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Based on the method of density functional theory B3LYP with a 6-311++G(d, p) basis set, the potential energy surface of conformational isomerization along the two-dimensional coordinates formed by the dihedral angles ϕ1(C9N1C2C5) and ϕ2(C16N1C9C12) in a range of –180°–180° is investigated. And 12 ground state conformers of triethylamine are identified. Furthermore,with the second-order Moller-Plesset perturbation theory MP2 on the same basis set level, the structures of six lower-energy conformers are optimized and their energy values are estimated. The results show that G1 and G1' with C3 symmetry are the most stable conformers and G4 and G4' with new methyl orientations are identified. In addition, some vibrational modes in the infrared spectra of G1–G4 are assigned and discussed. The infrared spectra of G1–G4 show that the intensity is weak in a range of 0–1600 cm–1, while the intensity is strong in a range of 2800–3300 cm–1. The characteristic vibration modes such as umbrella vibration and CH stretching vibration are assigned. The average shift of the corresponding infrared peaks on different conformations is estimated at less than 20 cm–1. -
Keywords:
- conformation isomerization /
- density-functional theory calculation /
- potential energy surface /
- infrared spectra
- PACS:
36.20.Ey (Conformation (statistics and dynamics)) 31.15.es (Applications of density-functional theory (e.g., to electronic structure and stability; defect formation; dielectric properties, susceptibilities; viscoelastic coefficients; Rydberg transition frequencies)) 31.50.Bc (Potential energy surfaces for ground electronic states) 33.20.Ea (Infrared spectra) Disclaimer: The English version of this article is automatically generated by iFLYTEK Translation and only for reference. We therefore are not responsible for its reasonableness, correctness and completeness, and will not bear any commercial and legal responsibilities for the relevant consequences arising from the English translation.1. Introduction
Molecular conformation refers to the different molecular spatial structures formed by isomerization through intramolecular single bond rotation, which is closely related to biological functions.For example, the spatial conformation of protein biomacromolecules determines the primary structure of protein molecules and the order of amino acids, and then determines the biological function of proteins.Molecular conformation exists not only in rigid molecules with low conformational freedom, but also in flexible molecules with high conformational freedom.The energy difference between conformers of flexible molecules is very small (about 0 — 42 kJ · mol –1 or 0 — 435 MeV) [1,2], these conformers can rapidly interconvert at room temperature and form a dynamic equilibrium in a certain proportion.Due to the high degree of conformational freedom of flexible molecules, it is still difficult to identify the rich conformer structures of flexible molecules and to observe the conformational isomerization dynamics of flexible molecules both theoretically and experimentally.In recent years, people have gradually focused on some flexible small molecule systems, hoping that the research results can provide corresponding information and powerful guidance for the conformation study of macromolecules such as proteins.Gosselin et al [3] proposed the method of using the change of Rydberg electron binding energy to detect the change of flexible molecular structure for the first time, and successfully realized the discrimination and calibration of the conformational structure of some amine molecules. [4-7].Dian et al [8] The energy threshold for the interconversion of tryptamine conformers was directly determined by laser spectroscopy.
Triethylamine is a relatively less complex flexible molecule in tertiary amines, with three C-N single bonds and three C-C single bonds, such as Shown in Fig. 1.The rotation of the C — N and C — C single bonds in the triethylamine molecule results in the different directions of the methyl groups at the end of the three ethyl chains, which makes the triethylamine molecule have abundant conformers.Kumar [9] pointed out that there were 27 conformers in the ground state of triethylamine, and two stable conformers TGG 'and GGG in liquid and solid phases were distinguished by Raman spectroscopy, while the stable conformer in gas phase was TGG'.Where T represents the Trans orientation of the methyl group at the end of the ethyl chain, i.e. C5H 3, C12H 3 and C19H The 3 methyl group and the N atom are located on both sides of the CCC plane formed by the carbon atoms C2, C9, and C16 in the middle of the three ethyl chains, respectively; G represents the Gauche orientation of the methyl group at the end of the ethyl chain, that is, the methyl group and the N atom are located on the same side of the CCC plane; G 'represents the other orientation when the methyl group is located on the same side as the N atom in the CCC plane, that is, the methyl groups in the G and G' orientations are.Crocker et al It was found that there was only one stable conformer TGG in the ground state of triethylamine in solid phase, while there were three stable conformers TGG, TGG 'and GGG in the ground state of triethylamine in liquid phase by combining infrared spectroscopy and Raman spectroscopy.Brushweller et al [11] Seven relatively stable conformers of triethylamine in the ground state were identified by MM2 molecular mechanics and dynamic NMR spectroscopy.These conformers have C 1, C s and C 3 3 symmetries, where one has C The conformer of 3 symmetry, G 'G' G ', is the lowest in energy; with C The conformer GAG (A represents the T orientation of the methyl group) of 1 symmetry has the second highest energy, which is only 0.01 kcal/mol (0.4 meV); with C The conformer GAG 'of s symmetry has the highest energy, with a C The G 'G' G 'energy of 3 symmetry is higher by ~ 0.22 kcal/mol (9.5 meV).Further, at 97 K, it is measured to have C 1 and C The sum of the relative proportions of the conformers with s symmetry can reach 94%, but C cannot be distinguished experimentally. 1 and C Proportion of s [11,12].Konaka et al The conformational structure of triethylamine in the ground state in gas phase was studied by using the experimental technique of gas phase electron diffraction, and three symmetries C in the conformation of triethylamine in the ground state were obtained. 1, C s and C The population of 3 accounted for 33%, 11% and 56% respectively.At the same time, the results based on the MM2 calculation method show that C The conformer of 3 symmetry is the most stable, which is similar to Brushweller et al. The results of [11] are consistent, but the results obtained by the ab initio method based on the 4-21 G basis set show that C The conformer of 1 symmetry is the most stable [13].Weber et al The electronic excited state of triethylamine in gas phase was detected to have three conformers R by time-resolved Rydberg electron spectroscopy combined with quantum chemical calculation. 1, R 2 and R 3, and speculate that there may be four lowest energy conformers G in the triethylamine ground state. 1, G 2, G 3 and G 4.However, this study did not give the specific molecular structure parameters and infrared vibrational spectra of the four conformers in the ground state.To sum up, there is no unified knowledge and understanding of the number, structure, energy and infrared spectrum of the stable conformers of triethylamine in the ground state. More advanced experimental techniques and more accurate theoretical calculations are needed to clarify the molecular conformation structure and infrared spectrum of triethylamine.
