Supporting Information To Microhydration of caesium compounds: Cs, CsOH, CsI and Cs 2 I 2 complexes with one to three H 2 O molecules of nuclear safety interest Journal of Molecular Modeling Mária Sudolská 1, Laurent Cantrel, Ivan Černušák 1 Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina, 84215 Bratislava, Slovakia m.sudolska@gmail.com Table S1 Geometry parameters of H 2 O molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using augcc-pvtz basis set) and comparison with experimental data (bond lengths in Å, bond angles in deg.) Table S2 Geometry parameters of CsOH molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using aug-cc-pvtz basis set for O and H atoms, and ECP46MDF basis set on Cs atom) and comparison with experimental data (bond lengths in Å, bond angles in deg.) Table S3 Geometry parameters of CsI molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using augcc-pvtz-pp on I and ECP46MDF basis set on Cs atom) and comparison with experimental data (bond lengths in Å, bond angles in deg.) Table S4 Geometry parameters of Cs 2 I 2 molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using augcc-pvtz-pp on I and ECP46MDF basis set on Cs atom) and comparison with experimental data (bond lengths in Å, bond angles in deg.) Table S5 XYZ coordinates of atoms in Cs(H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å) Table S6 XYZ coordinates of atoms in CsOH(H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å) Table S7 XYZ coordinates of atoms in CsI(H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å)
Table S8 XYZ coordinates of atoms in Cs 2 I 2 (H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å). Relative MP2/aug-cc-pVTZ-PP energies of the local minima with respect to the global minimum energy (including zero point vibrational energy, scaling factor 0.959, in kj/mol) for complexes with n=2 and 3 in brackets Table S9 MP2/aug-cc-pVTZ-PP entropies of the most stable complexes of Cs, CsOH, CsI and Cs 2 I 2 at 298K, 500K and 700K (in J K -1 mol -1 )
Table S1 Geometry parameters of H 2 O molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using augcc-pvtz basis set) and comparison with experimental data (bond lengths in Å, bond angles in deg.) r(oh) α(hoh) Δr(OH) Δα(HOH) MP2 0.961 104.10 0.003-0.38 MP4(SDQ) 0.959 104.41 0.001-0.07 PBE 0.970 104.16 0.012-0.32 PBE0 0.959 104.86 0.001 0.38 PBE-D3 0.970 104.16 0.012-0.31 PBE0-D3 0.959 104.87 0.001 0.39 B97D3 0.965 104.38 0.007-0.09 exp. 0.958 104.48 ref. [1]
