Supplementary Material
Infrared spectroscopy of Sc+(H2O) and Sc2+(H2O) via argon complex predissociation:
The charge dependence of cation hydration
P. D. Carnegie, B. Bandyopadhyay and M. A. Duncan*
Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556, U.S.A.
*Email: [email protected]; Fax: 706-542-1234
S1
Notes on calculations:
All the calculations are done with DFT-B3LYP level of theory with 6-311+G (d, p) basis set
a. Total binding energy in the complex relative to Sc+ or Sc2+ and separated ligands (in kcal/mol). The energies are not ZPVE
corrected.
b. Dissociation energy in kcal/mol for the elimination of the outermost ligand. In case of certain argon-tagged isomers first number is
the energy for the water and the second is that for argon.
c. Harmonic frequencies are unscaled. Intensities are in km/mol.
S2
H2O
State
1
A1(C2v)
B.Ea
Deb
Frequencies (int.)c/Symmetries
O-H
H-O-H
1602(67)/a1, 3819(9)/a1,
3924(57)/b2.
0.962
105.07
S3
Sc+(H2O)
State
B.Ea
Deb
Frequencies (int.)c/Symmetries
M+-O
MOHH dihedral
3
37.1
37.1
354 (13)/ a1, 442 (214)/ b1, 549 (28)/ b2 ,
1673 (123)/ a1, 3739 (122)/ a1, 3811 (209)/ b2.
2.201
180.0
B2(C2v)
S4
Sc+(H2O)Ar isomer a
State
B.Ea
Deb
3
45.2
37.6(8.0)
A1(C2v)
Frequencies (int.)c/Symmetries
M+-O
38 (0.38)/b1, 39 (0.18)/b2 ,113 (14)/a1
2.193
365 (15)/a1, 388 (214)/b1, 468 (15)/b2,
1651 (170)/a1, 3747 (102)/a1, 3823(192)/b2.
S5
M+-Ar
MOHH dihedral
2.816
180.0
Sc+(H2O)Ar isomer b
State
3
A′ (Cs)
B.Ea
Deb
Frequencies (int.)c/Symmetries
M+-O
H-Ar
MOHH dihedral
38.2
30.6(1.0)
32(3)/a', 77(11)/a', 177(7)/a", 364(14)/a',
477(181)/ a", 568(26)/a', 1675(104)/a',
3704(340)/a', 3794(256)/a'.
2.195
2.487
180.0
S6
Sc+(H2O)Ar2 isomer a
State
3
A′ (Cs)
B.Ea
Deb
Frequencies (int.)c/Symmetries
40.9
33.4(2.7)
26(0.8)/ a", 40(0.5)/ a', 58(12)/ a',
2.224
85(12)/ a', 115(3)/ a', 120(0.007)/ a",
344(11)/ a', 420(187)/ a", 592(59) / a',
1677(95)/ a', 3757(62)/ a', 3832(273)/ a'.
S7
M+-O
M+-Ar
MOHH dihedral
2.925
3.078
180.0
Sc+(H2O)Ar2 isomer b
State
3
A′ (Cs)
B.Ea
Deb
46.2
38.6(8.0),
(1.0)
Frequencies (int.)c/Symmetries
9(3)/ a', 42(3)/ a', 53(0.3)/ a", 75 (6)/ a',
113(17)/ a', 166(9)/ a", 369(15)/ a',
439(179)/ a", 486(13)/ a', 1651(155)/ a',
3708(317)/ a', 3804(228)/ a'
S8
M+-O
M+-Ar
MOHH dihedral
2.184
2.819
180.0
Sc+(H2O)Ar2 iso-c (2 Ar on water)
State
3
A′ (Cs)
B.Ea
Deb
Frequencies (int.)c/Symmetries
M+-O
MOHH dihedral
39.2
31.6(2.0)
14(2)/ a',15(1)/ a",29(2)/ a', 54(10)/ a',89(11)/ a'
236(0)/ a"375(14)/ a', 500(164)/ a",585(23)/ a',
1675(89)/ a',3688(359)/ a',3751(508)/ a'.