Figure 1. Schematic structure of triethylamine in Cartesian coordinate system.This work takes advantage of DFT in molecular conformational structure calculations [14-19], the hybrid density functional method B3LYP was used to fully optimize the different conformations of the gas-phase triethylamine ground state, along the dihedral angle ϕ 1 (c9n1c2c5) with ϕ The potential energy surface of conformational isomerization in the range of – 180 ° — 180 ° was scanned by the two-dimensional coordinate composed of 2 (C16N1C9C12), and 12 ground state isomers of triethylamine were identified. The structures and energies of 6 conformers with lower energy among these conformers were calculated and analyzed in detail, and the similarities and differences of infrared spectra and special vibrational modes of 4 conformers were compared.These results can provide important reference information for understanding the electronic excited state structure and dynamic mechanism of triethylamine molecule, and also provide some guidance for the study of the conformation structure and properties of more complex amino acid and polypeptide systems.
2. Theoretical calculation method
The theoretical calculation of this work is based on Gaussian09 quantum chemistry calculation software. [20] complete.Konaka et al. The lowest symmetry C obtained by [21] The three dihedral angle parameters in the triethylamine conformer (TG 'G') of 1 symmetry are used as benchmarks, and the hybrid density functional method B3LYP of density functional theory is used in 6-311 + + G (d, p) Its molecular structure was optimized at the [22] basis set level, and its stable conformation was obtained.On this structural basis, with a step size of 10 ° per step, along the dihedral angle ϕ 1 (C9N1C2C5) with ϕ 2 (C16N1C9C12), 12 stable conformers were identified by scanning the potential energy surface of conformational isomerization in the range of – 180 ° — 180 °, and their symmetry and methyl orientation were identified and defined.There is no imaginary frequency in the frequencies of all conformers, indicating that the optimized configurations are stable.Then, the structures of six conformers in the region of relatively small energy on the potential energy surface were optimized at B3LYP/6-311 + + G (d, p) level, and the frequencies and single-point energies were calculated. At the same time, the zero-point energies of different conformers were corrected.To verify the accuracy of the calculation, the second-order perturbation method MP2 is further used [23] They were calculated at the 6-311 + + G (d, p) basis set level and the results were compared.Finally, four conformers G1, G2, G3 and G4 were selected to calculate their infrared spectra at B3LYP/6-311 + + G (d, p) level, and the vibrational modes and their corresponding vibrational frequencies of the four conformers were obtained.According to the infrared spectrum obtained in the experiment, the vibration frequency obtained by calculation needs to be corrected, and the correction factor is 0.98.
3. Calculation results and discussion
3.1 Conformational structure and potential energy surface of triethylamine in ground state
Along the dihedral angle is exhibited in Fig. 2 ϕ 1 (C9N1C2C5) with ϕ The conformational isomerization potential energy surface of 2 (C16N1C9C12) was obtained by two-dimensional scanning in the range of – 180 ° — 180 °.According to the energy information, 12 conformers were labeled, which were G1, G1 ', G2, G3, G4, G4', G5 — G10.These 12 conformers were further optimized at the B3LYP/6-311 + + G (d, p) level, and the stable conformers obtained by frequency and single point energy calculation had C 3, C 1 and C s Symmetry.No imaginary frequency was found in the frequencies of all the conformers, indicating that the optimized conformers were stable. The corresponding dihedral angles and energies of the 12 optimized stable conformers are listed in 表1 middle.By 表1 It can be seen that G1 is the most stable structure with the lowest energy. The energy difference between G2-G9 and G1 is about 40-50 meV, while the relative energy difference between G2-G9 is very small, indicating that their stability is similar.The energy of G10 is 118.59 meV higher than that of G1, which is the highest among the 12 stable conformers. Fig. 2 also reflects that G10 is located at the height of the depression of the local potential energy surface region formed by G8, G9 and G10.These 12 conformers can rotate around the corresponding dihedral angles. ϕ 1, ϕ 2 and ϕ 3 (C2N1C16C19) is interconverted by rotation of a single bond, dihedral angle ϕ 1, ϕ 2 and ϕ The rotation of 3 is the main reason for the conformational change of triethylamine.
