Investigation of the Electrical and Optical Activity of Halogen-substituted 2- nitrotoulene by Density Functional Theory

doi:10.21203/rs.3.rs-2111123/v1

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Investigation of the Electrical and Optical Activity of Halogen-substituted 2- nitrotoulene by Density Functional Theory

https://doi.org/10.21203/rs.3.rs-2111123/v1

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published 04 Feb, 2023

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The enhancement of NLO activity of the 2-nitrotoulene (2NT) after the substitution of the halogens (F, Cl, Br and I) at the para position of the benzene ring was reported in the paper. All the computational details were mentioned using density functional theory with B3LYP/6-311G basis set. The engagement of the electrophilic and nucleophilic regions in molecules was established using counter plots. Mulliken charge analysis and frontier molecular orbital parameters laid the high chemical reactivity of 2NT molecule after the substitution of F, Cl, Br, and I. Electronic properties were analyzed by computing absorption and emission spectra using time-dependent density functional theory. The Higher Raman intensity modes and higher absorbance intensity curve for iodine substituted 2NT (2NT-I) highlighted the highest reactivity. The lowest band gap was reported for 2NT-I (4.03 eV) that better correlates with the charge and spectral findings. The polarizability parameters set a fair comparison between the NLO activities of the molecules. 2NT-I has the highest values of polarizability parameters among the other molecules.

Density functional theory

Nonlinear optics

2-nitrotoulene

Halogens

Hyperpolarizability

Nitrotoulene (NT) is an aromatic compound having numerous applications in pigments, antioxidants, agricultural chemicals, and photographic chemicals [1–4]. It mainly comprises of nitro group that is highly electronegative in nature and a methyl group that acts as a strong electron donor moiety [5]. The inductive effect leads to the liberation of the electrons from the methyl group towards the nitro group and the charge get transferred to the benzene ring. The free electrons thus, result in hyperconjugation and benzene ring behaves as resonating moiety. This can be considered as the main reason for the high chemical reactivity of the nitrotoluene. The use of NT and its derivatives are active research trends among researchers. The application of NT as a catalytic reducer was examined [6]. It has potential applications in paints, dyes, rubber and leather industry as well. the high electro availability in the benzene ring of NT also leads to its development as charge transport materials [7, 8]. Thus, the high utilization of NT in industrial applications reflects its potent uses over the material science researches.

Meanwhile, the requirement of highly efficient nonlinear optical (NLO) materials have given an enormous hight to the research field of nonlinear optics. The introduction of new organic NLO materials has revolutionized the photonic and optoelectronics. Nonlinear optics is the science that accounts the collaboration of the electromagnetic (EM) light upon the sample [9]. The variation of different properties in the sample after introducing it with the EM light leads to their applicability in optical switching, optical power limiting, picture control, telecommunications frequency mixing and generating, photovoltaics and fluorescence, picture preparing, high sensing materials etc. [10, 11]. Modifications in the technology have laid the fact of high efficiency of the organic NLO materials over the inorganic ones. This has elevated the interest of the researchers in developing the organic NLO materials. Pyrenes [12], pyrrolidine [13], pyrazine [14], succinimide [15], anthracenes [16], quinones [17], curcumins [18], creatininium [19], azines [20], pyrrole [21], etc., are a few categories of the organic compounds that had been widely worked upon in the past few years. Apart of this, NLO activities of the plant-derived compounds like curcumin [18], clitorin [22], carotenoid [23], coriandrum [24], cyclea peltate [25], were also established using the density functional theory (DFT) approach. Moreover, the substitution of halogen had seen to enormously enhance the chemical reactivity. This is probably due to the high chemical reactivity of the halogen atoms. Very high electronegativity of the halogens, are also reported high that can also be considered as the reason for risen reactivity of the compounds. The availability of the seven valence electrons in the outermost shell of the halogen atoms makes it highly desirable to rapidly complete the octet and attain the stable configuration [26]. Thus, the halogen-substituted compounds have gained attention of the researchers to a great extent. Literature had reported many studies that had accounted the enhanced NLO activity of molecules right after the substitution of halogens. The research work had been reported for the investigation of NLO activity of the p-idoaniline and p-bromoaniline [27], Schiff’s base material: 4-chloro-4′bromobenzylidene aniline [28], N-methyl-4-piperiodones curcumin [29], chalcones [30], after the substitution of the halogens. Immense rise in the NLO activity of the molecules was seen in the mentioned studies that motivated us to proceed the present study.

