<p> Supporting Information</p><p>Infrared Spectroscopy and Structures of</p><p>+ Manganese Carbonyl Cations, Mn(CO)n (n=1-9)</p><p>Z.D. Reed and M.A. Duncan</p><p>Department of Chemistry, University of Georgia, Athens GA 30602-2556</p><p>Email. [email protected]; Fax . 706-542-1234</p><p>S1 Table S1. The electronic states calculated for Mn(CO)+ with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3Mn(CO)+ -1264.0568491 +33.6</p><p>5Mn(CO)+ -1264.1104673 +0.74</p><p>7Mn(CO)+ -1264.1116475 0.0</p><p>S2 Figure S1. The optimized geometry of the triplet MnCO+ calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S2. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>351.5 1.56 351.5 1.56 454.1 9.62 2176.9 402.1</p><p>Figure S2. The optimized geometry of the quintet MnCO+ calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S3. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>279.5 0.52 296.3 3.59 387.4 1.45 2203.5 409.7 </p><p>S3 Figure S3. The optimized geometry of the septet MnCO+ calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S4. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>117.8 4.59 117.8 4.59 150.9 35.4 2283.2 520.1 </p><p>S4 Table S5. The electronic states calculated for Mn(CO)+Ar with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3Mn(CO)+Ar -1791.624557 +33.5</p><p>5Mn(CO)+Ar -1791.6779615 +0.75</p><p>7Mn(CO)+Ar -1791.679162 0.0</p><p>S5 Figure S4. The optimized geometry of the triplet MnCO+Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S6. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>70.6 4.62 174.7 10.1 384.6 0.13 384.6 0.18 455.0 7.33 2169.2 516.7</p><p>Figure S5. The optimized geometry of the quintet MnCO+Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S7. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>41.7 5.19 65.0 3.74 169.9 7.90 291.4 0.27 336.2 1.40 403.8 1.04 2192.7 545.0 </p><p>S6 Figure S6. The optimized geometry of the septet MnCO+Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S8. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>42.3 5.19 66.0 3.73 172.7 7.90 296.3 0.27 341.8 1.40 410.5 1.04 2229.6 544.9 </p><p>S7 + Table S9. The electronic states calculated for Mn(CO) Ar2 with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO) Ar2 -2319.18677207 +30.6</p><p>5 + Mn(CO) Ar2 -2319.2354864 +1.46</p><p>7 + Mn(CO) Ar2 -2319.2378266 0.0</p><p>S8 + Figure S7. The optimized geometry of the triplet MnCO Ar2 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S10. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>67.5 0.88 79.6 3.82 80.4 0.76 154.0 11.4 164.7 8.43 396.2 0.11 428.5 0.49 461.7 10.1 2150.3 556.2 </p><p>S9 + Figure S8. The optimized geometry of the quintet MnCO Ar2 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S11. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>22.5 4.21 41.7 0.88 41.8 4.49 132.8 14.1 141.4 9.20 289.0 0.33 310.0 2.72 404.5 0.87 2182.8 591.1 </p><p>S10 + Figure S9. The optimized geometry of the septet MnCO Ar2 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S12. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>32.5 6.13 41.1 0.46 92.5 12.2 177.6 6.69 188.9 22.5 319.5 4.04 485.9 13.4 2211.8 852.7 </p><p>S11 + Table S13. The electronic states calculated for Mn(CO)2 with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>5 + Mn(CO)2 -1377.5260269 0.0</p><p>3 + Mn(CO)2 -1377.4810479 +28.2</p><p>1 + Mn(CO)2 -1377.4360506 +56.4</p><p>S12 + Figure S10. The optimized geometry of the singlet MnCO2 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S14. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>83.8262 3.496 306.3249 0 306.3285 0.0008 346.2978 0.0001 379.9617 84.5977 511.4033 6.3032 511.4538 6.3984 2195.9135 1184.122 2248.9814 0.0293 </p><p>S13 + Figure S11. The optimized geometry of the triplet MnCO2 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S15. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>86.7587 3.5912 305.5303 0 305.5353 0.0003 351.2383 0.0001 382.5427 97.0855 519.3888 6.89 519.4352 6.9845 2181.8451 1352.4584 2241.5233 0.0302 </p><p>S14 + Figure S11. The optimized geometry of the quintet MnCO2 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S16. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>53.8068 4.7225 266.7266 0.0001 273.2929 0 302.3241 0.0088 304.2598 0.0003 346.6147 81.9415 423.1696 1.0879 2198.0229 1457.6683 2258.613 0.0288 </p><p>S15 + Table S17. The electronic states calculated for Mn(CO)2 Ar with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>5 + Mn(CO)2 Ar (C2v) -1905.0813517 0.0</p><p>3 + Mn(CO)2 Ar (C2v) -1905.0415629 25.0</p><p>1 + Mn(CO)2 Ar (C2v) -1904.9991976 51.6</p><p>3 + Mn(CO)2 Ar (D∞h) -1905.0310439 31.6</p><p>1 + Mn(CO)2 Ar (D∞h) -1377.4360506 59.8</p><p>S16</p><p>+ Figure S12. The optimized geometry of the C2v singlet MnCO2 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S18. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>79.6 1.07 86.2 3.11 86.6 0.44 163.8 10.3 307.1 0 344.0 3.34 346.7 0.21 381.0 93.2 518.9 6.73 527.9 5.38 2180.3 1256.0 2235.8 8.64 </p><p>S17 + Figure S13. The optimized geometry of the C2v triplet MnCO2 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S19. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>80.7 0.38 83.2 0.60 88.3 3.16 142.5 11.8 309.6 0 341.8 1.84 352.2 0.18 384.0 104.4 526.6 7.17 534.8 6.26 2166.4 1406.4 2228.2 7.23 </p><p>S18 + Figure S14. The optimized geometry of the C2v quintet MnCO2 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S20. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>36.1 0.66 51.1 3.78 62.2 3.10 93.7 14.7 268.8 0 272.0 0.20 296.6 0.09 311.0 0.10 337.7 0.06 339.7 89.9 2185.0 1566.8 2249.3 14.5 </p><p>S19 + Table S21. The electronic states calculated for Mn(CO)3 with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO)3 -1490.8678704 0.0</p><p>1 + Mn(CO)3 -1490.8521369 +9.8</p><p>S20 + Figure S15. The optimized geometry of the singlet MnCO3 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S22. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>86.0 1.64 86.1 3.69 91.9 2.31 309.0 0 332.1 0.27 338.6 2.51 348.1 0.16 364.2 61.0 414.5 6.71 512.0 6.77 547.0 29.1 564.5 12.9 2171.8 485.8 2195.3 1096.0 2247.2 0.19 </p><p>S21 + Figure S16. The optimized geometry of the triplet MnCO3 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S23. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>52.1 0.80 52.4 0.80 151.8 0.06 261.8 0 262.5 0 272.1 0 279.7 0 324.1 13.3 324.4 12.7 338.0 9.63 338.3 10.1 2217.0 677.5 2217.2 677.1 2253.5 0.01 </p><p>S22 + Table S4. The electronic states calculated for Mn(CO)3 Ar with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO)3 Ar -1490.8678704 0.0</p><p>1 + Mn(CO)3 Ar -1490.8521369 +16.8</p><p>S23 + Figure S17. The optimized geometry of the singlet MnCO3 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S25. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>46.2 0.21 84.1 0 86.3 0.52 97.8 1.59 100.3 3.38 140.8 7.83 310.7 0 342.3 1.42 363.7 5.73 374.2 59.8 378.0 0 419.2 5.20 525.9 9.57 566.2 26.5 579.2 20.1 2165.9 508.4 2185.8 1111.1 2239.6 12.8 </p><p>S24 + Figure S18. The optimized geometry of the triplet MnCO3 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S26. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>30.4 0.25 71.1 1.12 88.7 0.45 90.7 0.47 91.1 3.09 139.8 8.04 307.8 0.34 312.1 0 352.1 1.23 352.3 0.28 358.8 2.66 375.0 72.6 494.0 29.5 526.7 7.58 566.9 22.6 2160.5 1382.7 2200.9 220.4 2242.1 140.7 </p><p>S25 + Table S27. The electronic states calculated for Mn(CO)4 with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO)4 -1604.2834421 +8.8</p><p>1 + Mn(CO)4 -1604.2974166 0.0</p><p>S26 + Figure S19. The optimized geometry of the singlet MnCO4 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S28. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>75.5 0.02 87.0 2.06 89.3 0 99.8 3.75 107.6 2.65 333.0 0.96 334.8 0.03 337.0 3.18 358.4 0.81 359.4 47.2 402.6 2.68 414.6 11.4 507.0 6.33 535.9 0 553.1 37.6 592.6 22.3 613.0 22.9 2162.1 648.1 2179.3 348.0 2193.5 1045.5 2245.5 0.58 </p><p>S27 + Figure S20. The optimized geometry of the triplet MnCO4 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S29. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity</p><p>46.0 0.23 46.1 0.24 69.9 1.55 83.6 2.50 83.8 2.49 264.1 2.98 271.8 0 299.7 6.66 300.2 6.67 311.3 7.75 311.5 7.53 328.7 1.99 328.8 2.05 349.8 0.06 461.3 19.5 519.0 2.28 519.3 2.27 2145.9 557.8 2221.4 612.7 2221.7 612.9 2254.2 0.93 </p><p>S28 + Table S30. The electronic states calculated for Mn(CO)4 Ar with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO)4 Ar -2131.8435635 +9.5</p><p>1 + Mn(CO)4 Ar -2131.8586255 0.0</p><p>S29 + Figure S21. The optimized geometry of the singlet MnCO4 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S31. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity</p><p>49.6 0.19 2156.0 656.3 78.3 0 2173.4 357.4 81.1 0.02 2173.4 357.4 90.7 0 2239.3 13.9 91.0 1.15 105.6 1.11 106.1 2.59 138.9 8.43 338.2 0.07 341.6 2.00 364.7 13.6 370.6 36.4 378.2 1.02 409.8 1.73 420.2 11.3 519.9 6.17 546.6 0 567.0 38.3 600.9 31.3 626.8 27.8 </p><p>S30 + Figure S22. The optimized geometry of the triplet MnCO4 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S32. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity</p><p>44.1 0.01 2141.4 519.8 44.2 0.01 2209.5 643.7 73.1 0 2209.7 644.5 73.2 0 2244.9 5.73 80.6 0.45 95.3 2.07 95.4 2.07 131.9 6.34 269.4 2.34 277.4 0 318.0 18.9 318.3 18.8 335.7 1.58 335.8 1.59 341.8 0.01 342.0 0.02 401.8 0.10 463.3 15.5 548.0 5.53 548.1 5.54 </p><p>S31 + Table S33. The electronic states calculated for Mn(CO)5 with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO)5 -1717.7017608 +8.7</p><p>1 + Mn(CO)5 -1717.7156852 0.0</p><p>S32 + Figure S23. The optimized geometry of the singlet MnCO5 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S34. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity</p><p>63.4 0 2189.6 1016.8 83.9 0.03 2189.7 1018.9 83.9 0.03 2205.6 0.14 94.0 0 2253.8 0.01 103.7 2.70 103.7 2.70 107.0 1.96 339.3 0 339.3 0 342.3 0 346.0 1.87 346.8 0 377.1 36.9 377.2 37.0 414.2 4.74 481.5 0 532.4 0.08 532.9 4.30 532.9 4.29 611.9 68.9 612.0 68.6 615.2 73.2 2169.5 494.4 </p><p>S33</p><p>+ Figure S24. The optimized geometry of the triplet MnCO5 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S35. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity 40.4 0.05 2195.9 0.12 40.8 0.05 2219.7 534.7 78.6 2.85 2220.3 534.0 81.6 0 2254.2 0.06 81.8 0 98.7 1.20 98.7 1.20 271.6 0 276.7 0 311.6 7.36 311.7 7.43 321.9 0 322.0 0 340.6 3.22 341.0 3.33 350.8 24.0 357.0 0.04 479.0 58.9 497.2 0 497.5 0.01 574.6 46.0 574.8 46.1 </p><p>S34 + Table S36. The electronic states calculated for Mn(CO)5 Ar with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO)5 Ar -2245.2526065 +13.6</p><p>1 + Mn(CO)5 Ar -2245.2743638 0.0</p><p>S35 + Figure S25. The optimized geometry of the singlet MnCO5 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S37. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity</p><p>67.2 0 622.2 83.2 67.4 0 622.5 83.2 67.8 0 627.5 71.7 87.4 0 2166.6 505.1 87.5 0 2184.2 1007.0 94.6 0 2184.4 1008.9 98.2 0 2200.4 2.35 109.1 1.91 2249.5 8.52 109.2 1.92 124.5 6.11 344.7 0 349.1 0.86 351.1 0.01 364.8 0.03 364.9 0.04 384.2 36.4 384.4 36.5 418.7 3.70 496.9 0 534.6 0.03 537.9 4.27 538.2 4.43 </p><p>S36 + Figure S26. The optimized geometry of the triplet MnCO5 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S38. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity</p><p>12.5 0.48 479.7 58.3 24.3 1.42 574.2 46.7 </p><p>40.8 0.02 496.6 0.22 43.1 0.02 498.7 0.04 78.9 2.81 576.1 45.6 81.4 0 2165.4 1267.3 </p><p>82.0 0 2195.4 0.52 </p><p>98.3 1.16 2219.3 526.8 98.7 1.36 2219.7 532.8 271.4 0.02 2253.8 0.09 276.3 0.01 310.6 7.72 311.9 8.26 322.0 0 322.5 0 338.4 2.42 </p><p>S37 343.0 3.18 351.8 23.9 357.6 0.01 </p><p>S38 + Table S39. The electronic states calculated for Mn(CO)6 with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms. </p><p>Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)</p><p>3 + Mn(CO)6 -1831.0570285 +48.0</p><p>1 + Mn(CO)6 -1831.1335673 0.0</p><p>S39 + Figure S27. The optimized geometry of the singlet MnCO6 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S40. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity 71.8 0 635.0 159.1 72.0 0 635.3 159.3 72.1 0 2188.6 1061.8 97.5 0 2188.7 1061.9 97.5 0 2188.8 1061.7 97.6 0 2203.2 0 111.8 1.66 2203.3 0 112.0 1.65 2263.8 0 112.0 1.65 346.3 0 346.7 0 346.9 0 355.7 0 357.0 0 357.1 0 392.9 27.1 393.0 27.0 393.1 26.9 498.3 0 498.4 0 498.6 0 544.4 0 544.4 0 544.6 0 634.9 159.1 </p><p>S40 + Figure S28. The optimized geometry of the triplet MnCO6 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S41. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity 42.9 0 572.8 33.9 43.0 0 2142.9 1321.5 46.5 0 2183.5 0 53.0 0 2230.0 0.03 64.8 0 2230.3 507.6 64.9 0 2230.3 507.1 68.6 1.64 2260.4 0 88.4 3.65 88.4 3.63 115.8 2.11 116.1 2.14 146.0 0 219.2 0 240.8 0 241.0 0 264.6 0.77 264.8 0.76 299.0 0 306.6 0 343.0 0.23 360.3 0 425.9 0 426.0 0 448.9 130.8 572.8 33.9 </p><p>S41 + Figure S29. The optimized geometry of the singlet MnCO6 Ar calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S42. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity</p><p>-4.18 0.25 514.1 0 16.1 0.33 534.2 0.11 16.8 0.96 534.4 0 72.9 0 534.6 0.02 73.5 0 649.6 150.5 73.7 0 649.8 147.8 95.4 0 650.0 144.3 95.5 0 2189.0 968.1 96.5 0 2189.7 971.8 111.1 1.78 2189.8 978.5 111.1 1.78 2203.6 1.76 111.6 1.89 2204.1 2.58 347.8 0 2261.4 0.04 348.0 0 348.1 0 353.6 0 356.2 0 356.4 0.01 394.8 27.5 395.2 27.4 395.3 26.6 513.9 0.00 513.9 0.04 </p><p>S42 + Figure S30. The optimized geometry of the singlet MnCO7 calculated with the B3LYP functional using Gaussian03. The Def 2 TZVPP basis set was used for all atoms.</p><p>Table S43. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.</p><p>Frequency Intensity Frequency Intensity 19.1 0.19 514.4 0 21.0 0.18 534.2 0.33 38.4 1.12 534.4 0.04 62.1 0 534.7 0 62.4 0 649.5 162.1 72.8 0 650.3 144.0 74.6 0 650.4 143.8 75.1 0 2182.2 512.8 95.7 0 2189.0 950.5 95.9 0 2189.1 949.5 97.2 0.06 2190.0 655.4 111.0 1.76 2203.5 5.95 111.2 1.76 2203.7 6.47 113.1 1.91 2261.3 0.12 347.7 0 348.3 0 348.6 0 354.1 0 356.9 0 357.0 0 395.3 26.8 395.6 26.5 395.9 26.4 513.8 0 514.2 0 </p><p>S43</p>