Symmetry/Asymmetry of the NHN Hydrogen Bond in Protonated 1,8-Bis(dimethylamino)naphthalene
Abstract
:1. Introduction
2. Materials and Methods
2.1. Compound and Synthesis
Bis(dimethylamino)naphthalene Sulfate
8-Bis(dimethylamino)naphthalene Sulfate-d2
2.2. Infrared Spectra Measurements
2.3. Incoherent Inelastic Neutron Scattering (IINS) Measurements
2.4. NMR Measurements
2.5. Static DFT and D3-DFT Calculations
2.6. Symmetry-Adapted Perturbation Theory Calculations
2.7. Car–Parrinello Molecular Dynamics Simulations
3. Results and Discussion
3.1. SAPT Analysis of the DMANH+ HSO4− Complex
3.2. Metric Parameter Time-Evolution Analysis Based on Car–Parrinello Molecular Dynamics
3.3. DFT and D3-DFT Analysis of PES
3.4. Comparison of Experimental IINS, IR, and Calculated CPMD Spectra
4. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Appendix A
Mode № | IR | IINS | Wavenumber [cm−1] | Intensities [km/mol] |
---|---|---|---|---|
exp. | exp. | calc. | calc. | |
tr | 9, 14, 35, 46 | |||
1 | 56 | 51.74 | 0.52 | |
2 | 72 | |||
3 | 84 | 80 | ||
4 | 93 | 91 | 99.49 | 0.23 |
5 | 115.46 | 3.64 | ||
6 | 124 | 122 | 122.23 | 0.28 |
7 | 126.25 | 1.04 | ||
8 | 135 | 141 | 151.23 | 0.59 |
9 | 162 | 163 | 172.50 | 0.95 |
10 | 193 | 190 | ||
11 | 200 | 211.02 | 0.02 | |
12 | 243 | 222 | 231.19 | 0.68 |
13 | 263 | 259 | 261.03 | 4.05 |
14 | 286 | 277 | 295.65 | 1.52 |
15 | 304 | 296 | 303.45 | 1.05 |
16 | 310 | 312.48 | 4.87 | |
17 | 334 | 325.28 | 0.29 | |
18 | 351 | 351 | 350.55 | 1.38 |
19 | 363 | 361 | 367.12 | 4.21 |
20 | 382 | 385 | 385.57 | 3.15 |
21 | 443 | 446 | 442.71 | 1.12 |
22 | 468 | 474 | 478.21 | 5.77 |
23 | 484.85 | 2.56 | ||
24 | 525 | 528 | 535.68 | 5.75 |
25 | 536.21 | 1.67 | ||
26 | 538.78 | 0.01 | ||
27 | 577 | 551.01 | 1.67 | |
28 | 643 | 620 | 632.15 | 2.95 |
29 | 661 | 649 | 654.22 | 8.74 |
30 | 677.28 | 7.42 | ||
31 | 752 | 766 | 766.11 | 0.11 |
32 | 779 | 771.44 | 0.69 | |
33 | 775.50 | 79.16 | ||
34 | 793.09 | 3.25 | ||
35 | 818 | 839.55 | 27.81 | |
36 | 870 | 876.68 | 0.14 | |
37 | 887 | 892.78 | 1.88 | |
38 | 897.72 | 2.49 | ||
39 | 937 | 947.92 | 40.51 | |
40 | 956 | 971 | 973.02 | 0.65 |
41 | 980.44 | 0.31 | ||
42 | 1032 | 1041.07 | 95.25 | |
43 | 1056 | 1053.03 | 25.44 | |
44 | 1072.89 | 23.97 | ||
45 | 1092 | 1073.11 | 9.06 | |
46 | 1108.97 | 12.30 | ||
47 | 1113 | 1112.14 | 4.67 | |
48 | 1122.56 | 0.38 | ||
49 | 1136 | 1131.23 | 4.10 | |
50 | 1152 | 1158.87 | 0.66 | |
51 | 1162.50 | 44.36 | ||
52 | 1185 | 1178.07 | 1.90 | |
53 | 1197 | 1188.05 | 2.11 | |
54 | 1200 b | 1205.20 | 27.08 | |
55 | 1220.59 | 6.34 | ||
56 | 1226 | 1224.03 | 4.29 | |
57 | 1242.37 | 18.36 | ||
58 | 1248.75 | 14.89 | ||
59 | 1324 | 1333.17 | 15.30 | |
60 | 1343 | 1348.38 | 47.07 | |
61 | 1360.88 | 23.49 | ||
62 | 1384 | 1369.77 | 22.02 | |
63 | 1420 | 1407.98 | 74.73 | |
64 | 1448 | 1443.03 | 0.43 | |
65 | 1443.45 | 0.39 | ||
