ELECTRONIC SUPPLEMENTARY MATERIAL
A Density Functional Theory Study on the Interaction
of Paraffins, Olefins and Acetylenes with Na-ETS-10
Renjith S. Pillai,1 Miguel Jorge,2 José R. B. Gomes1,*
1
CICECO, Departamento de Química, Universidade de Aveiro, Campus Universitário de
Santiago, P-3810-193 Aveiro, Portugal
2
Department of Chemical and Process Engineering, University of Strathclyde, 75 Montrose
Street, Glasgow G1 1XJ, United Kingdom
*Corresponding author.
E-mail: jrgomes@ua.pt
Phone: +351 234401423
Fax: +351 234401470
Table S1. Comparison of selected geometrical parameters for the bare ETS-10 cluster model
with M06-L, experimental and ONIOM taken from the literature.
Parametera
Exptl. [1]
ONIOM
M06L
method [2]
1
a
Tix-Oy
1.99±0.01
1.91 - 2.13
1.90-2.12
Tix-O5
1.872±0.001
1.94
1.85-1.88
Na2-Oz
2.57±0.01
2.402.42
Na2-O5
2.62±0.03
2.25
Ti1-O5-Ti2
177.9
172.23
Atomic labeling in Figure 1 with x=1 or 2, y=1-4 or 6-9, z=1, 2, 6 or 7; distances in Å and
angles in degrees.
2
Table S2. Sodium to adsorbate and sodium to framework oxygens distances (Å) optimized at the M06-L/6-31G(d,p) level of theory
using BSSE corrections.a
Bare
CH4b
C2H6
C2H4
C2H2
C3H8
C3H6
C3H4
Na2-adsorbate
―
2.88
2.96
2.77
2.74
3.25
2.73
2.91
Na2-O1
2.42
2.42
2.40
2.41
2.41
2.40
2.42
2.41
Na2-O2
2.42
2.42
2.43
2.42
2.41
2.43
2.43
2.42
Na2-O5
2.25
2.25
2.24
2.24
2.23
2.23
2.24
2.24
Na2-O6
2.42
2.42
2.43
2.41
2.43
2.43
2.41
2.42
Na2-O7
2.42
2.42
2.41
2.42
2.43
2.41
2.41
2.44
a
b
Distances in the bare model are also provided for comparison purposes. Nearest neighbor distances, except for methane where the
Na2-C distance is given. bFrom our previous study.
b
3
(a)
(b)
4
(c)
Figure S1. Views of the most relevant BCP for the interaction of C3Hx hydrocarbons (top,
propane; middle, propene; bottom, propyne) with Na-ETS-10. Small black and orange spheres
correspond to the BCP between the hydrocarbon and the Na2 ion, and between the terminal
methyl group and framework oxygen atoms, respectively. Color code for molecular model:
Bluish-green for Ti, yellow for Si, red for O, violet for Na, grey for C and white for H. Values of
the electron density, ρ, at the BCP are provided in ea0-3 units.
5
Figure S2. Variation of the enthalpy for the interaction between different sorbates and Na-ETS10 with the corresponding electron densities at the bond critical points in the region between the
sorbates and the Na2 ion. Equation and trendline were adjusted with interaction enthalpies for
C3Hx hydrocarbons subtracted by -14 kJ·mol-1. Notice that the enthalpies were multiplied by -1.
6
Table S3. Comparison of relevant calculated and experimental vibrational frequencies (cm-1) for
ethane in vacuum.
Calculateda
Unscaled
3161 (CH3 de-st)
3138 (CH3 de-st)
3061 (CH3 s-st)
3061 (CH3 s-st)
1494 (CH3 de-d)
1494 (CH3 de-d)
1422 (CH3 s-d)
1397 (CH3 s-d)
1215 (CH3 r)
1034 (C-C st)
829 (CH3 r)
312 (tr)
Scaled
3000 (CH3 de-st)
2978 (CH3 de-st)
2905 (CH3 s-st)
2905 (CH3 s-st)
1418 (CH3 de-d)
1418 (CH3 de-d)
1350 (CH3 s-d)
1326 (CH3 s-d)
1153 (CH3 r)
981 (C-C st)
829 (CH3 r)
312 (tr)
Experimental
Band
2985 (CH3 de-st)
2969 (CH3 de-st)
2954 (CH3 s-st)
2896 (CH3 s-st)
1468 (CH3 de-d)
1469 (CH3 de-d)
1388 (CH3 s-d)
1379 (CH3 s-d)
1190 (CH3 r)
995 (C-C st)
822 (CH3 r)
289 (tr)
Ref.