Figure 2. The conformational isomerization potential energy surface in the range of –180°–180° scanning along the two-dimensional coordinates formed by the dihedral angles of ϕ1 (C9N1C2C5) and ϕ2 (C16N1C9C12).Table 1. The energies and dihedral angles of the 12 conformers of triethylamine calculated on B3LYP/6-311++G(d, p) levelConformers ϕ1/(°) ϕ2/(°) ϕ3/(°) Energy/Hartree Relative E/meV G1 (GGG) 155.42 155.60 155.64 –292.501669 0 G1' (G'G'G') 77.67 77.63 77.63 –292.501620 1.33 G2 (TG'G') –66.62 76.02 63.21 –292.500061 43.76 G3 (TGG) –64.76 165.17 151.59 –292.500061 43.76 G4 (GG'G'') 162.85 67.24 115.28 –292.499824 50.21 G4' (G'G''G) 67.24 115.26 162.86 –292.499824 50.21 G5 (G'GT) –167.71 –60.28 65.25 –292.499826 50.15 G6 (GGT) –75.99 –63.21 66.63 –292.500061 43.76 G7 (G'G'T) –165.17 –151.59 64.75 –292.500061 43.76 G8 (G'TG) 60.28 –65.24 167.73 –292.499826 50.15 G9 (GTG) 151.58 –64.74 165.19 –292.500061 43.76 G10 (TG'T) 56.64 –156.48 76.67 –292.497311 118.59 | Show Table
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A new methyl group orientation was found in these 12 conformers, which is on the same side of the C2C9C16 plane as the N1 atom, different from the G and G 'orientations, and is named G' 'orientation.The previously reported G and G 'orientations are located on both sides of the N — C bond, respectively. The NCC plane formed by the ethyl chain and the N atom is not perpendicular to the C2C9C16 plane, while the NCC plane in the G' 'orientation is perpendicular to the C2C9C16 plane, which makes it impossible for the methyl group in the G' 'orientation to be distinguished on either side of the N — C bond, that is, the C — C bond coincides with the N-C bond in the Z axis direction of the molecule.C5H 3, C12H 3 and C19H The orientation of the three methyl groups of 3 is arranged in sequence, which allows the structural assignment of all conformers of triethylamine.G1 has C 3 symmetry, 3 methyl groups C5H 3, C12H 3 and C19H The orientation of 3 is the same and is assigned to the GGG conformation.While G2 has C 1 symmetry, C5H The 3 methyl group and the N1 atom are located on both sides of the C2C9C16 plane (T orientation), C12H 3 and C19H The 3 methyl groups are all on the same side of the C2C9C16 plane as the N1 atom, and the C12H 3 and C19H The orientation of the methyl group in 3 is different from that of the methyl group in G1. They are located on both sides of the NCC plane, that is, the G 'orientation. Therefore, G2 is assigned to the TG' G 'conformation.The methyl group of both conformers G4 and G4 'are on the same side of the C2C9C16 plane as the N1 atom, but G4 and G4' do not have the C of G1 and G1 'because they have two different methyl orientations, G' and G ''. 3 symmetry, but instead has C s Symmetry.The nomenclature of other conformers is detailed in Fig. 3.
Figure 3. The 12 stable conformers of triethylamine calculated on B3LYP/6-311++G(d, p) level.From Fig. 3 It can be seen that the N1 atoms in the 12 stable conformers form a tetrahedral shape with the plane formed by C2C9C16, where the average value of the N1-C2, N1-C9, or N1-C16 bond lengths is between 1.Around 4680 Å, the average value of the ∠ C2N1C9 or ∠ C9N1C16 or ∠ C2N1C16 bond angles is around 111.98 °, so that the triethylamine molecule has a similar NH Stable structure of 3 molecular configuration, see for specific parameters 表1.The methyl groups in the triethylamine molecule will hinder each other in space because they are close to each other, resulting in steric hindrance effect.Dihedral angle ϕ 1, ϕ 2 and ϕ The rotation of 3 can characterize the triethylamine 3 methyl group C5H 3, C12H 3 and C19H Relative spatial position of 3.When the steric hindrance is relatively small, the relatively stable orientation of the three methyl groups is reflected in the dihedral angle ϕ 1, ϕ 2 and ϕ Size of 3.
Based on ab initio methods, it is pointed out that one has C The conformer of 1 symmetry is the most stable [13].At the B3LYP/6-311 + + G (d, p) level, the results show that G1 is the most stable structure with the lowest energy, which is similar to Konaka et al. [13] The results calculated by MM2 method are consistent.In order to further verify the influence of the calculation method on the optimization of molecular conformation structure, frequency and single point energy, 6 conformers (G1, G1 ′, G2, G3, G4 and G4 ′) in the lower energy region of the potential energy surface in Fig. 2, such as Fig. 4, the structure was further optimized at the MP2/6-311 + + G (d, p) level, and the frequency and single point energy were calculated.The dihedral angle parameters and energies obtained for G1, G1 ′, G2, G3, G4 with G4 ′ are listed in 表2. Compared with the MP2 method, the energies of the six conformers obtained at the B3LYP level are smaller, and the energy difference between G1 and G1 'is only 1.33 meV, while the energies between G2 and G3, G4 and G4 'are indistinguishable. The energies between G1 and G1' calculated by MP2/6-311 + + G (d, p) are indistinguishable, while the energies between G2 and G3, G4 and G4 'are slightly different.The calculated results show that the energy order of the six conformers is G1/G1 '< G2/G3 < G4/G4', indicating that the most stable conformer is the one with C 3 symmetry of G1 and G1 ', which is similar to Konaka et al. Identified in the [13] experiment with C The conclusion that the conformer of 3 symmetry is dominant is consistent.Such as As shown in Fig. 4, G1, G1 ', G4 and G4' are located in the same region of the potential energy surface, while G2 and G3 are located in another energy region of the potential energy surface. There is a potential barrier of about 250-300 meV between the two regions, indicating that the transformation of different conformers in the same region is relatively easy, and the structural transformation between isomers is not easy due to the higher potential barrier between different regions.