66 | 1456.69 | 21.91 | ||
67 | 1463 | 1466 b | 1464.24 | 5.54 |
68 | 1473.32 | 1.03 | ||
69 | 1479 | 1477.99 | 0.62 | |
70 | 1481.23 | 3.35 | ||
71 | 1485.18 | 9.10 | ||
72 | 1492.70 | 20.46 | ||
73 | 1493.08 | 30.41 | ||
74 | 1500.92 | 2.48 | ||
75 | 1511 | 1502.60 | 16.87 | |
76 | 1521.37 | 11.25 | ||
77 | 1524.98 | 22.79 | ||
78 | 1576 | 1542.86 | 22.63 | |
79 | 1605 | 1608.92 | 191.50 | |
80 | 1722 | 1632.70 | 1.17 | |
81 | 1641.10 | 11.45 | ||
82 | 2926.35 | 160.99 | ||
83 | 2777 | 2926.67 | 11.27 | |
84 | 2824 | 2939.86 | 267.58 | |
85 | 2852 | 2941.71 | 37.29 | |
86 | 2928 | 3051.65 | 27.31 | |
87 | 2971 | 3051.81 | 17.97 | |
88 | 3013 | 3056.51 | 12.52 | |
89 | 3048 | 3057.11 | 96.53 | |
90 | 3093 | 3101.58 | 16.29 | |
91 | 3101.61 | 24.04 | ||
92 | 3158.93 | 4.96 | ||
93 | 3159.18 | 17.51 | ||
94 | 3159.31 | 0.06 | ||
95 | 3161.34 | 1.11 | ||
96 | 3176.94 | 10.44 | ||
97 | 3180.00 | 43.23 | ||
98 | 3204.39 | 11.51 | ||
99 | 3204.41 | 8.22 |
№ | IR | IINS | Raman | Wavenumber [cm−1] | Intensities [km/mol] |
---|---|---|---|---|---|
exp. | exp. | exp. | calc. | calc. | |
1 | 14.57 | 0.03 | |||
2 | 17.59 | 1.10 | |||
3 | 36.81 | 1.37 | |||
4 | 42.72 | 0.88 | |||
5 | 60.97 | 1.86 | |||
6 | 83.84 | 25.22 | |||
7 | 90 | 90.41 | 5.08 | ||
8 | 93.29 | 0.17 | |||
9 | 147.02 | 43.61 | |||
10 | 152.75 | 31.05 | |||
11 | 162 | 161.14 | 3.03 | ||
12 | 185 | 185.56 | 9.32 | ||
13 | 185.81 | 15.51 | |||
14 | 194 | 198 | 198.61 | 0.12 | |
15 | 242.02 | 3.42 | |||
16 | 243.48 | 2.73 | |||
17 | 249 | 252.75 | 10.81 | ||
18 | 256.74 | 0.23 | |||
19 | 262 | 262 | 263.71 | 0.50 | |
20 | 274 | 288.84 | 3.22 | ||
21 | 325 | 325.96 | 0.01 | ||
22 | 329 | 332.45 | 8.04 | ||
23 | 378.53 | 3.30 | |||
24 | 382 | 383 | 384.15 | 6.38 | |
25 | 399.35 | 13.15 | |||
26 | 419 | 422.01 | 12.28 | ||
27 | 440 | 439 | 441.72 | 3.17 | |
28 | 466 | 470 | 481.60 | 0.24 | |
29 | 503 | 498.35 | 10.20 | ||
30 | 511 | 525.17 | 5.77 | ||
31 | 525.65 | 52.86 | |||
32 | 533 | 533 | 534 | 536.22 | 9.97 |
33 | 539.01 | 0.17 | |||
34 | 540.81 | 3.02 | |||
35 | 545.32 | 31.75 | |||
36 | 584 | 585 | 593 | 583.61 | 12.63 |
37 | 642 | 649.80 | 0.00 | ||
38 | 676 | 674.12 | 35.07 | ||
39 | 687 | 678.86 | 0.26 | ||
40 | 732.25 | 299.92 | |||
41 | 776.12 | 0.93 | |||
42 | 779 | 781.77 | 1.30 | ||
43 | 787 | 789.15 | 71.35 | ||
44 | 796.76 | 0.78 | |||
45 | 841 | 844 | 853.32 | 15.88 | |
46 | 846 | 877 | 866.23 | 13.02 | |
47 | 908.56 | 22.33 | |||
48 | 922.62 | 0.27 | |||
49 | 949 | 938.58 | 1.60 | ||
50 | 989.33 | 3.63 | |||
51 | 995.53 | 4.04 | |||
52 | 1002.12 | 1.26 | |||
53 | 1004.20 | 115.91 | |||
54 | 1007 | 1013 | 1007 | 1004.66 | 102.37 |
55 | 1031 | 1025 | 1047.32 | 17.60 | |
56 | 1049 | 1049 | 1047.85 | 18.21 | |
57 | 1087 | 1088.53 | 0.09 | ||
58 | 1099 | 1104.66 | 212.72 | ||
59 | 1108.80 | 8.72 | |||
60 | 1112 | 1110.39 | 10.96 | ||