[3]
a
M06-L/6-31++G** level of theory; scale factor for vibrations above 1000 cm-1 is 0.949 while
vibrations below are unscaled; as = asymmetric, d = deformation, de =degenerate, r = rock, s =
symmetric, sc = scissors, st = stretch, tr = torsion, tw = twist, w = wag.
7
Table S4. Comparison of relevant calculated and experimental vibrational frequencies (cm-1) for
ethene in vacuum.
Calculateda
Unscaled
3255 (CH2 as-st)
3228 (CH2 as-st)
3165 (CH2 s-st)
3145 (CH2 s-st)
1705 (C=C st)
1455 (CH2 sc)
1377 (CH2 sc)
1227 (CH2 r)
1070 (CH2 tw)
969 (CH2 w)
951 (CH2 w)
819 (CH2 r)
Scaled
3089 (CH2 as-st)
3063 (CH2 as-st)
3004 (CH2 s-st)
2984 (CH2 s-st)
1618 (C=C st)
1381 (CH2 sc)
1306 (CH2 sc
1164 (CH2 r)
1016 (CH2 tw)
969 (CH2 w)
951 (CH2 w)
819 (CH2 r)
Experimental
Band
3106 (CH2 as-st)
3103 (CH2 as-st)
3026 (CH2 s-st)
2989 (CH2 s-st)
1623 (C=C st)
1444 (CH2 sc)
1342 (CH2 sc)
1236 (CH2 r)
1023 (CH2 tw)
949 (CH2 w)
943 (CH2 w)
826 (CH2 r)
Ref.
[3]
a
M06-L/6-31++G** level of theory; scale factor for vibrations above 1000 cm-1 is 0.949 while
vibrations below this value are unscaled ; as = asymmetric, d = deformation, de =degenerate, r =
rock, s = symmetric, sc = scissors, st = stretch, tr = torsion, tw = twist, w = wag.
.
Table S5. Comparison of relevant calculated and experimental vibrational frequencies (cm-1) for
ethyne in vacuum.
Calculateda
Unscaled
3503 (CH st)
3399 (CH st)
2058 (C≡C st)
782 (CH b)
572 (CH b)
Scaled
3324 (CH st)
3226 (CH st)
1953 (C≡C st)
782 (CH b)
572 (CH b)
Experimental
Band
3374 (CH st)
3289 (CH st)
1974 (C≡C st)
730 (CH b)
612 (CH b)
Ref.
[3]
a
M06-L/6-31++G** level of theory; scale factor for vibrations above 1000 cm-1 is 0.949 while
vibrations below this value are unscaled; as = asymmetric, d = deformation, de =degenerate, r =
rock, s = symmetric, sc = scissors, st = stretch, tr = torsion, tw = twist, w = wag.
Table S6. Comparison of relevant calculated and experimental vibrational frequencies (cm-1) for
propane in vacuum.
8
Calculateda
Unscaled
3136 (CH3 de-st)
3134 (CH3 de-st)
3132 (CH3 de-st)
3126 (CH3 de-st)
3083 (CH3 s-st)
3041 (CH2 as-st)
3041 (CH3 s-st)
3038 (CH2 s-st)
1502 (CH3 de-d)
1497 (CH3 de-d)
1486 (CH3 de-d)
1482 (CH2 sc)
1479 (CH3 de-d)
1416 (CH3 de-d)
1405 (CH3 s-d)
1364 (CH2 w)
1320 (CH2 tw)
1212 (CH3 r)
1179 (CH3 r)
1084 (C-C st)
926 (CH3 r)
904 (CH3 r)
896 (CC st)
745 (CH2 r)
364 (CCC d
264 (tr)
211 (tr)
Scaled
2976 (CH3 de-st)
2974 (CH3 de-st)
2973 (CH3 de-st
2966 (CH3 de-st)
2925 (CH3 s-st)
2886 (CH2 as-st)
2886 (CH3 s-st)
2883 (CH2 s-st)
1425 (CH3 de-d)
1420 (CH3 de-d)
1410 (CH3 de-d)
1406 (CH2 sc)
1403 (CH3 de-d)
1343 (CH3 de-d)
1333 (CH3 s-d)
1294 (CH2 w)
1252 (CH2 tw)
1150 (CH3 r)
1119 (CH3 r)
1029 (C-C st)
926 (CH3 r)
904 (CH3 r)
896 (CC st)
745 (CH2 r)
364 (CCC d)
264 (tr)
211 (tr)
Experimental
Band
2977 (CH3 de-st)
2973 (CH3 de-st)
2968 (CH3 de-st)
2967 (CH3 de-st)
2962 (CH3 s-st)
2962 (CH2 as-st)
2887 (CH3 s-st)
2887 (CH2 s-st)
1476 (CH3 de-d)
1472 (CH3 de-d)
1464 (CH3 de-d)
1462 (CH2 sc)
1451 (CH3 d-d)
1392 (CH3 s-d)
1378 (CH3 s-d)
1338 (CH2 w)
1278 (CH2 tw)
1192 (CH3 r)
1158 (CH3 r)
1054 (C-C st)
922 (CH3 r)
940 (CH3 r)
869 (CC st)
748 (CH2 r)
369 (CCC d)
268 (tr)
216 (tr)
Ref.