Table S2 Geometry parameters of CsOH molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using aug-cc-pvtz basis set for O and H atoms, and ECP46MDF basis set on Cs atom) and comparison with experimental data (bond lengths in Å, bond angles in deg.) r(cso) r(oh) α(csoh) Δr(CsO)* Δr(OH)* MP2 2.409 0.962 180.0 0.006 0.042 MP4(SDQ) 2.420 0.958 180.0 0.017 0.038 PBE 2.401 0.968 180.0-0.002 0.048 PBE0 2.390 0.957 180.0-0.013 0.037 PBE-D3 2.402 0.968 180.0-0.001 0.048 PBE0-D3 2.392 0.957 180.0-0.011 0.037 B97D3 2.430 0.963 180.0 0.027 0.043 exp. 2.391 ± 0.002 0.96 ± 0.01 180.0 ref. [2] 2.395 0.92 180.0 ref. [3] 2.403 0.92 180.0 ref. [4] *with respect to ref. [4]
Table S3 Geometry parameters of CsI molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using augcc-pvtz-pp on I and ECP46MDF basis set on Cs atom) and comparison with experimental data (bond lengths in Å, bond angles in deg.) r(csi) Δr(CsI)* MP2 3.321 0.006 MP4(SDQ) 3.349 0.034 PBE 3.323 0.008 PBE0 3.321 0.006 PBE-D3 3.330 0.015 PBE0-D3 3.328 0.013 B97D3 3.398 0.083 exp. 3.314 ref. [5] 3.315 ref. [6] *with respect to ref. [6]
Table S4 Geometry parameters of Cs 2 I 2 molecule optimized at MP2, MP4(SDQ), DFT and DFT-D3 (using augcc-pvtz-pp on I and ECP46MDF basis set on Cs atom) and comparison with experimental data (bond lengths in Å, bond angles in deg.) Cs 2 I 2 r(csi) α(csics) α(icsi) Δr(CsI) Δα(CsICs) MP2 3.522 88.0 92.0-0.050-4.5 MP4(SDQ) 3.564 87.3 92.7-0.008-3.8 PBE 3.568 86.3 93.7-0.004-2.8 PBE0 3.559 86.5 93.5-0.013-3.0 PBE-D3 3.584 87.0 93.0 0.012-3.5 PBE0-D3 3.578 87.4 92.6 0.006-3.9 B97D3 3.690 87.1 92.9 0.118-3.6 exp. 3.572 96.5 ref. [3]
Table S5 XYZ coordinates of atoms in Cs(H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å) A1 Cs 0.0000 0.0000 0.4808 O 0.0000 0.0000-2.5268 H 0.0000 0.7637-3.1158 H 0.0000-0.7637-3.1158 A2-1 Cs 0.0000 0.7506 0.0000 A2-2 Cs 0.0000 0.8468 0.0000 O -1.3167-2.1637 0.0000 O 1.3417-1.7741 0.0000 O 1.4506-1.8496 0.0000 O -1.2314-2.8254 0.0000 H -1.9103-2.1618 0.7650 H -1.7502-2.5312 0.7608 H -1.9103-2.1618-0.7650 H -1.7502-2.5312-0.7608 H 0.6092-2.3339 0.0000 H 0.5372-2.3265 0.0000 H 2.1401-2.5196 0.0000 H 2.0809-2.3886 0.0000 A2-3 Cs 0.0000 0.0000 0.0000 O 0.0000 0.0000 3.0268 O 0.0000 0.0000-3.0268 H 0.0000 0.7633 3.6164 H 0.0000-0.7633 3.6164 H 0.0000 0.7633-3.6164 H 0.0000-0.7633-3.6164 A3-1 Cs 1.0657-0.0014-0.0324 A3-2 Cs -0.1968-0.6628 0.0001 O -3.2353-0.1559-0.1291 O 2.6991 0.0325-0.0002 O -1.3788 1.9246 0.1808 O 1.0101 2.2242 0.0002 O -1.1678-1.9364 0.1618 O -2.6235 1.0876-0.0002 H -3.7617-0.0594-0.9282 H 3.6601 0.0467-0.0011 H -2.7363 0.6778-0.0504 H 2.4223 0.9656-0.0001 H -1.9926-1.4205 0.0423 H 0.5888 2.6538 0.7652 H -1.4475-2.7742 0.5410 H 0.5892 2.6548-0.7644 H -1.1248 2.5449-0.5245 H -2.5626 1.6898-0.7593 H -1.2939 2.4478 0.9944 H -2.5610 1.6899 0.7587