Figure 4. The conformational isomerization potential energy surface of the six conformers in ϕ1(–100°–180°) and ϕ2 (40°–180°).Table 2. The energies and dihedral angles of the six stable conformers of triethylamine on the level of MP2/6-311++G(d, p)Conformers ϕ1/(°) ϕ2/(°) ϕ3/(°) Energy/Hartree Relative E/meV G1 (GGG) 157.62 157.63 157.63 –291.559737 0 G1' (G'G'G') 79.53 79.53 79.53 –291.559737 0 G2 (TG'G') –66.91 75.27 57.80 –291.558559 32.06 G3 (TGG) –59.62 175.87 158.42 –291.558563 31.95 G4 (GG'G'') 166.11 67.66 117.32 –291.558516 33.23 G4' (G'G''G) 67.74 117.11 166.19 –291.558517 33.20 | Show TableDownLoad:
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Dihedral angle of G1 ϕ 1, ϕ 2 and ϕ 155.42 °, 155.60 ° and 155 ° for 3 respectively.64 °, while the dihedral angle of G1 ' ϕ 1, ϕ 2 and ϕ 3 are 77.67 °, 77.63 ° and 77.63 ° respectively.Such as As shown in Fig. 3, the conformational structures of G1 and G1 'are very similar, both having C 3 symmetry, G1 is GGG conformation, G1 'is G' G 'G' conformation.The main difference between G1 and G1 'is the three methyl groups C5H 3, C12H 3 and C19H The relative spatial orientation of 3 is different, and this subtle structural difference results in a very small energy difference between G1 and G1 '. As mentioned earlier, the energy difference based on B3LYP is only 1.33 meV, while MP2-based results are indistinguishable. In the reported study [4,9-13], none of the G1 conformers were identified, but only G1 'was considered to be present.The energies of G4 and G4 'are ~ 50 meV and 33 meV higher than those of G1 and G1' at B3LYP and MP2, respectively. In addition, the energy difference between G4 and G4 'is 0 at B3LYP and about 0.03 meV at MP2.Dihedral angle of G4 ϕ 1, ϕ 2 and ϕ 3 are 162.85 °, 67.24 ° and 115.28 °, while the dihedral angle of G4 ' ϕ 1, ϕ 2 and ϕ 3 are 67.24 °, 115.26 ° and 162.86 ° respectively, such as Fig. 3.Among them, the G4 'conformer has been studied in previous reports. [4,9-13] is also not recognized. In general, the three ethyl chains of triethylamine can be considered equivalent, as indicated by It can be seen from 表1 that the energies of conformers with the same three methyl orientations are almost the same.The energies of G2 (TG 'G'), G3 (TGG), G6 (GGT) and G7 (G 'G' T) are all 43.76 meV, and the energies of G5 (G 'GT) and G8 (G' TG) are all 50.18 meV, etc.However, in this work, these conformers are in the potential wells of different dihedral coordinates on the potential energy surface and are considered to be different configurations.G2, G3, G6 and G7 have C 1 symmetry, the energy difference of the four configurations is 0 under the B3LPY method, and the energy difference of G2 and G3 is only 0.11 meV under the MP2 method. These structures cannot be distinguished by the difference of energy.Considering that the difference between G1 and G1 ', G4 and G4' conformations is very small, and G2 and G3 conformations can not be distinguished in energy.Therefore, the infrared spectra of conformers G1-G4 were further analyzed and compared by B3LYP/6-311 + + G (d, p) calculation.
3.2 Infrared spectra of triethylamine ground state stable conformer
The infrared spectra of four conformers G1, G2, G3 and G4 were further calculated on the basis of B3LYP/6-311 + + G (d, p), such as Shown in Fig. 5.The infrared spectra of G1-G4 are shown at 2800-3300 cm. There is strong absorption in the range of –1, and in the range of 0 — 1600 cm The absorption in the range of –1 is weak, which is similar to the infrared spectrum obtained by NIST gas phase experiment.The vibrational frequencies of the corresponding G1 — G4 are listed in Among 表3, it is found that the frequencies of various vibrational modes of G1-G4 are slightly shifted relative to the G1 conformer with the smallest energy, and the average shift is less than 20 cm. –1, which is mainly caused by the different polarizability changes of atoms during vibration due to the different orientations of methyl groups in conformers.In particular, G2 (TG 'G') has the same C as G3 (TGG) The infrared spectra of 1 are very similar because of their symmetry but different methyl orientation.