[3]
a
M06-L/6-31++G** level of theory; scale factor for vibrations above 1000 cm-1 is 0.949 while
vibrations below are unscaled; as = asymmetric, d = deformation, de =degenerate, r = rock, s =
symmetric, sc = scissors, st = stretch, tr = torsion, tw = twist, w = wag.
9
Table S7. Comparison of relevant calculated and experimental vibrational frequencies (cm-1) for propene in vacuum.
Calculateda
Unscaled
3260 (CH2 as-st
3165 (CH st)
3156 (CH2 s-st + CH st)
3143 (CH3 as-st + CH st)
3131 (CH3 as-st)
3052 (CH3 s-st)
1728 (C=C st + CH2 sc)
1481 (CH3 as-d + CH2 sc)
1479 (CH3 as-d)
1440 (CH2 sc + CH b + CH3 s-d)
1396 (CH3 s-d + CH2 sc)
1323 (CH b + CH2 b)
1193(CH2 r + CH3 r)
1063 (CH3 r)
1031 (CH b + CH2 tw)
948 (CH3 r + CH b + CH2 r)
942 (C-C st + CH2 r)
915 (CH2 w)
591 ( C-CH2 tw )
421
225
Scaled
3094 (CH2 as-st)
3003 (CH st)
2995 (CH2 s-st + CH st)
2983 (CH3 as-st + CH st)
2971 (CH3 as-st)
2896 (CH3 s-st)
1639 (C=C st + CH2 sc)
1405 (CH3 as-d + CH2 sc)
1403 (CH3 as-d)
1366 (CH2 sc + CH b + CH3 s-d)
1324 (CH3 s-d + CH2 sc)
1255 (CH b + CH2 b)
1132 (CH2 r + CH3 r)
1009 (CH3 r)
979 (CH b + CH2 tw)
948 (CH3 r + CH b + CH2 r)
942 (C-C st + CH2 r)
915 (CH2 w)
591 ( C-CH2 tw )
421
225
Experimental
Band
3075 (CH2 as-st)
3008 (CH st)
2977 (CH2 s-st + CH st)
2958 (CH3 as-st + CH st)
2933 (CH3 as-st)
2912 (CH3 s-st)
1645 (C=C st + CH2 sc)
1449 (CH3 as-d + CH2 sc)
1433 (CH3 as-d)
1411 (CH2 sc + CH b + CH3 s-d)
1370 (CH3 s-d + CH2 sc)
1293 (CH b + CH2 b)
1169 (CH2 r + CH3 r)
1040 (CH3 r)
988 (CH b + CH2 tw)
932 (CH3 r + CH b + CH2 r)
916 (C-C st + CH2 r)
908 (CH2 w)
578 ( C-CH2 tw )
―
―
Ref.
[4]
a
M06-L/6-31++G** level of theory; scale factor for vibrations above 1000 cm-1 is 0.949 while vibrations below are unscaled; as =
asymmetric, d = deformation, de =degenerate, r = rock, s = symmetric, sc = scissors, st = stretch, tr = torsion, tw = twist, w = wag.
10
Table S8. Comparison of relevant calculated and experimental vibrational frequencies (cm-1) for
propyne in vacuum.