In the current study, the computational investigations on the NLO activities of halogen-substituted 2NT were performed. Theoretical investigations on the structural parameters, spectral properties, and NLO activity was established using DFT.

All the computational calculations were performed using Gaussian 09 software packages (https://gaussian.com/) [31]. The 3-dimensional geometry of 2NT (PubChem ID: 6944) was downloaded from database PubChem (https://pubchem.ncbi.nlm.nih.gov/) and the halogens were substituted on the para position of toluene using the builder function over Gauss View program (https://gaussian.com/gaussview6/) [32]. The halogens are known for their exceptionality of being para-directors despite of being highly electronegative atoms. Thus, para position was better for halogen-substitution [33]. The geometry optimization of probe 2NT and 2NT after substitution of halogens (Cl, F, Br, and I) was performed using DFT with B3LYP/6-311G set of functions [34, 35]. The chemical reactivity and the active participation of the halogen within the 2NT was established using counter plots and chemical reactivity parameters. Different reactivity parameters like bandgap (ΔE), ionization potential (IP), electron affinity (EA), chemical potential (CP), electronegativity (χ), softness (S), and hardness (η) are calculated with the help of Koopman’s equations used in previously done studies [36–39]. The molecular orbital map (HOMO-LUMO) and band gap was illustrated using software Spartan (https://store.wavefun.com/Spartan_Software_s/12.htm). The vibrational activities of the probe and substituted molecules were also examined by computing Raman spectra. The Raman intensity was calculated for high frequency modes using expression:

$$I=\frac{f{\left({{\nu }}_{o}-{{\nu }}_{i}\right)}^{4} {\text{S}}_{i}}{{{\nu }}_{i}\left[1-\text{exp}\left(-\frac{hc{{\nu }}_{i}}{\text{k}\text{T}}\right)\right]}$$

…………………….

where I is Raman intensity of the vibrational mode, f is a constant with value 10^− 12, ν_o has value 9398.5 cm^− 1. ν_i and S_i is the vibrational wavenumber and Raman activity of selected mode respectively. h is Planck constant with value 4.1357×10^− 15eV K^− 1, c is speed of light having value 3×10⁸m/s, K is Boltzmann constant with value 8.6173×10^− 5 eV K^− 1, and T is temperature 293.5K. Time-dependent DFT (TD-DFT) was used for computing the absorption and emission spectra of the probe and substituted molecule with same set of functions as used for optimization. The values for polarizability parameters like total isotropic polarizability (α_total), and anisotropy of polarizability (Δα) and first order hyperpolarizability (β_total) was evaluated for the set of title molecules for the detection of the rise in the NLO activity of the probe 2NT and halogen substituted 2NT. These parameters were computed using the equations mentioned in the references [40, 41].

3.1 Structural analysis

All the structural parameters like bond lengths, and bond angles were analyzed and are listed in SD 1, and SD 2 respectively. The probe geometry of 2NT was optimized and computed dipole moment of the molecule was 4.91 Debye. The geometry of 2NT is planar and the methyl group (15H – 8C – 13H) attached to 4C is non-planar part. The 16H – 9C bond has bond length 1.08 Å. the ground state energy for 2NT was computed as -12953.7 eV. The 16H atom attached to the para position (9C) of the benzene ring was substituted by the halogen atoms (F, Cl, Br, and I) and the geometries of 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I are shown on Fig. 1. Halogens are the most electronegative elements of the periodic table. Due to their one valency, they are capable to gain single electron more easily, increasing the chemical reactivity of the molecule. Thus, the introduction of the halogen into the 2NT molecule results in the increment of overall chemical reactivity of the complex. Similar to the probe 2NT, the geometries of 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I are also planar except the 15H – 8C – 13H methyl group that leads to the non-planarity in the complex. The bond lengths of 17F – 9C, 17Cl – 9C, 17Br – 9C and 17I – 9C were observed as 1.39, 1.82, 1.94, and 2.13 Å respectively. There seems a rise in the bond length after the introduction of the halogen atom. However, 2NT-I had the largest bond length. The large bond lengths are promising in inducing more chemical reactivity as the large the bond is, easily it will dissociate to give free electrons [42]. So, the increasing bond length from F to I reveals that the 2NT-I has the ability to generate charge cloud more easily. The ground state energies of the 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I are − 360999.34, -587126.73, -1913610.98, and − 305451.91 Kcal/mol respectively. The structural parameters show the enhanced possibility of halogen atoms in inducing the intramolecular charge transfer (ICT) within the compounds.