61 | 1114 | 1114.95 | 4.13 | ||
62 | 1155 | 1170.56 | 30.47 | ||
63 | 1173 | 1175.17 | 65.76 | ||
64 | 1181.23 | 21.65 | |||
65 | 1193 | 1195.65 | 20.18 | ||
66 | 1196.71 | 26.24 | |||
67 | 1199.61 | 175.54 | |||
68 | 1200.30 | 166.15 | |||
69 | 1210 | 1217.08 | 170.92 | ||
70 | 1223 | 1228.08 | 9.32 | ||
71 | 1239.64 | 13.43 | |||
72 | 1245.05 | 26.67 | |||
73 | 1264.43 | 4.50 | |||
74 | 1305.30 | 11.88 | |||
75 | 1354.70 | 48.76 | |||
76 | 1365 | 1365.64 | 3.30 | ||
77 | 1379 | 1386.47 | 15.33 | ||
78 | 1414 | 1415 | 1436.10 | 1.65 | |
79 | 1431 | 1438.56 | 79.01 | ||
80 | 1443 | 1451.21 | 3.09 | ||
81 | 1469 | 1465.77 | 1.48 | ||
82 | 1480.31 | 7.45 | |||
83 | 1482.26 | 0.71 | |||
84 | 1488.20 | 15.25 | |||
85 | 1488.98 | 0.97 | |||
86 | 1490 | 1497.56 | 0.69 | ||
87 | 1495 | 1498.85 | 20.69 | ||
88 | 1503.20 | 8.53 | |||
89 | 1505.92 | 5.75 | |||
90 | 1511.50 | 82.43 | |||
91 | 1518 | 1514.96 | 23.30 | ||
92 | 1521.21 | 24.25 | |||
93 | 1578 | 1580 | 1551.47 | 22.12 | |
94 | 1603 | 1612.85 | 5.43 | ||
95 | 1626 | 1627 | 1617.33 | 8.56 | |
96 | 1644.36 | 9.08 | |||
97 | 1664.89 | 16.75 | |||
98 | 2600 | 2529.78 | 977.93 | ||
99 | 2809 | 2984.75 | 30.16 | ||
100 | 2940 | 2866 | 2989.37 | 66.45 | |
101 | 2952 | 3056.91 | 10.25 | ||
102 | 3015 | 3060.71 | 59.04 | ||
103 | 3065 | 3081.84 | 19.34 | ||
104 | 3082.70 | 19.25 | |||
105 | 3134.13 | 0.65 | |||
106 | 3137.65 | 8.34 | |||
107 | 3148.81 | 1.78 | |||
108 | 3150.19 | 9.61 | |||
109 | 3154.58 | 2.99 | |||
110 | 3160.22 | 69.10 | |||
111 | 3168.92 | 0.48 | |||
112 | 3172.93 | 0.06 | |||
113 | 3181.07 | 9.40 | |||
114 | 3186.35 | 13.84 | |||
115 | 3192.70 | 10.19 | |||
116 | 3198.99 | 4.40 | |||
117 | 3794.06 | 87.38 |
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Electrostatics | Exchange | Induction | Dispersion | Total HF | Total SAPT2 |
---|---|---|---|---|---|
−87.17 | 24.98 | −14.64 | −11.44 | −79.25 | −88.28 |
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Piękoś, P.; Jezierska, A.; Panek, J.J.; Goremychkin, E.A.; Pozharskii, A.F.; Antonov, A.S.; Tolstoy, P.M.; Filarowski, A. Symmetry/Asymmetry of the NHN Hydrogen Bond in Protonated 1,8-Bis(dimethylamino)naphthalene. Symmetry 2020, 12, 1924. https://doi.org/10.3390/sym12111924
Piękoś P, Jezierska A, Panek JJ, Goremychkin EA, Pozharskii AF, Antonov AS, Tolstoy PM, Filarowski A. Symmetry/Asymmetry of the NHN Hydrogen Bond in Protonated 1,8-Bis(dimethylamino)naphthalene. Symmetry. 2020; 12(11):1924. https://doi.org/10.3390/sym12111924
Chicago/Turabian StylePiękoś, Patrycja, Aneta Jezierska, Jarosław J. Panek, Eugene A. Goremychkin, Alexander F. Pozharskii, Alexander S. Antonov, Peter M. Tolstoy, and Aleksander Filarowski. 2020. "Symmetry/Asymmetry of the NHN Hydrogen Bond in Protonated 1,8-Bis(dimethylamino)naphthalene" Symmetry 12, no. 11: 1924. https://doi.org/10.3390/sym12111924