Table S5 (cont.) A3-3 Cs -0.9787 0.0000 0.1078 A3-4 Cs 0.8657-0.0003 0.0406 O 1.2210 1.8107-0.8074 O -1.4162-1.9612-0.6794 O 1.2210-1.8107-0.8075 O -1.4141 1.9627-0.6789 O 2.7159 0.0000 0.7964 O -1.8157 0.0002 1.4506 H 1.4109 2.7518-0.7417 H -1.5848-1.5258-1.5362 H 1.9274 1.3780-0.2963 H -1.5606-2.8995-0.8606 H 1.9274-1.3780-0.2964 H -1.5834 1.5275-1.5357 H 1.4104-2.7519-0.7410 H -1.5575 2.9012-0.8601 H 2.2390-0.0001 1.6501 H -2.0788 0.7603 0.9112 H 3.6516 0.0001 1.0442 H -2.0791-0.7592 0.9103 A3-5 Cs 0.0000 0.0000 0.7922 O 0.0000 2.0382-1.3369 O 1.7651-1.0191-1.3369 O -1.7651-1.0191-1.3369 H 1.1747-1.0651-2.1123 H -1.5098-0.4848-2.1123 H 0.3350 1.5499-2.1123 H 2.6026-0.7182-1.7152 H -1.9233-1.8948-1.7152 H -0.6793 2.6130-1.7152
Table S6 XYZ coordinates of atoms in CsOH(H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å) B1 Cs 0.0000 0.6404 0.0000 B2 Cs -0.1681 0.7608 0.0000 O 1.2459-1.5918 0.0000 O 1.2298-1.6090 0.0000 O -1.2500-1.9176 0.0000 O -0.1681-1.2316 2.0897 H 1.8692-2.3232 0.0000 O -0.1681-1.2316-2.0897 H -0.2178-2.0207 0.0000 H 2.0427-2.1214 0.0000 H -1.6185-2.8034 0.0000 H 0.4489-1.5743 1.3510 H -0.4220-1.9993 2.6067 H 0.4489-1.5743-1.3510 H -0.4220-1.9993-2.6067 B3-1 Cs 0.0000 0.0000 0.9042 B3-2 Cs -0.0529-0.8033 0.0184 O 0.0000 0.0000-2.1154 O -0.9188 1.7469 0.8203 O 0.0000 2.2726-0.8727 O 1.0957 2.0151-0.5737 O 1.9681-1.1363-0.8727 O -2.6974 0.3761-0.4201 O -1.9681-1.1363-0.8727 O 2.8085 0.0886 0.0605 H 1.2998-0.7504-1.5255 H -1.0967 2.3907 1.5111 H -1.2998-0.7504-1.5255 H 0.2296 2.0592 0.0401 H 0.0000 1.5008-1.5255 H 1.0496 2.7452-1.1949 H 2.6610-1.5363-1.4027 H -2.1604 1.0697 0.0841 H -2.6610-1.5363-1.4027 H -3.4595 0.8358-0.7792 H 0.0000 3.0726-1.4027 H 2.3737 0.9405-0.1790 H 0.0000 0.0000-3.0773 H 3.6709 0.3267 0.4088 B3-3 Cs -0.9760 0.0000-0.0068 O 1.2351 0.0004-1.6732 O 1.3807 1.9353-0.0457 O 1.3809-1.9352-0.0464 O 1.2528-0.0004 2.0195 H 1.7252 0.0006-2.5002 H 1.4767 1.2448-0.8004 H 1.9336 2.6836-0.2834 H 1.4765-1.2446-0.8010 H 1.9338-2.6834-0.2845 H 1.5692-0.7624 1.5047 H 1.5692 0.7618 1.5050
Table S7 XYZ coordinates of atoms in CsI(H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å) C1 Cs 0.0000 1.6707 0.0000 I -0.4597-1.7264 0.0000 O 2.4116 0.0768 0.0000 H 1.7842-0.6830 0.0000 H 3.2854-0.3242 0.0000 C2-1 Cs -1.0611 1.3412 0.0000 C2-2 Cs 1.5598-0.6508 0.0119 I 0.7778-1.6954 0.0000 I -1.8599-0.2961-0.0103 O 0.7778 0.8873 2.2241 O -0.6014 2.8656-0.0150 O 0.7778 0.8873-2.2241 O 2.0072 2.2169-0.0445 H 0.9891 0.0413 1.7711 H -1.0617 1.9961-0.0793 H 1.3551 0.9057 2.9927 H -1.0315 3.2950 0.7312 H 0.9891 0.0413-1.7711 H 1.0820 2.5619-0.0089 H 1.3551 0.9057-2.9927 H 2.5470 2.9762-0.2789 C3-1 Cs 0.0000 