Infrared Spectroscopy and Structures of Manganese Carbonyl Cations, Mn(CO)N+ (N=1-9)
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Supporting Information
Infrared Spectroscopy and Structures of
+ Manganese Carbonyl Cations, Mn(CO)n (n=1-9)
Z.D. Reed and M.A. Duncan
Department of Chemistry, University of Georgia, Athens GA 30602-2556
Email. [email protected]; Fax . 706-542-1234
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3Mn(CO)+ -1264.0568491 +33.6
5Mn(CO)+ -1264.1104673 +0.74
7Mn(CO)+ -1264.1116475 0.0
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.
Table S2. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
351.5 1.56 351.5 1.56 454.1 9.62 2176.9 402.1
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.
Table S3. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
279.5 0.52 296.3 3.59 387.4 1.45 2203.5 409.7
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.
Table S4. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
117.8 4.59 117.8 4.59 150.9 35.4 2283.2 520.1
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3Mn(CO)+Ar -1791.624557 +33.5
5Mn(CO)+Ar -1791.6779615 +0.75
7Mn(CO)+Ar -1791.679162 0.0
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.
Table S6. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
70.6 4.62 174.7 10.1 384.6 0.13 384.6 0.18 455.0 7.33 2169.2 516.7
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.
Table S7. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S8. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO) Ar2 -2319.18677207 +30.6
5 + Mn(CO) Ar2 -2319.2354864 +1.46
7 + Mn(CO) Ar2 -2319.2378266 0.0
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.
Table S10. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S11. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S12. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
5 + Mn(CO)2 -1377.5260269 0.0
3 + Mn(CO)2 -1377.4810479 +28.2
1 + Mn(CO)2 -1377.4360506 +56.4
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.
Table S14. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S15. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S16. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
5 + Mn(CO)2 Ar (C2v) -1905.0813517 0.0
3 + Mn(CO)2 Ar (C2v) -1905.0415629 25.0
1 + Mn(CO)2 Ar (C2v) -1904.9991976 51.6
3 + Mn(CO)2 Ar (D∞h) -1905.0310439 31.6
1 + Mn(CO)2 Ar (D∞h) -1377.4360506 59.8
S16
+ 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.
Table S18. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S19. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S20. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO)3 -1490.8678704 0.0
1 + Mn(CO)3 -1490.8521369 +9.8
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.
Table S22. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S23. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO)3 Ar -1490.8678704 0.0
1 + Mn(CO)3 Ar -1490.8521369 +16.8
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.
Table S25. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S26. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO)4 -1604.2834421 +8.8
1 + Mn(CO)4 -1604.2974166 0.0
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.
Table S28. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Table S29. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO)4 Ar -2131.8435635 +9.5
1 + Mn(CO)4 Ar -2131.8586255 0.0
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.
Table S31. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity Frequency Intensity
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
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.
Table S32. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity Frequency Intensity
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO)5 -1717.7017608 +8.7
1 + Mn(CO)5 -1717.7156852 0.0
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.
Table S34. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity Frequency Intensity
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
S33
+ 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.
Table S35. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
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
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO)5 Ar -2245.2526065 +13.6
1 + Mn(CO)5 Ar -2245.2743638 0.0
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.
Table S37. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity Frequency Intensity
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
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.
Table S38. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity Frequency Intensity
12.5 0.48 479.7 58.3 24.3 1.42 574.2 46.7
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
82.0 0 2195.4 0.52
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
S37 343.0 3.18 351.8 23.9 357.6 0.01
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.
Isomer Total Energy (Hartrees) Relative Energy (kcal/mol)
3 + Mn(CO)6 -1831.0570285 +48.0
1 + Mn(CO)6 -1831.1335673 0.0
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.
Table S40. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
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
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.
Table S41. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
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
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.
Table S42. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
Frequency Intensity Frequency Intensity
-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
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.
Table S43. The unscaled normal mode frequencies and intensities (km/mol) are reported from this same level of theory.
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
S43