Table 1

Variation in the bond lengths of halogen substituted location in (a) 2NT, (b) 2NT-F, (c) 2NT-Cl, (d) 2NT-Br, and (e) 2NT-I using B3LYP/6-311G.
Compound	Bond	Bond length
2NT	9C – 16H	1.08
2NT-F	17F – 16H	1.39
2NT-Cl	17F – 16H	1.82
2NT-Br	17F – 16H	1.94
2NT-I	17I – 16H	2.13

3.2 Mulliken charge and Counter plots analysis

The charge distribution was also examined for the 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I and the Mulliken charge distribution of these molecules are listed in SD 3. The Mulliken charge distribution of the molecules shows the negative charge contribution of the oxygen and nitrogen atoms. The hydrogen atoms however, contribute positively. The 9C atom attached to the para hydrogen 16H have negative charge of -0.111e. This charge seems to decrease as the atomic number of the halogens increased. This can be due to the decreasing order of electronegativity of the halogen atoms i.e., F > Cl > Br > I. The 17H atom has positive charge 0.167e. The 17F has negative charge (-0.323 e) but the rest of the halogen atoms imparts positively (17Cl (0.012e), 17Br (0.216 e), 17I (0.165 e)) in the total charge of the molecules. There seems a huge charge variation in the Mulliken charge among the halogenated hydrogen and the nitro group. This variation identifies the intramolecular interaction within the molecules [43]. The chemical reactivity was also verified by counter maps of the molecules (Fig. 2). The counter maps generally symbolize the behavior of the field lines when the material is placed in the electrostatic field [44]. The gathering of field lines near nitro group in 2NT shows that this area is highly under influence of the electrostatic field. The bonds settled near such areas experience a regular stretching and shrinking of the bonds resulting in the weakening of the bonds [45]. Such bonds have more probability of undergoing dissociation resulting in the evolution of charge cloud. The red counter lines indicate the electron donating part. Thus, the free charge cloud is seen to generate from the nitro group. The substitution of halogens enhanced the ability of ICT. The counterplots of the halogen substituted molecules (Fig. 2(b), 2(c), 2(d), and 2(e)) exhibits the highly accumulated yellow lines surrounding the halogen atoms showing electron withdrawing behavior of the halogen atoms. It reveals the active participation of the halogens in accepting charge cloud. Thus, the counter plots indicated the dislocation of charge cloud from the nitro group towards the halogen atoms. Therefore, the Mulliken charge distribution and the counter plots convey that the introduction of the halogen atoms enhances the ability of the molecules to induce ICT within the molecules.