0.0000 1.7624 C3-2 Cs -1.5467-0.7029 0.0000 I 0.0000 0.0000-1.9460 I 1.9898-0.1546 0.0000 O -2.2283-1.2865 0.3188 O -0.2599 1.2047-2.1298 O 0.0000 2.5730 0.3188 O -0.2599 1.2046 2.1298 O 2.2283-1.2865 0.3188 O -1.8617 2.2698 0.0000 H 0.0000 2.0508-0.5109 H 0.5596 0.9175-1.6655 H 1.7761-1.0254-0.5109 H 0.0395 1.4973-2.9964 H -1.7761-1.0254-0.5109 H 0.5596 0.9175 1.6655 H 0.0000 3.4900 0.0302 H 0.0394 1.4972 2.9964 H 3.0224-1.7450 0.0302 H -1.2679 2.2941 0.7661 H -3.0224-1.7450 0.0302 H -1.2679 2.2941-0.7661 C3-3 Cs -1.5864-0.5445-0.2813 C3-4 Cs 1.4463-0.7714-0.0146 I 1.9424-0.0992-0.2598 I -2.0171-0.0755-0.2888 O 0.4344 2.8086 0.7082 O 0.3284 2.4147 0.1682 O -0.0930-1.6298 2.0093 O 2.6568 1.7047-1.0122 O -2.1515 2.3020 0.1091 O -0.0235 0.4960 2.3738 H 0.9618 2.0407 0.3918 H -0.4628 1.9383-0.1585 H 0.7554 2.9547 1.6034 H 0.2968 2.2309 1.1178 H 0.7006-1.2743 1.5535 H 1.8577 2.1577-0.6656 H 0.2494-2.0698 2.7925 H 3.1468 2.3734-1.4972 H -1.2460 2.5967 0.3608 H -0.3684 0.4880 3.2724 H -2.6362 3.1111-0.0728 H -0.8066 0.3157 1.8018
Table S7 (cont.) C3-5 Cs 1.6112-0.6830-0.0295 I -1.9166-0.3808-0.1714 O -0.5913 2.7279 0.0345 O 1.8391 2.0657-1.0446 O 0.3023 0.8357 2.2030 H -1.1000 1.8908-0.0936 H -1.2133 3.4268-0.1922 H 0.1961 1.7684 1.9742 H -0.5242 0.4510 1.8521 H 0.9817 2.4428-0.7535 H 2.2209 2.7293-1.6249
Table S8 XYZ coordinates of atoms in Cs 2 I 2 (H 2 O) n (n=1-3) complexes optimized at MP2/aug-cc-pVTZ-PP level of theory (in Å). Relative MP2/aug-cc-pVTZ-PP energies of the local minima with respect to the global minimum energy (including zero point vibrational energy, scaling factor 0.959, in kj/mol) for complexes with n=2 and 3 in brackets D1-1 Cs 2.4344 0.8469 0.0000 D1-2 Cs -2.5616 0.0000 0.0764 Cs -2.2941-1.2289 0.0000 Cs 2.5616 0.0000 0.0764 I -0.0621-0.0313 2.4449 I 0.0000 2.4586-0.2754 I -0.0621-0.0313-2.4449 I 0.0000-2.4586-0.2754 O -0.0621 2.5424 0.0000 O 0.0000 0.0000 2.1978 H -0.3176 1.9970 0.7652 H 0.0000 0.7751 1.6023 H -0.3176 1.9970-0.7652 H 0.0000-0.7751 1.6023 D1-3 Cs 0.1629 0.1778 2.2674 D1-4 Cs 1.5055-1.8582-0.2339 Cs 0.1629 0.1778-2.2674 Cs -1.7863 1.8167 0.1258 I 2.2883-1.4659 0.0000 I 1.7349 1.7906-0.2758 I -2.6390 0.6251 0.0000 I -2.0335-1.6725 0.0282 O 0.1629 2.4303 0.0000 O 3.0980-0.5076 1.8738 H 0.1602 3.3933 0.0000 H 2.8451 0.3382 1.4518 H -0.7881 2.1721 0.0000 H 3.6424-0.2557 2.6250 D2-1 Cs 0.7720 2.3773-0.0694 D2-2 Cs 0.0011-2.7110 0.0000 (0.0) Cs -0.6825-2.3547-0.1328 (0.3) Cs -0.0003 2.7111 0.0000 I -2.4464 0.7887-0.4162 I -0.0003 0.0001 2.3870 I 2.4910-0.7944-0.2839 I -0.0003 0.0001-2.3870 O -1.5344-0.7999 2.4175 O -2.4424-0.9247 0.0000 O 0.9291 0.7583 2.4307 O 2.4415 0.9225 0.0000 H -2.1291-0.7742 3.1745 H -2.0086-0.5027 0.7629 H -1.9572-0.2196 1.7428 H -2.0086-0.5027-0.7629 H 0.1339 0.2254 2.5921 H 2.0071 0.5012 0.7629 H 1.5104 0.1579 1.9291 H 2.0071 0.5012-0.7629 D2-3 Cs 0.2353-2.2966 0.6126 D2-4 Cs 2.6285-0.6248-0.1998 (3.0) Cs -0.1002 2.4124 0.3122 (3.4) Cs -2.3987 0.8270-0.4013 I -2.5414-0.1084-0.5845 I 0.7451 2.4036 0.0947 I 2.5691 0.2435-0.3949 I -0.5746-2.3263-0.2267 O 0.2270-1.6126-2.3054 O 0.9899-0.3573 2.3044 O -0.9889 0.1536 2.3685 O -3.1160-1.0983 1.7287 H -0.5823-1.0888-2.1919 H 0.7592 0.5272 1.9676 H 0.9401-0.9785-2.1139 H 0.3476-0.9399 1.8647 H -1.6626 0.0507 1.6574 H -2.4214-1.6909 1.3802 H -1.4951 0.1561 3.1879 H -3.3526-1.4705 2.5832
Table S8 (cont.) D2-5 Cs -2.5357-0.3708 0.0000 D2-6 Cs 2.5274-0.7141-0.4316 (3.5) Cs 2.7119 0.0439 0.0000 (4.5) Cs -2.4001 0.8839 0.1160 I 0.1347-0.2766 2.4270 I 0.8059 2.4017-0.0428 I 0.1347-0.2766-2.4270 I -0.6373-2.3115 0.3202 O 0.1347 2.1723 0.0000 O 1.4138-0.1641 2.3101 O -2.5906 2.5799 0.0000 O -2.9381-1.1626-1.9578 H 0.1073 1.5683 0.7737 H 1.1427 0.6911 1.9295 H 0.1073 1.5683-0.7737 H 0.6817-0.7592 2.0775 H -1.6134 2.6649 0.0000 H -2.2940-1.7333-1.4934 H -2.9260 3.4800 0.0000 H -3.2746-1.7036-2.6777 D2-7 Cs 0.0000 0.0000 2.0864 D2-8 Cs 1.7420-1.7885-0.1327 (6.1) Cs 0.0000 0.0000-2.0864 (6.2) Cs -1.7420 1.7885-0.1327 I 0.0000 2.9935 0.0000 I 1.8302 1.8350-0.2683 I 0.0000-2.9935 0.0000 I -1.8302-1.8350-0.2683 O 2.2692 0.5709 0.0000 O 2.9922-0.3298 2.1187 O -2.2692-0.5709 0.0000 O -2.9923 0.3298 2.1187 H 1.8983 1.4826 0.0000 H 2.7616 0.4914 1.6379 H -1.8983-1.4826 0.0000 H 3.4128-0.0309 2.9298 H 3.2259 0.6776 0.0000 H -2.7616-0.4914 1.6379 H -3.2259-0.6776 0.0000 H -3.4130 0.0309 2.9297 D2-9 Cs -2.3973-0.8634-0.0633 D2-10 Cs 0.0000 2.6127-0.6468 (6.4) Cs 2.5947 0.6832-0.2676 (6.5) Cs 0.0000-2.6127-0.6468 I 0.9063-2.3764-0.0562 I -2.3169 0.0000 0.2571 I -0.4624 2.3650 0.3264 I 2.3169 0.0000 0.2571 O -0.7299-0.4860 2.4608 O 0.0000 1.8830 2.2319 O -2.8247 1.3923-1.9783 O 0.0000-1.8830 2.2319 H -0.0896-1.0547 1.9970 H -0.7603 1.3054 2.0482 H -0.5299 0.4036 2.1239 H 0.7603 1.3054 2.0482 H -2.1600 1.9017-1.4740 H -0.7603-1.3054 2.0482 H -3.1663 2.0119-2.6291 H 0.7603-1.3054 2.0482 D2-11 Cs 2.5010 0.0000 0.0000 D2-12 Cs -0.7229 2.2880 0.0719 (6.6) Cs -2.5010 0.0000 0.0000 (6.6) Cs 0.5518-2.0938 0.4946 I 0.0000-2.5891 0.0000 I -2.6540-0.6952-0.5773 I 0.0000 2.5891 0.0000 I 2.5218 0.9003-0.1630 O 2.5360 1.9647-2.2176 O -1.1193 0.0808 2.2832 O -2.5360-1.9647 2.2176 O 2.7996-2.2741-1.4381 H 1.7544 2.3681-1.7881 H -1.5617 0.0164 3.1361 H -1.7544-2.3681 1.7881 H -1.7907-0.2146 1.6252 H 2.6854 2.4940-3.0061 H 2.9434-1.3201-1.2756 H -2.6854-2.4940 3.0061 H 3.3848-2.4897-2.1697
