Conformational Structures of Neutral and Cationic Pivaldehyde Revealed by IR-Resonant VUV-MATI Mass Spectroscopy
Abstract
:1. Introduction
2. Results and Discussion
2.1. Conformer-Specific Photoionization of Pivaldehyde
2.2. Conformational Structure of Neutral Pivaldehyde
2.3. Cationic Structure of Pivaldehyde
2.4. HOMO and SOMO of Pivaldehyde
3. Materials and Methods
3.1. Experimental Methods
3.2. Theoretical Methods
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Mode a | S0 (C1) | D0 (CS) | ||||||
---|---|---|---|---|---|---|---|---|
VUV-MATI | FC (CS→) d | FC (C1→) c | ||||||
Exp b | Cal c | Freq | Int e | Freq | Int e | Freq | Int e | |
Fundamentals | ||||||||
421 | 70 | 77 | 55 | 0.013 | 54 | 54 | 0.014 | |
411 | 222 | 196 | 199 | 0.004 | 195 | 195 | 1 × 10−4 | |
391 | 330 | 322 | 309 | 0.012 | 308 | 308 | 5 × 10−4 | |
241 | 267 | 250 | 235 | 0.031 | 239 | 0.012 | 239 | 0.013 |
231 | 278 | 275 | 246 | 0.082 | 242 | 0.059 | 242 | 0.058 |
221 | 348 | 346 | 270 | 0.242 | 267 | 0.475 | 267 | 0.472 |
211 | 389 | 385 | 363 | 0.676 | 361 | 0.814 | 361 | 0.815 |
201 | 593 | 590 | 416 | 1.000 | 417 | 1.000 | 417 | 1.000 |
191 | 764 | 759 | 473 | 0.126 | 480 | 0.330 | 480 | 0.331 |
161 | 1041 | 1038 | 996 | 0.081 | 989 | 0.069 | 989 | 0.069 |
151 | 1217 | 1222 | 1025 | 0.070 | 1032 | 0.146 | 1032 | 0.147 |
141 | 1277 | 1279 | 1117 | 0.171 | 1131 | 0.347 | 1131 | 0.347 |
111 | 1406 | 1410 | 1387 | 0.089 | 1398 | 0.006 | 1398 | 0.006 |
101 | 1457 | 1453 | 1437 | 0.067 | 1435 | 0.003 | 1435 | 0.003 |
81 | 1484 | 1489 | 1473 | 0.132 | 1483 | 0.002 | 1483 | 0.002 |
71 | 1774 | 1805 | 1867 | 0.086 | 1888 | 0.075 | 1888 | 0.074 |
Overtones and combinations | ||||||||
422 | 130 | 154 | 110 | 0.009 | 108 | 0.016 | 108 | 0.013 |
423 | 166 | 0.001 | 162 | 162 | 0.001 | |||
241221 | 504 | 0.036 | 506 | 0.001 | 506 | 0.001 | ||
222 | 538 | 0.045 | 535 | 0.069 | 535 | 0.067 | ||
241211 | 596 | 0.027 | 600 | 0.007 | 600 | 0.008 | ||
231211 | 610 | 0.039 | 603 | 0.086 | 603 | 0.085 | ||
221211 | 632 | 0.156 | 628 | 0.375 | 628 | 0.373 | ||
241201 | 650 | 0.039 | 656 | 0.011 | 656 | 0.013 | ||
231201 | 662 | 0.076 | 660 | 0.100 | 660 | 0.099 | ||
221201 | 685 | 0.196 | 685 | 0.476 | 685 | 0.472 | ||
212 | 726 | 0.185 | 722 | 0.339 | 722 | 0.340 | ||
221191 | 750 | 0.081 | 748 | 0.213 | 748 | 0.211 | ||
211201 | 780 | 0.507 | 778 | 0.882 | 778 | 0.882 | ||
202 | 833 | 0.494 | 835 | 0.579 | 835 | 0.578 | ||
201191 | 888 | 0.105 | 898 | 0.351 | 898 | 0.352 | ||
222201 | 955 | 0.054 | 952 | 0.036 | 952 | 0.035 | ||
222191 | 1015 | 0.050 | 1015 | 0.033 | 1015 | 0.032 | ||
221211201 | 1051 | 0.135 | 1046 | 0.274 | 1046 | 0.272 | ||
213 | 1090 | 0.070 | 1082 | 0.065 | 1082 | 0.066 | ||
221211191 | 1106 | 0.153 | 1108 | 0.115 | 1108 | 0.115 | ||
212201 | 1145 | 0.144 | 1139 | 0.280 | 1139 | 0.280 | ||
211202 | 1200 | 0.220 | 1196 | 0.401 | 1196 | 0.400 | ||
203 | 1251 | 0.199 | 1252 | 0.191 | 1252 | 0.191 | ||
202191 | 1306 | 0.057 | 1315 | 0.155 | 1315 | 0.155 | ||
211161 | 1357 | 0.057 | 1350 | 0.060 | 1450 | 0.060 | ||
201161 | 1413 | 0.008 | 1406 | 0.084 | 1406 | 0.084 | ||
211141 | 1482 | 0.157 | 1492 | 0.349 | 1492 | 0.349 | ||
191151 | 1496 | 0.068 | 1513 | 0.062 | 1513 | 0.063 | ||
201141 | 1536 | 0.225 | 1548 | 0.435 | 1548 | 0.435 | ||
212201191 | 1619 | 0.108 | 1619 | 0.028 | 1619 | 0.028 | ||
211202191 | 1671 | 0.095 | 1676 | 0.056 | 1676 | 0.056 | ||