2.184
180.0
S9
Sc+(H2O)Ar3 iso-a (2 Ar on water 1 on metal)
State
3
A′ (Cs)
B.Ea
Deb
Frequencies (int.)c/Symmetries
47.1
39.6(2.0)(1.0)
9(3)/ a",14(1)/ a',16(1)/ a',
2.179
39(3)/ a",47(0)/ a',48(4)/ a',86(10)/ a',
112(18)/ a',226(0)/ a",382(17)/ a',451(165)/ a",
515(11)/ a',1654(130)/ a',3699(307)/ a',3764(478)/ a'.
S10
M+-O
MOHH dihedral
180.0
Sc+(H2O)Ar3 iso-b (1 Ar on water 2 on metal)
State
3
A′ (Cs)
B.Ea
Deb
Frequencies (int.)c/Symmetries
41.8
34.3(4.4)(1.0)
11(5)/ a",17(2)/ a',40(1)/ a',
2.220
46(1)/ a",47(1)/ a',62(14)/ a',88(11)/ a',
142(7)/ a',182(5)/ a",350(11)/ a',449(162)/ a",
635(113)/ a',1678(76)/ a',3733(178)/ a',3818(364)/ a'.
S11
M+-O
MOHH dihedral
180.0
Sc2+(H2O)
State
B.Ea
Deb
Frequencies (int.)c/Symmetries
M+-O
MOHH dihedral
2
72.3
72.3
453(49)/a1, 609(388)/b1, 633(103)/b2,
1688(134)/a1, 3609(354)/a1, 3652(366)/b2.
2.106
180.0
A1(C2v)
S12
Sc2+(H2O)Ar isomer-a
State
2
A′ (Cs)
B.Ea
86.4
Deb
66.3(14.1)
Frequencies (int.)c/Symmetries
M+-O
MOHH dihedral
28(4.4)/ a', 57(2.6)/ a",
179(38.3)/ a', 438(73.6)/ a',604 (370.1)/ a',
617(94.7)/ a",1690 (132.7)/ a',3633(356.2)/ a',
3678(341.4)/ a".
2.128
180.0
S13
Sc2+(H2O)Ar isomer-b
State
B.Ea
2
77.0
A' (Cs)
Deb
56.9(4.7)
Frequencies (int.)c/Symmetries
M+-O
H-Ar
MOHH dihedral
58(16)/ a', 143(35)/ a', 283(36)/ a", 2.081
485(48)/ a', 684(73)/ a', 701(278)/ a",
1679(122)/ a', 3273(1562)/ a',
3643(341)/ a'.
2.100
180.0
S14
Sc2+(H2O)Ar2 isomer-a
State
B.Ea
Deb
2
97.4
64.0(20.7)
A (C1)
Frequencies (int.)c/Symmetries
M+-O
28(0.3)/ a, 32(7.7)/ a, 44(4)/ a,
2.130
110(0.4)/ a, 171(30.1)/ a, 182(39.7)/ a,
430(51.9)/ a, 588(369.1)/ a, 605(86.3)/ a,
1687(139.4)/ a, 3647(338.1)/ a, 3696(319.1)/ a.
S15
M+-Ar
MOHH dihedral
2.682
179.9
Sc2+(H2O)Ar2 isomer-b
State
2
A′ (Cs)
B.Ea
90.5
Deb
70.0(13.5)
Frequencies (int.)c/Symmetries
M+-O
-1(12.7)/ a, 46(3.5)/ a, 58(12.3)/ ,
2.104
128(18.8)/ a,182(49.8)/ a' 281(29.0)/ a,
471(69.5)/ a, 666(68.4)/ a,683(273.3)/ a,
1684(123.2)/ a, 3357(1386.8)/ a,3666(336.7)/ a.