Figure 5. The infrared spectra of the G1–G4 conformers calculated at B3LYP/6-311++G(d, p) level.Table 3. The vibrational modes and their frequencies of the G1-G4 conformers calculated on B3LYP/6-311++G(d, p) levelModes Frequency /cm–1 Infrared /(arb. units) G1 G2 G3 G4 G1 G2 G3 G4 ν1 87.22 55.02 55.10 50.35 0.1532 0.0639 0.0639 0.0004 ν2 90.98 87.43 87.41 96.49 0.1978 0.1857 0.1857 0.0238 ν3 95.03 109.27 109.28 140.35 0.1084 0.2932 0.2933 0.7795 ν4 188.06 178.51 178.54 178.16 1.1011 2.0829 2.0830 1.1365 ν5 208.61 203.62 203.58 205.94 0.0793 0.0717 0.0724 0.0393 ν6 214.02 224.68 224.73 223.87 0.0468 0.0690 0.0687 0.1212 ν7 294.38 268.43 268.36 256.33 1.0986 0.3758 0.3757 0.1000 ν8 304.06 290.93 290.98 328.65 0.3330 1.0227 1.0225 1.6826 ν9 305.06 331.61 331.61 332.28 0.3301 0.6897 0.6908 0.3791 ν10 427.73 407.68 407.74 390.84 3.0184 1.9295 1.9286 1.8981 ν11 465.12 465.26 465.28 449.38 1.9245 2.3956 2.3948 1.6278 ν12 466.51 519.32 519.35 495.27 1.9272 6.0474 6.0464 0.2229 ν13 732.52 721.09 721.08 734.07 12.9402 9.4813 9.4797 10.9942 ν14 786.67 769.53 769.53 763.17 3.8307 4.3371 4.3412 6.1536 ν15 787.30 788.70 788.71 790.73 3.8921 2.6364 2.6346 1.2979 ν16 797.88 799.48 799.50 799.56 0.0602 1.6382 1.6374 1.5619 ν17 907.63 886.81 886.80 911.00 1.2513 1.6792 1.6806 1.3188 ν18 907.82 906.38 906.37 911.59 1.2450 1.3085 1.3102 0.5529 ν19 1002.59 983.42 983.41 1003.17 6.7677 11.0738 11.0739 5.7366 ν20 1059.24 1035.02 1035.00 1056.02 29.6466 8.2727 8.2697 18.7155 ν21 1059.73 1059.50 1059.46 1058.63 30.0288 30.8396 31.1034 16.0090 ν22 1065.72 1062.07 1062.06 1069.23 3.2100 8.4580 8.2166 30.8172 ν23 1078.10 1078.78 1078.77 1076.49 8.5384 3.6151 3.6028 1.3100 ν24 1078.68 1090.02 1090.04 1102.40 8.3190 28.7911 28.7831 8.1051 ν25 1145.20 1130.09 1130.09 1132.97 12.0682 10.1819 10.1824 19.8481 ν26 1208.09 1204.99 1204.96 1210.21 23.0883 18.4553 18.4412 17.6571 ν27 1208.58 1213.11 1213.11 1213.26 23.1735 25.1079 25.1196 35.4460 ν28 1295.98 1286.87 1286.86 1275.96 6.1543 5.5069 5.5346 4.4355 ν29 1299.90 1291.74 1291.73 1307.05 19.8870 19.0478 19.0085 20.9498 ν30 1301.08 1338.30 1338.29 1319.27 19.5949 13.3278 13.3106 1.2005 ν31 1368.21 1352.09 1352.09 1354.63 1.9917 11.3690 11.3924 37.8361 ν32 1369.16 1366.65 1366.64 1357.26 1.2772 3.0836 3.0821 5.3537 ν33 1377.64 1375.36 1375.35 1377.69 0.3191 3.9451 3.9459 0.5963 ν34 1388.04 1377.00 1377.00 1381.06 17.8509 14.4179 14.4269 19.6423 ν35 1388.15 1386.56 1386.55 1382.64 18.3740 20.6580 20.6282 12.8529 ν36 1388.87 1390.27 1390.26 1404.98 19.7944 15.6998 15.6974 5.4524 ν37 1457.17 1452.04 1452.05 1453.70 2.7473 4.8488 4.8565 5.2712 ν38 1457.42 1458.81 1458.81 1455.34 1.6935 4.5549 4.5301 0.3420 ν39 1457.69 1461.08 1461.08 1458.89 2.2572 2.7707 2.7867 3.6730 ν40 1462.71 1465.68 1465.67 1462.41 1.8527 2.0538 2.0584 4.0415 ν41 1470.31 1469.26 1469.25 1465.41 1.2048 3.4122 3.4014 0.0857 ν42 1470.92 1470.19 1470.18 1473.12 1.5336 1.3596 1.3783 3.1465 ν43 1480.41 1477.89 1477.88 1478.47 7.1590 2.9233 2.9249 1.5156 ν44 1481.40 1480.62 1480.60 1484.66 7.0152 14.8916 14.8851 10.1121 ν45 1485.83 1490.87 1490.86 1487.68 12.4306 1.4478 1.4478 14.3785 ν46 2840.18 2846.52 2846.55 2823.87 23.2447 36.5331 36.7500 30.6694 ν47 2840.74 2855.55 2855.62 2833.67 23.3082 133.4917 133.2390 190.3336 ν48 2852.73 2964.14 2964.10 2931.98 238.2268 28.9250 28.9420 52.7107 ν49 2966.71 2965.86 2965.83 2961.43 29.7433 22.5935 22.5842 24.4676 ν50 2967.27 2967.80 2967.77 2962.15 29.7303 26.9332 26.9495 32.0017 ν51 2967.73 2969.71 2969.69 2966.69 20.4277 26.6680 26.6499 55.0959 ν52 3005.55 2985.78 2985.82 2967.51 12.9188 19.0174 18.9607 9.9999 ν53 3006.00 2999.96 2999.91 2982.63 12.0858 16.2484 16.2880 1.3433 ν54 3009.33 3003.92 3003.90 2993.29 0.0669 7.0967 7.1223 29.3355 ν55 3025.88 3022.39 3022.35 3025.08 9.0331 39.4849 39.4879 51.7362 ν56 3028.87 3026.72 3026.71 3026.92 48.6932 15.0249 15.0950 24.4990 ν57 3029.12 3029.64 3029.64 3028.60 44.4949 61.7552 61.8929 54.1919 ν58 3037.74 3031.73 3031.72 3036.45 53.6899 42.2463 42.0251 3.3194 ν59 3039.70 3037.26 3037.24 3037.37 45.2729 52.3351 52.2987 69.7071 ν60 3040.26 3040.20 3040.20 3041.40 46.0316 44.4987 44.5093 31.7214 | Show TableDownLoad:
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For four conformers, 2800 — 3300 cm was observed There are many vibration peaks in the range of –1, which are mainly attributed to the vibration of C-H.The strongest peak in G1 is at 2852 cm –1, corresponding to symmetric stretching vibration of C2 — H3, C9 — H11 and C16 — H17; 3027 cm –1, corresponding to the asymmetric stretching vibration of the H atom on the methyl group of C5 or C12; 3028 cm –1, corresponding to the symmetric stretching vibration of the H atom on the methyl group of C5, C12, C19; 3037 cm –1, corresponding to the asymmetric stretching vibration of the H atom on the methyl group of C5, C12, C19.For 0 — 1600 cm Vibration peak in the range of –1, whose intensity ratio is 2800-3300 cm The intensity of the vibration peaks in the range of –1 is much weaker, which is mainly attributed to the various vibration modes of ethyl or the various vibration modes of ethyl accompanied by the skeleton vibration of N.For example, 732 cm –1, corresponding to the umbrella-shaped vibration mode of N1 and C2, C9, C16 frameworks, that is, the symmetrical bending vibration of N1 and C2, C9, C16 frameworks, accompanied by the rocking vibration of ethyl.With NH Similar to the 3 molecule, when the lone pair of electrons on the N1 atom is excited to form the Rydberg electronic state 3p, the N1 atom on the triethylamine molecule and the skeleton formed by C2, C9 and C16 will undergo planar motion, that is, the umbrella vibration mode of triethylamine will be excited, which is crucial to the understanding of the excited state conformational isomerism dynamics of triethylamine molecule.In addition, 427 cm –1, corresponding to the symmetric stretching vibration of the skeleton composed of N1 and C2, C9, C16, accompanied by the rocking vibration of the ethyl group.
Fig. 6 shows the strongest C — H stretching vibration mode and umbrella vibration mode. The arrow at the atomic bond axis in the figure represents the unit vector of the transition dipole moment, and the arrow at each atom represents the displacement vector of the corresponding atom.
Figure 6. The umbrella vibration mode (upper panel) and C—H symmetric stretch mode (lower panel) and their frequencies of the G1—G4 conformers calculated on B3LYP/6-311++G(d, p) level.4. Conclusion
The stable conformation, frequency, energy and infrared spectrum of gas phase triethylamine ground state were calculated by density functional theory at B3LYP/6-311 + + G (d, p) level.Twelve stable conformers were identified by scanning the two-dimensional conformational potential energy surface related to conformational transformation, and the energy order of the conformers with different symmetries was further determined by MP2/6-311 + + G (d, p) calculation method, which confirmed that the most stable conformer was with C G1 and G1 'of 3 symmetry.Compared with the results of reported studies, a new C Conformer G1 (GGG) of 3 symmetry, whose dihedral angles ϕ 1, ϕ 2 and ϕ 3 are 155.42 °, 155.60 ° and 155.64 °. At the same time, a new methyl orientation G '' was identified, which was used to identify two new conformers G4 (GG 'G' ') and G4' (G 'G' 'G).The dihedral angles of the two structures are calculated. ϕ 1, ϕ 2 and ϕ 3 are 162.85 °, 67.24 °, 115.28 ° and 67.24 °, 115.26 °, 162.86 ° respectively.Based on the results calculated by different methods, it is found that the energies of G1/G1 ', G2/G3, G4/G4' are almost equal.The infrared spectra of G1, G2, G3 and G4 conformers were calculated at B3LYP/6-311 + + G (d, p) level. The results show that the infrared spectra of G1 — G4 are in the range of 0 — 1600 cm The intensity in the range of –1 is weak, while that in the range of 2800-3300 cm The intensity in the range of –1 is stronger, and the characteristic vibration modes such as the umbrella-shaped vibration mode and the strongest C-H stretching vibration mode are calibrated.The frequencies of various vibrational modes of G1-G4 shift due to different conformations, and the average shift is less than 20 cm –1.In this work, the structures, energies, infrared vibrational spectra of the molecular conformers in the ground state of triethylamine are revealed in detail, which provides important reference information and guidance for understanding the structure and dynamic mechanism of the electronic excited state of triethylamine molecule.
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图 1 三乙胺分子在笛卡尔坐标系下的结构示意图.
Figure 1. Schematic structure of triethylamine in Cartesian coordinate system.
图 2 沿二面角ϕ1(C9N1C2C5)与ϕ2(C16N1C9C12)构成的二维坐标扫描–180°—180°范围内三乙胺构象异构化势能面
Figure 2. The conformational isomerization potential energy surface in the range of –180°–180° scanning along the two-dimensional coordinates formed by the dihedral angles of ϕ1 (C9N1C2C5) and ϕ2 (C16N1C9C12).
图 3 基于B3LYP/6-311++G(d, p)水平计算得到的三乙胺的12种稳定构象异构体的分子结构
Figure 3. The 12 stable conformers of triethylamine calculated on B3LYP/6-311++G(d, p) level.
图 4 ϕ1 (–100°—180°)与ϕ2 (40°—180°)范围内的6种构象异构体的势能面
Figure 4. The conformational isomerization potential energy surface of the six conformers in ϕ1(–100°–180°) and ϕ2 (40°–180°).