221211141 | 1748 | 0.099 | 1759 | 0.151 | 1759 | 0.150 | ||
231201141 | 1776 | 0.082 | 1791 | 0.051 | 1791 | 0.051 | ||
221201141 | 1803 | 0.131 | 1816 | 0.196 | 1816 | 0.194 | ||
202161 | 1833 | 0.154 | 1824 | 0.045 | 1824 | 0.044 | ||
212141 | 1843 | 0.102 | 1853 | 0.134 | 1853 | 0.134 | ||
211201141 | 1899 | 0.188 | 1909 | 0.356 | 1909 | 0.356 | ||
202141 | 1952 | 0.191 | 1966 | 0.239 | 1966 | 0.238 | ||
201191141 | 2008 | 0.075 | 2029 | 0.150 | 2029 | 0.150 | ||
231202141 | 2195 | 0.064 | 2208 | 0.036 | 2208 | 0.036 | ||
203161 | 2248 | 0.075 | 2241 | 0.013 | 2241 | 0.013 | ||
211202141 | 2320 | 0.061 | 2327 | 0.151 | 2327 | 0.150 | ||
14181 | 2591 | 0.041 | 2614 | 0.001 | 2614 | 0.001 | ||
191151141 | 2614 | 0.049 | 2644 | 0.035 | 2644 | 0.035 |
S0 | D0 | |||
---|---|---|---|---|
Exp a | Cal (Cs) b | Cal (C1) c | Cal (Cs) b | |
Bond length (Å) | ||||
1C–2O | 1.206 | 1.199 | 1.199 | 1.159 (−0.040) d |
1C–4C | 1.516 | 1.516 | 1.516 | 1.724 (0.208) |
4C–5C | 1.537 | 1.523 | 1.523 | 1.505 (−0.018) |
4C–9C (4C–13C) | 1.537 | 1.535 | 1.535 | 1.515 (−0.020) |
1C–3H | 1.130 | 1.113 | 1.113 | 1.103 (−0.010) |
5C–6H | 1.118 | 1.091 | 1.091 | 1.093 (0.002) |
5C–7H (5C–8H) | 1.118 | 1.089 | 1.089 | 1.088 (−0.001) |
9C–10H (13C–14H) | 1.118 | 1.091 | 1.091 | 1.095 (0.004) |
9C–11H (13C–15H) | 1.118 | 1.092 | 1.092 | 1.089 (−0.003) |
9C–12H (13C–16H) | 1.118 | 1.091 | 1.091 | 1.089 (−0.002) |
Bond angle (°) | ||||
2O–1C–4C | 126.0 | 125.9 | 125.9 | 121.0 (−4.9) |
1C–4C–5C | 110.5 | 110.9 | 110.8 | 108.3 (−2.5) |
1C–4C–9C (1C–4C–13C) | 107.4 | 107.1 | 106.9 | 100.5 (−6.4) |
4C–1C–3H | 113.0 | 113.8 | 113.8 | 110.6 (−3.2) |
Dihedral angle (°) | ||||
2O–1C–4C–5C | 2.1 | 0.0 | 2.1 | 0.0 (−2.1) |
Mode (C1) a | IR(CS) b | Cal(CS) c (Har) | Cal(CS) d (Anhar) | Cal(C1) e (Anhar) | IR-Resonant VUV-PI | IR-Dip VUV-MATI | Mode Description f |
---|---|---|---|---|---|---|---|
101 | 2696 | 2727 | 2707 | 2710 | 2689 | 2689 | Cformyl-H stretch |
192 | 2768 | 2695 | 2802 | 2788 | 2762 | 2762 | Overtone of Cformyl-H bending |
191181 | 2791 | 2722 | 2833 | 2819 | 2788 | 2788 | Combination of bending |
182 | 2803 | 2750 | 2849 | 2833 | 2803 | 2803 | Overtone of Cformyl-H bending |
91 | 2876 | 2894 | 2852 | 2852 | 2876 | 2876 | Out-of-plane (CH3)2 asym. stretch |
71 | 2913 | 2904 | 2895 | 2895 | 2913 | 2913 | In-plane CH3 sym. stretch |
61 | 2922 | 2943 | 2943 | Out-of-plane (CH3)2 asym. stretch | |||
51 | 2969 | 2964 | 2925 | 2953 | 2964 | 2964 | Out-of-plane (CH3)2 sym. stretch |
21 | 2980 | 2976 | 2943 | 2970 | 2977 | 2977 | In-plane CH3 asym. stretch |
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Park, S.M.; Lee, Y.R.; Kwon, C.H. Conformational Structures of Neutral and Cationic Pivaldehyde Revealed by IR-Resonant VUV-MATI Mass Spectroscopy. Int. J. Mol. Sci. 2022, 23, 14777. https://doi.org/10.3390/ijms232314777
Park SM, Lee YR, Kwon CH. Conformational Structures of Neutral and Cationic Pivaldehyde Revealed by IR-Resonant VUV-MATI Mass Spectroscopy. International Journal of Molecular Sciences. 2022; 23(23):14777. https://doi.org/10.3390/ijms232314777
Chicago/Turabian StylePark, Sung Man, Yu Ran Lee, and Chan Ho Kwon. 2022. "Conformational Structures of Neutral and Cationic Pivaldehyde Revealed by IR-Resonant VUV-MATI Mass Spectroscopy" International Journal of Molecular Sciences 23, no. 23: 14777. https://doi.org/10.3390/ijms232314777