0000 -16.7360 0.0000 0.0000 C1-N3-C5-C7 16.7360 0.0000 -16.7360 0.0000 0.0000 C1-N3-C5-H6 12.5520 0.0000 -12.5520 0.0000 0.0000 C1-N3-C5-C7 16.7360 0.0000 -16.7360 0.0000 0.0000
C1-N3-C16-H17 0.6862 -2.0585 0.0000 2.7447 0.0000 C1-N3-C16-H18 0.6862 -2.0585 0.0000 2.7447 0.0000 C1-N3-C16-H19 0.6862 -2.0585 0.0000 2.7447 0.0000 C5-N3-C16-H17 1.0209 -3.0627 0.0000 4.0836 0.0000 C5-N3-C16-H18 1.0209 -3.0627 0.0000 4.0836 0.0000 C5-N3-C16-H19 1.0209 -3.0627 0.0000 4.0836 0.0000
C1-N4-C7-C5 16.7360 0.0000 -16.7360 0.0000 0.0000 C1-N4-C7-H8 16.7360 0.0000 -16.7360 0.0000 0.0000 C9-N4-C7-C5 16.7360 0.0000 -16.7360 0.0000 0.0000 C9-N4-C7-H8 12.5520 0.0000 -12.5520 0.0000 0.0000 C1-N4-C9-H10 0.6862 -2.0585 0.0000 2.7447 0.0000 C1-N4-C9-H11 0.6862 -2.0585 0.0000 2.7447 0.0000 C1-N4-C9-C12 0.9870 -0.9870 0.0000 0.0000 0.0000 C7-N4-C9-H10 1.0209 -3.0627 0.0000 4.0836 0.0000 C7-N4-C9-H11 1.0209 -3.0627 0.0000 4.0836 0.0000 C7-N4-C9-C12 0.9870 -0.9870 0.0000 0.0000 0.0000 N3-C5-C7-N4 100.4202 0.0000 -100.4202 0.0000 0.0000 N3-C5-C7-H8 12.5520 0.0000 -12.5520 0.0000 0.0000 H6-C5-C7-N4 12.5520 0.0000 -12.5520 0.0000 0.0000 H6-C5-C7-H8 12.5520 0.0000 -12.5520 0.0000 0.0000
N4-C9-C12-H13 0.6690 -2.0071 0.0000 2.6761 0.0000 N4-C9-C12-H14 0.6690 -2.0071 0.0000 2.6761 0.0000 N4-C9-C12-H15 0.6690 -2.0071 0.0000 2.6761 0.0000H10-C9-C12-H13 0.6280 -2.0071 0.0000 2.5121 0.0000H10-C9-C12-H14 0.6280 -2.0071 0.0000 2.5121 0.0000H10-C9-C12-H15 0.6280 -2.0071 0.0000 2.5121 0.0000H11-C9-C12-H13 0.6280 -2.0071 0.0000 2.5121 0.0000H11-C9-C12-H14 0.6280 -2.0071 0.0000 2.5121 0.0000H11-C9-C12-H15 0.6280 -2.0071 0.0000 2.5121 0.0000
Anion (Dmp)O21-P20-O23-C25 4.1422 -0.6150 -22.3384 0.0000 18.8113O22-P20-O23-C25 4.1422 -0.6150 -22.3384 0.0000 18.8113O24-P20-O23-C25 8.6818 14.5394 -19.8740 -20.0832 16.7360O21-P20-O24-C29 4.1422 -0.6150 -22.3384 0.0000 18.8113O22-P20-O24-C29 4.1422 -0.6150 -22.3384 0.0000 18.8113O23-P20-O24-C29 8.6818 14.5394 -19.8740 -20.0832 16.7360P20-O23-C25-H26 2.6137 -0.3732 -14.1900 0.0000 11.9495P20-O23-C25-H27 2.6137 -0.3732 -14.1900 0.0000 11.9495P20-O23-C25-H28 2.6137 -0.3732 -14.1900 0.0000 11.9495P20-O24-C29-H30 2.6137 -0.3732 -14.1900 0.0000 11.9495P20-O24-C29-H31 2.6137 -0.3732 -14.1900 0.0000 11.9495P20-O24-C29-H32 2.6137 -0.3732 -14.1900 0.0000 11.9495