Table S8 (cont.) D2-13 Cs 0.9670-2.1772 0.3376 D2-14 Cs 2.5069 0.2363-0.1125 (9.2) Cs -0.5074 2.1611 0.1244 (9.4) Cs -2.5039 0.2653-0.1124 I -2.3700-1.0334-0.6493 I -0.0139-2.4164-0.5092 I 2.7268 0.7622-0.3722 I 0.0159 2.7319 0.0977 O -0.7395-0.3216 2.1959 O 2.6152-2.1297 1.6891 O -3.4752 1.9400 0.6848 O -2.6410-2.1006 1.6876 H -1.1683-0.2982 3.0578 H 1.8237-2.4675 1.2255 H -1.4531-0.5605 1.5645 H -1.8532-2.4473 1.2241 H -3.4349 1.0398 0.3062 H 2.8091-2.7889 2.3614 H -4.4149 2.1329 0.7524 H -2.8437-2.7585 2.3585 D2-15 Cs -0.0078-2.3453 0.0001 D2-16 Cs 2.0841 0.0000-0.1481 (9.8) Cs 0.0089 2.6489 0.0000 (10.5) Cs -2.0841 0.0000-0.1481 I -2.5735 0.2788 0.3421 I 0.0000 0.0000 3.0563 I 2.5754 0.2618-0.3423 I 0.0000 0.0000-2.9994 O -2.3361-2.3245-1.8937 O 0.0000 2.2242 0.5641 O 2.3202-2.3384 1.8946 O 0.0000-2.2242 0.5641 H -2.6388-1.5288-1.4124 H 0.0000 1.8834 1.4838 H -3.0118-2.4790-2.5599 H 0.0000-1.8834 1.4838 H 2.6274-1.5440 1.4143 H 0.0000 3.1841 0.6381 H 2.9948-2.4974 2.5608 H 0.0000-3.1841 0.6381 D2-17 Cs -2.4854 0.1627-0.3759 D2-18 Cs -2.1600 0.9627 0.0000 (10.8) Cs 2.4707 0.2897 0.3776 (11.6) Cs 2.1962-1.4960 0.0000 I 0.0617-2.4536-0.0048 I -1.1074-2.5029 0.0000 I -0.0705 2.7144-0.0032 I 1.4500 2.0282 0.0000 O -2.8663-1.9053 1.7380 O -1.1074 2.6709 2.2213 O 2.9888-1.7800-1.7055 O -1.1074 2.6709-2.2213 H -2.0190-2.3047 1.4646 H -0.2359 2.6534 1.7811 H -3.1440-2.4154 2.5042 H -0.2359 2.6534-1.7811 H 2.1579-2.2178-1.4405 H -0.9789 3.2208 2.9993 H 3.3042-2.2850-2.4603 H -0.9789 3.2208-2.9993 D3-1 Cs -2.6454-0.2085 0.0110 D3-2 Cs 0.0001 2.3125 0.4477 (0.0) Cs 2.5676 0.2834 0.1937 (1.1) Cs 0.0000-2.1519-0.2479 I 0.1266-2.4653-0.4335 I -2.7109 0.2356-0.7036 I -0.2663 2.4945-0.2605 I 2.7109 0.2355-0.7034 O 1.1241-1.2071 2.5455 O -2.1819-1.6924 2.0074 O -1.1911 0.5447 2.5011 O -0.0002 0.0562 2.3473 O 1.2450 0.2059-2.5199 O 2.1814-1.6925 2.0073 H 1.2554-1.8275 3.2703 H -2.9380-1.9546 2.5423 H 0.7814-1.7546 1.8031 H -2.5576-1.1175 1.2997 H -0.4175-0.0159 2.6765 H -0.7735-0.5128 2.4997 H -0.8254 1.2829 1.9816 H 0.7731-0.5130 2.4992 H 0.7977-0.6104-2.2408 H 2.5573-1.1176 1.2998 H 0.6631 0.9087-2.1821 H 2.9372-1.9544 2.5426
Table S8 (cont.) D3-3 Cs 2.7673 0.0000-0.5627 D3-4 Cs 2.7487-0.4152-0.2794 (1.9) Cs -2.7673 0.0000-0.5627 (2.7) Cs -2.5419 0.6600-0.4461 I 0.0002 2.3007 0.3569 I 0.5084 2.4036 0.3804 I 0.0002-2.3007 0.3569 I -0.3972-2.3615 0.0180 O 1.9175 0.0000 2.2973 O 1.3643-0.3843 2.3888 O -0.0010 0.0000-2.2365 O 0.2177 0.1946-2.2817 O -1.9187 0.0000 2.2977 O -3.2395-1.3023 1.6554 H 1.3386 0.7586 2.1120 H 0.9892 0.4812 2.1499 H 1.3386-0.7586 2.1120 H 0.7090-1.0083 2.0346 H -0.0004 0.7645-1.6260 H 