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Supplemental Material for:
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A Molecular Dynamics study of chirality transfer from chiral
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surfaces to nearby solvents
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S. Wang and N. M. Cann1
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Department of Chemistry, Queen’s University, Kingston, Ontario, Canada K7L 3N6
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Telephone:
613-533-2651
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FAX:
613-533-6669
E-mail:
ncann@chem.queensu.ca
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Running title: Chirality transfer from surface to solvent
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Content: Details of the potentials for 2-propanol, including the potential parameters that
have been developed in this work, are provided.
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1
Author to whom correspondence should be addressed
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Semi-flexible models for 2-propanol developed in this work are described herein. Models
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for other solvents and the selectors can be found elsewhere1,2.
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The intramolecular potential, which dictates the energetic costs for changes in
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molecular conformations, consists of four parts: bond stretching, angle bending, dihedral
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torsion, and improper torsion. These potentials are listed in Eq.[4]-[7]. In this work, all
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bonds of 2-propanol are kept fixed using the Rattle algorithm3 during the simulations, and
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19 bends and 3 torsions are employed to represent the molecular flexibility. The
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equilibrium bond angles are obtained from the global energy minimum and bending
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potentials are obtained by least squares fits of Eq.[5] to nine energy calculations, where
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the angle is varied within sixteen degrees of the equilibrium value. As shown in Eq.[6],
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the torsions are represented by modified Rickaert-Bellemans4 potentials. Each torsional
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potential is extracted from 36 B3LYP/aug-cc-pVDZ calculations as the angle is varied
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from zero to 360 degrees, in steps of 10 degrees.
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Initial atomic positions and CHELPG charges5 are extracted from B3LYP/aug-cc-
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pVDZ global energy minimum. For the nonbonding potential parameters, the CHARMM
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parameters for Lennard-Jones (LJ) potential and CHELPG charges from the ab initio
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global minimum are applied.
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The parameterization of the fluctuating charge (FC) model has been discussed in
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detail previously6. Briefly, the molecule was placed in 30 diverse fields and atomic
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charges were evaluated by the CHELPG algorithm applied to B3LYP/aug-cc-pVDZ
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0
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calculations. Based on the fitting of the molecular response, the ~i and J ii parameters
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were extracted. Similar to the previous findings2, the atomic electronegativities derived
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specifically for 2-propanol were larger than the transferrable CHARMM-FQ values7 for
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most atoms. All electronic structure calculations are performed using the Gaussian 03
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program7.
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LJ and FC parameters
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Atom
No.
Atom
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O
0.312
2
H
3
σ(Å)
ε
(kJ/mol)
CHARMM
J
0
ii
J ii0 (this
CHARMM
~ o
~o
Shifted 
i
~io (this
Q i0 (|e|)
(kcal/mol.|e|)
364.85
(kcal/mol |e|)
0.7113
(kcal/mol.|e|2)
307.20
work)
(kcal/mol.|e|2)
317.07
101.66
work)
(kcal/mol.|e|)
107.41
0.05
0.1000
517.26
544.06
263.19
0.00
0.00
0.369
C
0.35
0.2761
196.88
212.95
306.79
43.60
71.68
0.591
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H
0.25
0.1255
501.42
470.07
319.83
56.64
66.18
-0.084
5
C
0.35
0.2761
240.34
283.89
319.65
56.46
66.16
-0.298
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C
0.35
0.2761
240.34
283.89
319.65
56.46
66.16
-0.298
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H
0.25
0.1255
501.42
576.59
315.56
52.37
50.94
0.067
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H
0.25
0.1255
501.42
576.59
315.56
52.37
50.94
0.067
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H
0.25
0.1255
501.42
576.59
315.56
52.37
50.94
0.067
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H
0.25
0.1255
501.42
576.59
315.56
52.37
50.94
0.067
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H
0.25
0.1255
501.42
576.59
315.56
52.37
50.94
0.067
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H
0.25
0.1255
501.42
576.59
315.56
52.37
50.94
0.067
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8
i
.
-0.685
Angle bending
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Angle
θ(deg)
kθ(kJ. mol-1 . deg-2)
3,1,2
108.81
0.065813
4,3,1
108.80
0.090213
5,3,1
108.72
0.121507
6,3,1
108.72
0.121507
5,3,4
108.81
0.077831
6,3,4
108.81
0.077831
6,3,5
112.87
0.107790
7,5,3
110.56
0.066107
8,5,3
110.56
0.066107
9,5,3
110.56
0.066107
8,5,7
108.36
0.060220
9,5,7
108.36
0.060220
9,5,8
108.36
0.060220
10,6,3
110.56
0.066107
11,6,3
110.56
0.066107
12,6,3
110.56
0.066107
11,6,10
108.36
0.060220
12,6,10
108.36
0.060220
12,6,11
108.36
0.060220
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Torsions
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4
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Torsion
c0, c1, c2, c3, c4, c5, c6 (kJ/mol)
2,1,3,4
7.76,1.89,6.06,10.76,-4.56,-0.94,2.44
1,3,5,7
6.66,-20.53,2.04,28.26,-7.61,-0.96,5.68
1,3,6,10
6.66,-20.53,2.04,28.26,-7.61,-0.96,5.68
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References for Supplemental Materials
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S. Nita and N. M. Cann, J. Phys. Chem. B 112 (41), 13022 (2008); C. F. Zhao and N. M. Cann,
Anal. Chem. 80 (7), 2426 (2008).
S. H. Wang and N. M. Cann, J. Chem. Phys. 129 (5), 21 (2008).
H. C. Andersen, J. Comput. Phys. 52 (1), 24 (1983).
J. P. Ryckaert and A. Bellemans, Faraday Discuss. 66, 95 (1978).
C. M. Breneman and K. B. Wiberg, J. Comput. Chem. 11 (3), 361 (1990).
S. H. Wang and N. M. Cann, J. Chem. Phys. 126 (21), 23 (2007).
S. Patel and C. L. Brooks, J. Comput. Phys. 25 (1), 1 (2004).
M.J.T. Frisch, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;
Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.;
Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.;
Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;
Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.;
Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A.
G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.;
Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.;
Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople,
J. A.;, in, Gaussian Inc., Wallingford CT, 2004.