图 5 在B3LYP/6-311++G(d, p)水平上计算得到的G1—G4构象异构体的红外光谱
Figure 5. The infrared spectra of the G1–G4 conformers calculated at B3LYP/6-311++G(d, p) level.
图 6 基于B3LYP/6-311++G(d, p)水平计算得到的G1—G4构象异构体的伞形振动(上排图)和C—H对称伸缩振动(下排图)及其频率
Figure 6. The umbrella vibration mode (upper panel) and C—H symmetric stretch mode (lower panel) and their frequencies of the G1—G4 conformers calculated on B3LYP/6-311++G(d, p) level.
表 1 基于B3LYP/6-311++G(d, p)水平计算得到的三乙胺的12种稳定构象异构体的二面角与能量
Table 1. The energies and dihedral angles of the 12 conformers of triethylamine calculated on B3LYP/6-311++G(d, p) level
Conformers ϕ1/(°) ϕ2/(°) ϕ3/(°) Energy/Hartree Relative E/meV G1 (GGG) 155.42 155.60 155.64 –292.501669 0 G1' (G'G'G') 77.67 77.63 77.63 –292.501620 1.33 G2 (TG'G') –66.62 76.02 63.21 –292.500061 43.76 G3 (TGG) –64.76 165.17 151.59 –292.500061 43.76 G4 (GG'G'') 162.85 67.24 115.28 –292.499824 50.21 G4' (G'G''G) 67.24 115.26 162.86 –292.499824 50.21 G5 (G'GT) –167.71 –60.28 65.25 –292.499826 50.15 G6 (GGT) –75.99 –63.21 66.63 –292.500061 43.76 G7 (G'G'T) –165.17 –151.59 64.75 –292.500061 43.76 G8 (G'TG) 60.28 –65.24 167.73 –292.499826 50.15 G9 (GTG) 151.58 –64.74 165.19 –292.500061 43.76 G10 (TG'T) 56.64 –156.48 76.67 –292.497311 118.59 
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表 2 三乙胺的6种稳定构象异构体在MP2/6-311++G(d, p)计算下的二面角与能量
Table 2. The energies and dihedral angles of the six stable conformers of triethylamine on the level of MP2/6-311++G(d, p)
Conformers ϕ1/(°) ϕ2/(°) ϕ3/(°) Energy/Hartree Relative E/meV G1 (GGG) 157.62 157.63 157.63 –291.559737 0 G1' (G'G'G') 79.53 79.53 79.53 –291.559737 0 G2 (TG'G') –66.91 75.27 57.80 –291.558559 32.06 G3 (TGG) –59.62 175.87 158.42 –291.558563 31.95 G4 (GG'G'') 166.11 67.66 117.32 –291.558516 33.23 G4' (G'G''G) 67.74 117.11 166.19 –291.558517 33.20
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表 3 基于B3LYP/6-311++G(d, p)水平计算得到的G1—G4构象异构体的振动模式与频率
Table 3. The vibrational modes and their frequencies of the G1-G4 conformers calculated on B3LYP/6-311++G(d, p) level
Modes Frequency /cm–1 Infrared /(arb. units) G1 G2 G3 G4 G1 G2 G3 G4 ν1 87.22 55.02 55.10 50.35 0.1532 0.0639 0.0639 0.0004 ν2 90.98 87.43 87.41 96.49 0.1978 0.1857 0.1857 0.0238 ν3 95.03 109.27 109.28 140.35 0.1084 0.2932 0.2933 0.7795 ν4 188.06 178.51 178.54 178.16 1.1011 2.0829 2.0830 1.1365 ν5 208.61 203.62 203.58 205.94 0.0793 0.0717 0.0724 0.0393 ν6 214.02 224.68 224.73 223.87 0.0468 0.0690 0.0687 0.1212 ν7 294.38 268.43 268.36 256.33 1.0986 0.3758 0.3757 0.1000 ν8 304.06 290.93 290.98 328.65 0.3330 1.0227 1.0225 1.6826 ν9 305.06 331.61 331.61 332.28 0.3301 0.6897 0.6908 0.3791 ν10 427.73 407.68 407.74 390.84 3.0184 1.9295 1.9286 1.8981 ν11 465.12 465.26 465.28 449.38 1.9245 2.3956 2.3948 1.6278 ν12 466.51 519.32 519.35 495.27 1.9272 6.0474 6.0464 0.2229 ν13 732.52 721.09 721.08 734.07 12.9402 9.4813 9.4797 10.9942 ν14 786.67 769.53 769.53 763.17 3.8307 4.3371 4.3412 6.1536 ν15 787.30 788.70 788.71 790.73 3.8921 2.6364 2.6346 1.2979 ν16 797.88 799.48 799.50 799.56 0.0602 1.6382 1.6374 1.5619 ν17 907.63 886.81 886.80 911.00 1.2513 1.6792 1.6806 1.3188 ν18 907.82 906.38 906.37 911.59 1.2450 1.3085 1.3102 0.5529 ν19 1002.59 983.42 983.41 1003.17 6.7677 11.0738 11.0739 5.7366 ν20 1059.24 1035.02 1035.00 1056.02 29.6466 8.2727 8.2697 18.7155 ν21 1059.73 1059.50 1059.46 1058.63 30.0288 30.8396 31.1034 16.0090 ν22 1065.72 1062.07 1062.06 1069.23 3.2100 8.4580 8.2166 30.8172 ν23 1078.10 1078.78 1078.77 1076.49 8.5384 3.6151 3.6028 1.3100 ν24 1078.68 1090.02 1090.04 1102.40 8.3190 28.7911 28.7831 8.1051 ν25 1145.20 1130.09 1130.09 