3.3 Molecular orbital analysis

Molecular orbital parameters are computed in the study to investigate the chemical reactivity and the values are listed in Table 2. The energies corresponding to HOMO-LUMO were used to compute the global reactivity parameters. The ΔE of the halogen-substituted molecules decreases with the increase in the atomic number of the halogens. The low ΔE value for 2NT-I that shows the easy drifting of the electrons from lower energy orbitals to higher energy orbitals. IP is the minimum energy that is required to eject the outermost valence electrons. Among halogen-substituted atoms, 2NT-I has the minimum value of 7.32 eV for IP that reveals the tendency of 2NT-I to ionize valence electrons more easily than the other halogen compounds. The high value of EA reveals the capability of molecule to attract the free electron pairs. The values of EA increases as 2NT-F < 2NT-Cl < 2NT-Br < 2NT-I. The CP value is also higher for 2NT-I (-5.3 eV), showing its active participation in the chemical reactions than the other halogen-substituted molecules. The high values of χ reveals the high chemical reactivity of the molecules. The halogens, alkali metals and alkali metals are known to be highly reactive and thus has high values of χ. F = Cl > Br > I is the order of χ. The chemical hardness (η) defines the rigidness of the molecules. 2NT-F has the highest chemical hardness among the other halogen-substituted molecules. In contrast, the low value of S revels the chemical stability of the molecule, that is lowest for 2NT-F and 2NT-I. The uniformly distributed HOMO-LUMO map of the molecules is shown in Fig. 3. The blue color indicates the donating (i.e., positive) moieties and the red color indicates the electron withdrawing (i.e., negative) moieties of the molecules [46]. The unavailability of the HOMO-LUMO surface over the 16H atom at the para position of the 2NT over indicates that it does not participate in the charge transfer, but as the 16H was substituted by the halogen atoms, the shifting of HOMO-LUMO surfaces over the halogen atoms was observed. This indicates the active participation of the halogen atoms in ICT. The red color surface over the halogens shown in Fig. 3(b), 3(c), 3(d), and 3(e), reveals that the halogen atoms readily behave as the strong electron-withdrawing moieties in the molecules. This is obviously due to the high electronegative nature of the halogens. There seems the shifting of charge cloud in halogen-substituted 2NT that shows the enhanced chemical reactivity of these molecules. Thus, the frontier molecular orbital (FMO) and HOMO-LUMO analysis highlights the rise in the active chemical reactivity of the 2NT molecule after the substitution of the halogen atoms. Although, the 2NT-I has comparatively higher chemical reactivity among the other halogen-substituted 2NT molecules. This is also in better agreement with the high possibility of ICT in 2NT-I stated by structural and charge analysis.

Table 2

FMO parameters for the (a) 2NT, (b) 2NT-F, (c) 2NT-Cl, (d) 2NT-Br, and (e) 2NT-I molecule (all values in eV and value of S in eV^− 1).
S No.	Molecular property	2NT	2NT-F	2NT-Cl	2NT-Br	2NT-I
1.	E_HOMO	-7.62	-7.98	-7.91	-7.66	-7.32
2.	E_LUMO	-3.02	-3.22	-3.3	-3.24	-3.29
3.	Energy gap (ΔE)	4.6	4.76	4.61	4.42	4.03
4.	Ionization potential (IP)	7.62	7.98	7.91	7.66	7.32
5.	Electron affinity (EA)	3.02	3.22	3.3	3.24	3.29
6.	Chemical potential (CP)	-5.32	-5.6	-5.6	-5.45	-5.3
7.	Electronegativity (χ)	5.32	5.6	5.6	5.45	5.3
8.	Chemical hardness (η)	2.3	2.38	2.3	2.21	2.01
9.	Softness (S)	0.43	0.42	1.19	1.1	0.49

3.4 Absorption and Emission analysis

The simulated absorption spectra for halogen-substituted 2NT was computed using TD-DFT and illustrated in Fig. 4 and the transition details are mentioned in SD 4. It is clearly observable that the absorbance intensity of the 2NT molecule increases after the substitution of the halogens. This shows the increment in the electronic transitions undergoing in the molecules. the high electronegativity of the halogens leads to the electronic transitions within the 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I molecules. Single broad spectra was observed for all the molecules ranging between 250 to 450 nm. The peak in the absorbance spectra of 2NT was observed due to the transition between HOMO + 4 and LUMO. The excitation energy of this transition was computed as 3.81 eV. The transition between HOMO + 1 to LUMO causes the peak of absorption spectra of 2NT-F, 2NT-Cl and 2NT-Br at 299.27, 303.72, and 306.34 nm respectively. The wavelengths of peaks for 2NT-F, 2NT-Cl and 2NT-Br donot significantly differ, but the intensity has subsequent variation. The peak of the 2NT-I has the highest intensity of the absorbance spectra that is mainly constituted due to the transition between HOMO-LUMO. The wavelength of this transition was reported as 330.53 nm that shows the existence of typical π → π^∗ transitions [47]. Thus, the absorbance spectra analysis reported that 2NT-I has absorption band with highest intensity. High intensity leads to the high chemical reactivity and thus, high polarizability of the 2NT-I.

