Matrix Isolation FTIR and Theoretical Study of Weakly Bound Complexes of Isocyanic Acid with Nitrogen
Abstract
:1. Introduction
2. Results and Discussion
2.1. Computational Results
2.1.1. Structure and Energetics of the 1:1 HNCO⋯N2 Complexes
2.1.2. Structure and Energetics of the 1:2 and 2:1 HNCO⋯N2 Complexes
2.2. Matrix Isolation Infrared Spectra
2.2.1. HNCO⋯N2 Complexes of the 1:1 Stoichiometry
2.2.2. HNCO⋯N2 Complexes of the 1:2 and 2:1 Stoichiometry
3. Experimental and Computational Details
3.1. Matrix Isolation FTIR Studies
3.2. Computational Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Complex | Intermolecular Parameters 1 | AIM Parameters | ||||
---|---|---|---|---|---|---|
Interatomic Distances | Angle | BCP | ρ(r) | ∇2ρ(r) | ||
H⋯Y | X⋯Y | X–H⋯Y | ||||
ON1 | 4.372 | 6.258 | 170.7 | H1⋯N5 | 0.0106 | 0.0419 |
ON2 | 6.187 | N2⋯N5 | 0.0048 | 0.0197 | ||
ON3 | 5.992 | C3⋯N5 | 0.0051 | 0.0215 |
Complex | MP2 | B2PLYPD3 | B3LYPD3 | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Eint | ΔE | ΔG | A | TΔS 1 | Eint | ΔE | ΔG | A | TΔS | Eint | ΔE | ΔG | A | TΔS | |
ON1 | −6.53 | 0.00 | 4.72 | 9 | −7.79 | −6.49 | 0.00 | 5.40 | 7 | −8.90 | −6.40 | 0.00 | 4.51 | 14 | −7.91 |
ON2 | −3.10 | 3.40 | 0.00 | 61 | 0.00 | −2.59 | 3.86 | 0.00 | 63 | 0.00 | −2.68 | 3.72 | 0.00 | 86 | 0.00 |
ON3 | −4.52 | 2.00 | 1.76 | 30 | −3.11 | −4.31 | 2.21 | 1.87 | 30 | −3.44 |
Complex | MP2 | B2PLYPD3 | B3LYPD3 | |||
---|---|---|---|---|---|---|
Eint | ΔE | Eint | ΔE | Eint | ΔE | |
O2N1 | −11.67 | 0.00 | −11.13 | 0.00 | −11.34 | 0.00 |
O2N2 | −11.00 | 0.69 | −10.17 | 0.98 | −10.04 | 1.26 |
O2N3 | −9.58 | 2.10 | −9.04 | 2.08 | −9.04 | 2.27 |
O2N4 | −9.25 | 2.47 |
Complex | MP2 | B2PLYPD3 | B3LYPD3 | |||
---|---|---|---|---|---|---|
Eint | ΔE | Eint | ΔE | Eint | ΔE | |
2ON1 | −24.77 | 0.00 | −24.60 | 0.00 | −24.85 | 0.00 |
2ON2 | −23.81 | 1.09 | −23.97 | 0.71 | −24.81 | 0.19 |
2ON3 | −22.89 | 2.02 | −22.64 | 2.07 | −23.56 | 1.43 |
2ON4 | −22.13 | 2.62 | −22.72 | 1.86 | −24.31 | 0.63 |
2ON5 | −21.17 | 3.88 | −22.13 | 2.70 | −22.84 | 2.26 |
2ON6 | −20.38 | 4.31 | −20.67 | 3.83 | −21.80 | 2.96 |
2ON7 | −19.50 | 5.19 | −19.66 | 4.84 | −20.88 | 3.89 |
2ON8 | −18.37 | 6.32 | −18.70 | 5.79 | −20.84 | 3.97 |
2ON9 | −18.28 | 6.43 | −18.62 | 5.90 | −19.75 | 5.04 |
2ON10 | −16.48 | 8.18 | −17.03 | 7.44 | −18.74 | 6.06 |
MP2 | B2PLYPD3 | B3LYPD3 | Mode | Exp.1 | |||||
---|---|---|---|---|---|---|---|---|---|
ON1 | ON2 | ON3 | ON1 | ON2 | ON3 | ON1 | ON2 | ||