1132.97 12.0682 10.1819 10.1824 19.8481 ν26 1208.09 1204.99 1204.96 1210.21 23.0883 18.4553 18.4412 17.6571 ν27 1208.58 1213.11 1213.11 1213.26 23.1735 25.1079 25.1196 35.4460 ν28 1295.98 1286.87 1286.86 1275.96 6.1543 5.5069 5.5346 4.4355 ν29 1299.90 1291.74 1291.73 1307.05 19.8870 19.0478 19.0085 20.9498 ν30 1301.08 1338.30 1338.29 1319.27 19.5949 13.3278 13.3106 1.2005 ν31 1368.21 1352.09 1352.09 1354.63 1.9917 11.3690 11.3924 37.8361 ν32 1369.16 1366.65 1366.64 1357.26 1.2772 3.0836 3.0821 5.3537 ν33 1377.64 1375.36 1375.35 1377.69 0.3191 3.9451 3.9459 0.5963 ν34 1388.04 1377.00 1377.00 1381.06 17.8509 14.4179 14.4269 19.6423 ν35 1388.15 1386.56 1386.55 1382.64 18.3740 20.6580 20.6282 12.8529 ν36 1388.87 1390.27 1390.26 1404.98 19.7944 15.6998 15.6974 5.4524 ν37 1457.17 1452.04 1452.05 1453.70 2.7473 4.8488 4.8565 5.2712 ν38 1457.42 1458.81 1458.81 1455.34 1.6935 4.5549 4.5301 0.3420 ν39 1457.69 1461.08 1461.08 1458.89 2.2572 2.7707 2.7867 3.6730 ν40 1462.71 1465.68 1465.67 1462.41 1.8527 2.0538 2.0584 4.0415 ν41 1470.31 1469.26 1469.25 1465.41 1.2048 3.4122 3.4014 0.0857 ν42 1470.92 1470.19 1470.18 1473.12 1.5336 1.3596 1.3783 3.1465 ν43 1480.41 1477.89 1477.88 1478.47 7.1590 2.9233 2.9249 1.5156 ν44 1481.40 1480.62 1480.60 1484.66 7.0152 14.8916 14.8851 10.1121 ν45 1485.83 1490.87 1490.86 1487.68 12.4306 1.4478 1.4478 14.3785 ν46 2840.18 2846.52 2846.55 2823.87 23.2447 36.5331 36.7500 30.6694 ν47 2840.74 2855.55 2855.62 2833.67 23.3082 133.4917 133.2390 190.3336 ν48 2852.73 2964.14 2964.10 2931.98 238.2268 28.9250 28.9420 52.7107 ν49 2966.71 2965.86 2965.83 2961.43 29.7433 22.5935 22.5842 24.4676 ν50 2967.27 2967.80 2967.77 2962.15 29.7303 26.9332 26.9495 32.0017 ν51 2967.73 2969.71 2969.69 2966.69 20.4277 26.6680 26.6499 55.0959 ν52 3005.55 2985.78 2985.82 2967.51 12.9188 19.0174 18.9607 9.9999 ν53 3006.00 2999.96 2999.91 2982.63 12.0858 16.2484 16.2880 1.3433 ν54 3009.33 3003.92 3003.90 2993.29 0.0669 7.0967 7.1223 29.3355 ν55 3025.88 3022.39 3022.35 3025.08 9.0331 39.4849 39.4879 51.7362 ν56 3028.87 3026.72 3026.71 3026.92 48.6932 15.0249 15.0950 24.4990 ν57 3029.12 3029.64 3029.64 3028.60 44.4949 61.7552 61.8929 54.1919 ν58 3037.74 3031.73 3031.72 3036.45 53.6899 42.2463 42.0251 3.3194 ν59 3039.70 3037.26 3037.24 3037.37 45.2729 52.3351 52.2987 69.7071 ν60 3040.26 3040.20 3040.20 3041.40 46.0316 44.4987 44.5093 31.7214
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[1] Park S T, Kim S K, Kim M S 2002 Nature 415 306
Google Scholar
[2] Kim M H, Shen L, Tao H, Martinez T J, Suits A G 2007 Science 315 1561
Google Scholar
[3] Gosselin J L, Weber P M 2005 J. Phys. Chem. A 109 4899
Google Scholar
[4] Deb S, Bayes B A, Minitti M P, Weber P M 2011 J. Phys. Chem. A 115 1804
Google Scholar
[5] Minitti M P, Weber P M 2007 Phys. Rev. Lett. 98 253004
Google Scholar
[6] Kuthirummal N, Weber P M 2003 Chem. Phys. Lett. 378 647
Google Scholar
[7] Kuthirummal N, Weber P M 2006 J. Mol. Struct. 787 163
Google Scholar
[8] Dian B C, Clarkson J R, Zwier T S 2004 Science 303 1169
Google Scholar
[9] Kumar K 1971 Chem. Phys. Lett. 9 504
Google Scholar
[10] Crocker C, Goggin P L 1978 J. Chem. Soc. Dalton Trans 388
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Google Scholar
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Google Scholar
[13] Takeuchi H, Kojima T, Egawa T, Konaka S 1992 J. Phys. Chem. 96 4389
Google Scholar
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Google Scholar
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Google Scholar
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