Figure 5 illustrates the emission spectra of the halogen substituted 2NT. The S₀→S₄ transitions were seen to be mainly responsible for the broad emission spectrum of the 2NT, 2NT-F, 2NT-Cl and 2NT-Br with f value 0.1989, 0.1997, 0.2481, and 0.2057v respectively. However, the transition S₀→S₃ with f value of 0.2322 was responsible for the formation of emission spectra of 2NT-I. The 2NT-I has the highest wavelength for emission as compared to the 2NT, 2NT-F, 2NT-Cl and 2NT-Br. The details of the emission spectra of all the molecules had been mentioned in SD 5. The radiative lifetime (τ) was calculated by below given formula for observing the emissive nature of the transitions [48]:

$$\tau =\frac{{c}^{3}}{2f{E}^{2 }}$$

…………………….

where c is the speed of light, f and E are the oscillator strength and the excitation energy of the crucial transition (transition having larger value of f obtained in the emission spectra). The value of τ reveals whether the molecules emit radiation during the transitions or the transitions are non-radiative. The transition with value of τ < 10 ns, can be attributed to emissive radiation, however the radiative lifetimes larger than 10 ns leads to the nonradiative transitions. The computed values of τ for 2NT, 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I have values 6.58, 8.12, 5.97, 6.59, and 8.28 ns respectively. All the values are lower than 10 ns are known to be radiative and these transitions eject energy in the form of photons. Thus, this shows the radiative nature of the transitions.

3.5 Vibrational analysis

Vibrational modes were analysed for major modes of the title molecules. Figure 6 illustrates a fair comparison between the simulated vibrational spectra. The detailed modes were mentioned in SD 6. The linear symmetric stretching (ν) of the para C – H bond was observed around 1230.33 cm^− 1. After the substitution of the halogen, there seems a rise in the Raman intensity of the bond. The ν mode of C – F, C – Cl, C – Br, and C – I were observed at 1256.76, 1271.48, 1271.16, and 1284.74 cm^− 1 respectively. The symmetric bending of C – C bonds of benzene ring was observed between 1300–1600 cm^− 1 for all the molecules. The intensity was however, seems to rise with the rise in the atomic number of halogens (say F < Cl < Br < I). The asymmetric stretching (α) of C – H bonds were observed above 3000 cm^− 1 and gradually increase from F to I. The other important modes are defined in Fig. 6. As the high Raman intensity leads to the high polarizability of the molecules [49]. The gradual rise in the Raman intensity of the vibrational modes related to nitro group and halogen atom indicates the high polarizability of the halogen-substituted NT molecule.

3.5 NLO analysis

The computed polarizability parameters were used for developing the NLO activity of the molecules. These polarizability parameters are actually the coefficients of Taylor series expansion of the energy of a material placed in electromagnetic field and their higher magnitudes are responsible for NLO activity of the materials [50]. The tensor components of the polarizability and hyperpolarizability are listed in SD 7 and SD 8 respectively. The values of α_total, Δα, and β_total for 2NT was computed as 12.95×10^− 24, 31.64×10^− 24, and 2.81×10^− 30 esu respectively. There seems a rise in the values of the polarizability parameters after the substitution of the halogen atom. Moreover, the respective values rise as the atomic number of the halogen atoms rises, i.e., the values of polarizability parameters increase as the atomic number rises. The values of polarizability parameters are listed in Table 3. The values of α_total for 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I are in increasing order of 13.06×10^− 24, 14.94×10^− 24, 15.87×10^− 24 and 16.64×10^− 24 esu respectively (Fig. 7). Similarly, the values of Δα are also in increasing order of 2NT-F (31.64×10^− 24 esu) < 4T-Cl (32.62×10^− 24esu) < 4T-Br (41.93×10^− 24 esu) < 4T-I (45.73×10^− 24esu). β_total is the parameter that mainly constitutes the NLO activity of the molecule. 2NT-I (18.72×10^− 30 esu) has the highest value of β_total compared to 2NT-F (5.42×10^− 30 esu), 2NT-Cl (9.54×10^− 30 esu), and 2NT-Br (12.37×10^− 30 esu). The introduction of halogens into 2NT shows an immense rise in the β_total that reveals their high ability to act as NLO material (Fig. 7). This might be due to the high chemical reactivity of the halogens. Although, the Iodine-substituted 2NT molecule has best potentiality of as an NLO active molecule other than the F, Cl, and Br compounds. For better validation of the results, the β_total was compared with most generally used reference materials Urea (0.781×10^− 30 esu) and KDP (7.39×10^− 30 esu) [51, 52]. The β_total of 2NT-I seem to be 24 times higher than Urea and two and a half times higher than KDP which shows the high NLO activity of 2NT-I molecule. The computed results are compared with halogen-substituted N-methyl-4-piperidone curcumin derivatives mentioned in reference study [53]. The values of β_total for 10 different halogen-substituted compounds ranged from 6.62×10^− 30 esu to 13.005×10^− 30 esu [54]. These values are comparatively less than the β_total of 2NT-I. Thus, the present study conveys the NLO activity of the halogen-substituted molecules.