−25 (405) | −6 (169) | −9 (163) | −25 (401) | −5 (155) | −8 (149) | −23 (392) | −4 (155) | νNH | −17.5, −12.0 |
+2 (706) | −2 (631) | −2 (636) | +2 (732) | −1 (654) | −2 (654) | +2 (798) | 0 (712) | νasNCO | +1.5, −1.0 |
+21 (76) | −3 (83) | −6 (97) | +22 (63) | −3 (72) | −4 (81) | +20 (67) | −3 (75) | δNCO | +5.0, −5.5 |
MP2 | B2PLYPD3 | B3LYPD3 | Mode | Exp.1 | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|
O2N1 | O2N2 | O2N3 | O2N4 | O2N1 | O2N2 | O2N3 | O2N1 | O2N2 | O2N3 | ||
−35 (380) | −33 (398) | −31 (397) | −11 (159) | −32 (376) | −31 (391) | −28 (394) | −29 (364) | −23 (345) | −26 (386) | νNH | −31.0 |
0 (662) | 0 (740) | 0 (661) | −1 (604) | 0 (687) | 0 (769) | 0 (688) | 0 (748) | 0 (837) | +1 (751) | νasNCO | |
+16 (73) | +22 (81) | +19 (69) | −6 (96) | +17 (61) | +21 (68) | +19 (58) | +16 (66) | +16 (78) | +17 (62) | δNCO | +22.5 |
MP2 | B2PLYPD3 | B3LYPD3 | Mode | Exp.1 | ||||||
---|---|---|---|---|---|---|---|---|---|---|
2ON1 | 2ON2 | 2ON3 | 2ON1 | 2ON2 | 2ON3 | 2ON1 | 2ON2 | 2ON3 | ||
−64 (361) | −61 (340) | −39 (177) | −64 (367) | −60 (339) | −36 (163) | −60 (344) | −53 (315) | −34 (163) | νNH | −51.5, −54.5, −68.5, −76,5 |
−145 (769) | −150 (770) | −153 (784) | −154 (780) | −157 (762) | −158 (780) | −170 (830) | −174 (810) | −171 (808) | −141.0, −154.5, −158.5 | |
+5 (486) | +5 (21) | +5 (697) | +7 (532) | +6 (32) | +7 (724) | +9 (635) | +8 (43) | +9 (799) | νasNCO | +9.0, +5.0 |
−6 (1090) | −7 (1553) | −9 (650) | −7 (1103) | −8 (1599) | −10 (679) | −7 (1145) | −8 (1738) | −9 (734) | −3.0, −7.0 | |
+66 (0) | +63 (37) | +61 (22) | +61 (1) | +62 (2) | +57 (2) | +64 (2) | +65 (3) | +61 (4) | δNCO | n.o. |
+4 (187) | +11 (26) | −5 (72) | +9 (145) | +13 (20) | −3 (60) | +10 (137) | +14 (22) | −1 (60) | +8.0, +2.5, −7.0 |
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Krupa, J.; Wierzejewska, M.; Lundell, J. Matrix Isolation FTIR and Theoretical Study of Weakly Bound Complexes of Isocyanic Acid with Nitrogen. Molecules 2022, 27, 495. https://doi.org/10.3390/molecules27020495
Krupa J, Wierzejewska M, Lundell J. Matrix Isolation FTIR and Theoretical Study of Weakly Bound Complexes of Isocyanic Acid with Nitrogen. Molecules. 2022; 27(2):495. https://doi.org/10.3390/molecules27020495
Chicago/Turabian StyleKrupa, Justyna, Maria Wierzejewska, and Jan Lundell. 2022. "Matrix Isolation FTIR and Theoretical Study of Weakly Bound Complexes of Isocyanic Acid with Nitrogen" Molecules 27, no. 2: 495. https://doi.org/10.3390/molecules27020495