S16
M+-Ar
MOHH dihedral
2.673,2.141
179.9
Sc2+(H2O)Ar3
State
B.Ea
Deb
2
108.3
59.5(10.9) 26(2)/a, 27(1)/a, 32(4)/a, 39(9)/a,
2.146
57(0.1)/a, 98(0.4)/a, 156(20)/a, 175(32)/a,
181(39)/a, 417(50) /a, 583(355) /a, 604(84) /a,
1691(137)/a, 3664(324)/a, 3714(301)/a.
A(C1)
Frequencies (int.)c/Symmetries
S17
M+-O
M+-Ar
MOHH dihedral
2.696
2.705
2.703
179.9
Sc2+(H2O)Ar4
State
B.Ea
Deb
Frequencies (int.)c/Symmetries
2
113.7
52.8(5.4)
16(4)/a, 16(2)/a, 43(3)/ a', 54(1)/ a",
2.173
58(8)/ a', 76(0.4)/ a', 78(0.7)/ a", 118(5)/ a",
121(2)/ a', 144(24)/ a', 170(25)/ a', 193(49)/ a",
396(43)/ a', 578(334)/ a", 608(87)/ a',
1698(123)/ a', 3693(260)/ a', 3747 (262)/ a'.
A' (Cs)
S18
M+-O
M+-Ar
MOHH dihedral
2.718
2.718
2.733
2.784
180.0
Sc2+(H2O)Ar5
State
B.Ea
Deb
Frequencies (int.)c/Symmetries
2
121.2
50.4(7.5)
30(3)/b1, 34(2)/b2 , 39(0.2)/a1, 41(0)/a2 , 48(3)/b2, 2.179
56(2)/b1, 67(5)/a1, 69(0)/a2, 71(1)/b1, 84(2)/b2,
109(0.0002)/a1, 117(2)/a1, 140(20)/a1, 177(40)/b2
179(50)/b1, 390(34)/a1, 391(34)/a1, 568(321)/b1,
568(321)/b1, 601(90)/b2,1695(128)/a1, 3705(224)/a1,
3760(247)/b2.
B2 (C2v)
S19
M+-O
MOHH dihedral
180.0
S20
Sc2+(H2O)Ar6
State
B.Ea
2
123.8
A (C1)
Deb
52.4(2.6)
Frequencies (int.)c/Symmetries
M+-O
MOHH dihedral
8(2)/a, 21(1)/a, 33(1)/a, 33(2)/a, 38(0.3)/a,
43(0.2)/a, 44(0.0004)/a, 57(2)/a, 59(2)/a,
71(5)/a, 73(0.6)/a,109(0.3)/a,110(5)/a,118(6)/a,
142(30)/a,177(45)/a, 178(40)/a, 243(22)/a,
410(33)/a, 627(252)/a,635(71)/a ,1698(118)/a
3584(772)/a, 3741(242)/a.
2.163
179.98
S21
Sc2+(H2O)Ar7
State
2
B2 (C2v)
B.Ea
126.2
Deb
Frequencies (int.)c/Symmetries
55.4(2.4)
4(0)/a2, 18(0.7)/a1, 20(0.5)/b1, 22(0.5)/b2
2.153
33(0.7)/b2, 35(2.6)/b1, 39(0.2)/a1, 41(0.1)/b2,
45(0)/a2, 55(0)/a1, 56(2.5)/b1, 64(3.1)/b2, 80(7.7)/a1,
91(0.0)/b1, 108(0.0)/a1, 115(2.5)/a1, 137(20.4)/b2,
141(31.8)/a1, 177(53.6)/b1, 178(36.1)/b2, 346(0)/a2,
427(34.7)/a1, 663(222.4)/b1, 667(58.5)/b2, 1699(95.7)/a1,
3583(707.9)/a1, 3617(774.8) /b2.
S22
M+-O
MOHH dihedral
180.0
H-Sc3+(HO-) (insertion product)
State : 2A′ (Cs)
Relative energy with respect to Sc2+(H2O) = +63.2 kcal/mol
Frequencies
162
573
578
645
941
3551
intensity
14
286
298
0
104
840
symmetry
a'
a'
a"
a'
a'
a'
S23