Table 3

Computed values of α_total, Δα and β_total for the (a) 2NT, (b) 2NT-F, (c) 2NT-Cl, (d) 2NT-Br, and (e) 2NT-I (All values are in esu).
Molecule	α_total	Δα	β_total
2NT	12.95×10^− 24	31.64×10^− 24	2.81×10^− 30
2NT-F	13.06×10^− 24	32.62×10^− 24	5.42×10^− 30
2NT-Cl	14.94×10^− 24	41.93×10^− 24	9.54×10^− 30
2NT-Br	15.87×10^− 24	45.73×10^− 24	12.37×10^− 30
2NT-I	16.64×10^− 24	51.55×10^− 24	18.72×10^− 30

The substitution of halogens in the 2NT molecule has enormously scaled the quantum mechanical properties of the 2NT. This was due to the high electronegativity of the halogens. The rise in the structural parameters and FMO parameters was observed due to the electronegativity of the halogens. Large variation in the charges of the atoms and the accumulation of the field lines near the halogen atoms justifies the active participation of the halogens in inducing the intramolecular interactions and shifting of charge cloud from nitro group towards the halogen atom. The absorbance intensity also undergoes a rise after the substitution of the halogens and increases with the increasing atomic number of the halogens i.e., F < Cl < Br < I. Thus, the highest absorbance intensity was observed for the 2NT-I molecule. The computed values of radiative lifetime for crucial transitions reveals the radiative nature of transitions. A similar kind of rise was observed in the Raman intensity after the substitution of the halogens. The 2NT-I has the vibrational modes with the highest Raman intensity. The values of β_total of the 2NT-F, 2NT-Cl, 2NT-Br, and 2NT-I are computed to be three times, seven times, twelve times, and twenty-four times higher than Urea. Thus, from the present study, it can be concluded that the halogen-substituted 2NT molecules possess promising NLO activity. In comparison, the 2NT-I has the highest value of β_total revealing its best NLO activity among the other halogen-substituted 2NT. We believe that the halogen-substituted 2NT has proven to be excellent candidates for promoting the upgrading and updating of NLO devices with greatly improved performance and novel functionalities. Moreover, the experimental demonstration of the present study will surely be rewarding.

Ethical Approval

This material is the authors' own original work, which has not been previously published elsewhere. All authors have been personally and actively involved in substantial work leading to the paper, and will take public responsibility for its content. The paper properly credits the meaningful contributions of all the co-authors.

Competing interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Authors' contributions

Shradha Lakhera: Data curation, Writing-Original draft preparation, Visualization, Investigation, Software, Validation.

Meenakshi Rana: Conceptualization, Methodology, Writing-Reviewing and Editing, Supervision

Kamal Devlal: Conceptualization, Writing- Reviewing and Editing

Funding

The authors declare that this research received no specific grant from any funding agency.

Availability of data and materials

All data generated or analysed during this study, which support the plots within this paper and the other findings of this study, are included in this article and it’s Supplementary Information. Source data are provided with this paper.

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Investigation of the Electrical and Optical Activity of Halogen-substituted 2- nitrotoulene by Density Functional Theory

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Abstract

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1. Introduction

2. Computational Methods

3. Results And Discussion

3.1 Structural analysis

3.2 Mulliken charge and Counter plots analysis

3.3 Molecular orbital analysis

3.4 Absorption and Emission analysis

3.5 Vibrational analysis

3.5 NLO analysis

4. Conclusion

Declarations

References

Additional Declarations

Supplementary Files

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