Calculateda
Unscaled
3460 (CH st)
3153 (CH3 de-st)
3064 (CH3 s-st)
2228 (C≡C st)
1463 (CH3 de-d)
1405 (CH3 s-d)
1048(CH3 r)
973(C-C st)
615(CH b)
352(CCC b)
Scaled
3283 (CH st)
2991 (CH3 de-st)
2908 (CH3 s-st)
2115 (C≡C st)
1388(CH3 de-d)
1334 (CH3 s-d)
994(CH3 r)
973(C-C st)
615(CH b)
352(CCC b)
Experimental
Band
3334 (CH st)
3008 (CH3 de-st)
2918 (CH3 s-st)
2142 (C≡C st)
1452 (CH3 de-d)
1382 (CH3 s-d)
1053 (CH3 r)
931 (C-C st)
633 (CH b)
328 (CCC b)
Ref.
[3]
a
M06-L/6-31++G** level of theory; scale factor for vibrations above 1000 cm-1 is 0.949 while
vibrations below are unscaled; as = asymmetric, d = deformation, de =degenerate, r = rock, s =
symmetric, sc = scissors, st = stretch, tr = torsion, tw = twist, w = wag.
11
(a)
(b)
(c)
(d)
(e)
(f)
-0.1 a.u.
0.1 a.u.
Figure S2. Electrostatic potential map for Na-ETS-10 model interaction with C2H6 (a), C2H4 (b), C2H2 (c), C3H8 (d), C3H6 (e), and
C3H4 (f).
12
Table S9. Calculated electrophilicities (atomic units) for some selected atoms in the bare
Na-ETS-10 cluster model.a
Atomb
ƒ+c
NPA
Mulliken
Na2
0.049
0.237
O1
0.005
-0.003
O2
0.005
-0.003
O5
0.017
0.009
O6
0.005
-0.003
O7
0.005
-0.003
a
b
The atom more prone to nucleophilic attach is highlighted in bold. For atomic labelling please
refer to Figure 1. cElectrophilicities are based on Natural (NPA) or Mulliken atomic populations
calculated at the BP86/6-31G(d) level of theory for anionic and neutral Na-ETS-10 systems.
13
Table S10. Calculated nucleophilicities (atomic units) for the gaseous hydrocarbon considered in
this work.a
ƒ-b
Hydrocarbon
Atom
NPA
C
C2H6
C2H4
C2H2
C3H8
C3H6
C2H4
Mulliken
Hc
C
C1
-0.021
C2
-0.021
C1
-0.342
C2
-0.342
C1
-0.420
C2
-0.420
C1
-0.010
C2
-0.004
C3
-0.010
-0.056
C1
-0.321
0.153
C2
-0.287
C3
0.062
-0.060
C1
-0.375
0.337
C2
-0.222
C3
0.053
-0.160
-0.079
-0.080
0.297
0.297
0.162
0.162
0.333
0.333
H
-0.266
0.169
0.167
-0.056
-0.109
-0.071
-0.066
-0.099
0.098
0.202
0.143
0.154
0.152
-0.048
The carbon atom which share double or triple bond shows higher nucleophilicity.
b
Nucleophilicities are based on Natural (NPA) or Mulliken atomic populations calculated at the
M06/6-31G(d) level of theory for neutral and cationic isolated gaseous hydrocarbon. cAn average
nucleophilicity of H atoms.
a
14
References
[1] X. Q. Wang, A. J. Jacobson. Crystal structure of the microporous titanosilicate ETS-10
refined from single crystal X-ray diffraction data. Chem Commun, (1999) 973-974.
[2] A. M. Zimmerman, D. J. Doren, R. F. Lobo. Electronic and geometric properties of ETS-10:
QM/MM studies of cluster models. J Phys Chem B, 110 (2006) 8959-8964.
[3] T. Shimanouchi. Tables of Molecular Vibrational Frequencies Consolidated Volume I.
National Bureau of Standards, 1972, 1-160. Data taken from NIST webbook,
http://webbook.nist.gov/.
[4] J. G. Radziszewski, J. W. Downing, M. S. Gudipati, V. Balaji, W. Thulstrup, J. Michl. How
Predictable Are IR Transition Moment Directions? Vibrational Transitions in Propene and
Deuterated Propenes. J. Am. Chem. Soc. 118 (1996) 10275-10284.
15