0.3132 0.9108-1.6226 H -0.0004-0.7645-1.6260 H 0.0129-0.5943-1.7454 H -1.3396 0.7586 2.1129 H -2.4547-1.8283 1.4094 H -1.3396-0.7586 2.1130 H -3.5755-1.7184 2.4545 D3-5 Cs -1.8000 1.9176 0.0278 D3-6 Cs -0.0080 2.2703-0.1413 (3.3) Cs 1.4890-1.8638-0.2442 (3.8) Cs -0.0505-2.1565-0.3289 I -2.1669-1.6242-0.3812 I -2.8849 0.0843-0.1243 I 1.8014 1.7855-0.4271 I 2.9489-0.1061 0.1494 O -0.2185-1.7143 2.3707 O -1.2869-1.4111 2.4333 O -0.1747 1.1726 2.4087 O 0.4824 0.8620 2.4228 O 4.0172-0.5848 0.7087 O 0.7651 0.1355-2.3664 H -0.5257-2.2145 3.1341 H -1.9385-0.9487 1.8559 H -0.9569-1.7625 1.7204 H -1.7887-1.6792 3.2102 H -0.1414 0.2115 2.5500 H -0.0775 0.0917 2.6145 H 0.6199 1.3590 1.8788 H 1.3146 0.4811 2.0936 H 3.6129 0.2739 0.4752 H 1.6121 0.0854-1.8697 H 4.8755-0.3587 1.0782 H 1.0168 0.1763-3.2948 D3-7 Cs 2.5806 0.0269-0.5272 D3-8 Cs 1.9178 1.7859-0.1901 (4.0) Cs -2.5806 0.0267-0.5272 (4.3) Cs -1.5249-1.8629 0.1099 I -0.0002 2.5086-0.1529 I -1.7018 1.9036-0.2057 I 0.0000-2.4886-0.1594 I 2.0190-1.7978-0.3669 O 0.0003 1.1240 2.9730 O -1.4083 0.0245 2.6032 O 1.9828-0.8167 2.2440 O 1.4816 0.3143 2.3602 O -1.9824-0.8166 2.2444 O -3.7445-0.5888-1.4348 H 0.0000 1.7960 3.6622 H -1.8743 0.3104 3.3959 H 0.0003 1.6250 2.1266 H -1.5861 0.7266 1.9388 H 1.3731-0.1863 2.6631 H 0.5501 0.1926 2.6048 H 1.3924-1.4927 1.8691 H 1.6949-0.4893 1.8507 H -1.3728-0.1859 2.6631 H -3.3539 0.2835-1.2335 H -1.3918-1.4924 1.8693 H -4.4773-0.3983-2.0274
Table S8 (cont.) D3-9 Cs -1.5118-1.9262 0.1750 D3-10 Cs -2.5610 0.6870 0.3420 (4.4) Cs 1.7186 1.8858-0.2624 (6.3) Cs 2.5947-0.4664-0.5155 I 2.0589-1.6849-0.4860 I -0.4667-2.3481-0.0156 I -1.8308 1.8475-0.0514 I 0.4868 2.4344-0.3754 O 2.0471 0.1940 2.3121 O 2.9141-0.3535 2.4110 O -0.8225-0.2498 2.5820 O 0.2261 0.2003 2.2298 O -3.6605-0.6896-1.4978 O -3.4080-1.4298-1.5524 H 2.6321-0.0512 3.0367 H 1.9694-0.1389 2.5683 H 2.1554-0.5231 1.6445 H 3.3252-0.3520 3.2791 H 0.1299-0.0735 2.6475 H 0.0162-0.5908 1.6917 H -1.1664 0.5237 2.1021 H 0.3337 0.9167 1.5662 H -3.3215 0.1874-1.2319 H -3.8166-1.9575-2.2444 H -4.4026-0.4988-2.0785 H -2.6016-1.9231-1.3041 D3-11 Cs 0.1633 2.2513-0.1321 D3-12 Cs -2.2958-0.5709-0.5660 (6.8) Cs 0.0729-2.1554-0.3470 (7.2) Cs 2.5588 0.6398 0.0684 I -2.9165 0.1271 0.0142 I 0.7966-2.4698-0.3909 I 2.9368-0.0939 0.0329 I -0.3942 2.5317-0.3973 O -1.1875-1.5251 2.4248 O 1.2549-0.8246 2.5021 O 0.5819 0.7849 2.4117 O -1.2305 0.5766 2.3202 O -0.6090 0.1243-2.4113 O -3.7320-0.4179 2.0238 H -1.6486-1.8225 3.2160 H 1.4394-1.3461 3.2907 H -1.8626-1.0366 1.9053 H 1.0771-1.4892 1.7946 H 0.0410 0.0065 2.6172 H -0.3975 0.1054 2.4952 H 1.4032 0.4174 2.0350 H -0.9800 1.3052 1.7184 H -1.4837 0.1418-1.9675 H -2.8965-0.0275 2.3529 H -0.7987 0.1847-3.3533 H -4.3720-0.2960 2.7293 D3-13 Cs 1.5533-1.8923-0.0404 D3-14 Cs -2.0053 1.4427-0.4242 (7.3) Cs -1.9179 1.7479-0.1169 (9.9) Cs 2.2657-1.2299-0.2048 I 1.6971 1.8409-0.4256 I -1.2369-2.1509-0.5271 I -2.1001-1.7620-0.3097 I 1.4997 2.2230-0.0529 O -0.1346 1.7754 2.4207 O 0.6084-1.9397 2.2888 O -0.0067-1.1523 2.4190 O -0.4597 0.7530 2.4246 O 4.2213-0.4882-0.0438 O -3.1070-0.2018 1.8603 H 0.1686 2.2552 3.1986 H 0.4423-2.5316 3.0303 H 0.5905 1.8710 1.7638 H -0.0771-2.1660 1.6197 H -0.0778-0.1982 2.5780 H -0.0151-0.1055 2.5174 H -0.8001-1.3598 1.8919 H 0.1785 1.2874 1.9139 H 3.7397 0.3542-0.1455 H -2.2822 0.1017 2.2751 H 5.1499-0.2394-0.0339 H -2.8287-1.0026 1.3885
Table S8 (cont.) D3-15 Cs 0.9265-2.0237-0.4177 (14.4) Cs -1.2541 2.1951 0.3167 I 2.1041 1.4038-0.6921 I -2.5238-1.1133-0.4167 O 3.4926-0.8585 1.3716 O 1.2803-1.7215 2.6656 O -0.9287 0.1201 2.3966 H 4.4067-0.6791 1.6132 H 3.2177-0.0801 0.8313 H 2.1681-1.3728 2.4409 H 1.3646-2.1291 3.5324 H -0.1642-0.4401 2.6060 H -1.4835-0.4440 1.8249
Table S9 MP2/aug-cc-pVTZ-PP entropies of the most stable complexes of Cs, CsOH, CsI and Cs 2 I 2 at 298K, 500K and 700K (in J K -1 mol -1 ) Complex ΔS 298 K 500 K 700 K Cs(H 2 O) -62.2-60.2-58.9 Cs(H 2 O) 2-115.1-109.1-104.2 Cs(H 2 O) 3-121.2-116.9-112.6 CsOH(H 2 O) -106.6-105.1-102.5 CsOH(H 2 O) 2-128.6-124.9-121.0 CsOH(H 2 O) 3-122.6-118.0-113.7 CsI(H 2 O) -55.7-54.2-52.2 CsI(H 2 O) 2-115.8-109.7-104.9 CsI(H 2 O) 3-125.1-118.8-113.8 Cs 2 I 2 (H 2 O) -124.3-119.5-115.0 Cs 2 I 2 (H 2 O) 2-136.4-131.2-126.6 Cs 2 I 2 (H 2 O) 3-136.1-130.9-126.3
References to Supporting Information 1. Hoy AR, Bunker PR (1979) A precise solution of the rotation bending Schrödinger equation for a triatomic molecule with application to the water molecule. J Mol Spectrosc 74 (1):1-8 2. Lide DR, Jr., Matsumura C (1969) Structure of the Alkali Hydroxides. IV. Interpretation of Vibration- Rotation Interactions in CsOH and RbOH and Refinement of Structures. J Chem Phys 50 (7):3080-3086 3. Cordfunke EHP, Konings RJM (1990) Thermochemical Data for Reactor Materials and Fission Products. Elsevier, Amsterdam 4. Gurvich LV, Bergman GA, Gorokhov LN, Iorish VS, Leonidov VY, Yungman VS (1997) Thermodynamic properties of alkali metal hydroxides. 2. Potassium, rubidium, and cesium hydroxides. J Phys Chem Ref Data 26 (4):1031-1110 5. Hartley JG, Fink M (1988) An electron diffraction study of alkali iodide vapors. J Chem Phys 89 (10):6053-6057 6. Linstrom PJ, Mallard WG (2005) NIST Chemistry Webbook, Standard Reference Database Number 69. National Institute of Standards and Technology, Gaithersburg, MD. http://webbook.nist.gov