In recent years, many studies have been done on the structure of fullerene as medicine nano carrier compounds. On this basis, Quantum mechanical calculations have been done and the effect of the nicotine compound in structure of Nanofullerene C 12 was studied. Density Functional Theory (DFT) can be used to calculate an accurate electronic structure, HOMO and LUMO energies, Mulliken charge of atoms, energetic orbital levels, global hardness, chemical potential and electrophilicity of systems, and finally chemical, physical properties of fullerene and fullerene derivatives. Theoretical calculations such as Natural Bond Orbital (NBO) are very important to understand the pathways of electron transfer in assemblies. Consequently, the obtained results showed that energy orbital levels decreased considerably by linking structure of Nanofullerene to the structure of Nicotine. The intramolecular interaction is formed by the orbital overlap between C-C, C-N, C-H anti bonding orbital which results an intermolecular charge transfer (ICT) from a Lewis valence orbital (donor), with a decreasing of its occupancy, to a non-Lewis orbital (acceptor). The interacting effect is also discussed in terms of the change in the C-C bond lengths, net atomic charge distribution, total dipole moment. The obtained results indicate that the C-C distances are enlarged interaction. Furthermore, there is a complete change in the net atomic charge distribution, as well as a corresponding increase in the value of the total dipole moment. On the basis of fully optimized ground-state structure, TDDFT//B3LYP/3-21G* calculations have been performed to determine the low-lying excited states of nanofullerene interacting with nicotine (NFN).
Nicotine is a nitrogen organic compound which is mostly found in plants such as tobacco and rarely found in tomato, potato, eggplant and green pepper. The 0.3% to 5% of the tobacco, dried plant is made by nicotine and is effectively on neural system which is used in many insecticides. Nicotine was obtained from tobacco for the first time in 1828 by a German chemist [
The aim of the present work is to investigate the interaction of fullerene with nicotine by using the hybrid DFT-B3LYP functional in conjugation with 3-21G* basis set. These interactions show the stability of the structure. Density Functional Theory is used for calculating the electronic structure, HOMO and LUMO energies, Mulliken charge of atoms, Molecular orbital analyses of the title compound. Electronic properties increase the surface modification which is leading to the novel medical application. By investigating HOMO-LUMO energy gap, the chemical stability against electronic excitation also has been studied. This was done by discussing quantum chemical parameters, local reactivity indices such as a Fukui function in nanofullerene interacting with nicotine by natural bond orbital (NBO) analysis. Thus, it would also possible to produce novel species for biomedical application; by attaching the nitrogen atom of nicotine with the carbon atom of fullerene.
All structures relating to the structure of Nicotine and Nano fullerene nicotine (NFN) were designed primarily with the use of Gabedit 2.3.8 software. The computationally predicted various possible conformers are shown in
Parameter | HF/3-21G* | DFT/3-21G* |
---|---|---|
Bond Length (Å) | ||
R (1,2) | 1.4298 | 1.43491 |
R (1,12) | 1.3315 | 1.3538 |
R (1,18) | 1.488 | 1.4496 |
R (2,7) | 1.1984 | 1.2239 |
R (3,4) | 1.3824 | 1.3649 |
R (3,8) | 1.2028 | 1.2337 |
R (4,9) | 1.2179 | 1.2514 |
R (5,6) | 1.3416 | 1.3143 |
R (5,10) | 1.2273 | 1.2693 |
R (6,11) | 1.2346 | 1.2821 |
R (7,8) | 1.3764 | 1.3665 |
R (9,10) | 1.3627 | 1.3437 |
R (11,12) | 1.3409 | 1.2946 |
R (13,14) | 1.3802 | 1.3858 |
R (13,18) | 1.3387 | 1.3708 |
R (13,20) | 1.0686 | 1.0812 |
Bond angle (˚) | ||
A (2,1,12) | 125.61 | 123.01 |
A (2,1,18) | 115.69 | 117.06 |
A (12,1,18) | 118.68 | 119.92 |
A (1,2,7) | 162.84 | 155.94 |
A (4,3,8) | 159.10 | 163.06 |
A (3,4,9) | 129.10 | 128.60 |
A (6,5,10) | 168.87 | 170.24 |
A (5,6,11) | 142.97 | 138.75 |
A (2,7,8) | 164.40 | 167.89 |
A (3,8,7) | 146.21 | 143.02 |
A (4,9,10) | 160.56 | 163.64 |
A (5,10,9) | 131.72 | 128.29 |
A (1,12,11) | 128.36 | 138.44 |
A (14,13,18) | 121.76 | 121.74 |
A (14,13,20) | 122.58 | 122.51 |
A (18,13,20) | 115.63 | 115.73 |
A (13,14,15) | 118.13 | 118.99 |
The energies of frontier molecular orbital (εHOMO, εLUMO), energy band gap (εLUMO-εHOMO), electro negativity (χ), chemical potential (µ), global hardness (η), global softness (S), and global electrophilicity index (ω) [
Dipole moment (µ), polarizability <α>, and total first static hyperpolarizability [
The isotropic polarizability is
and the average hyperpolarizability is
The total molecular dipole moment (μ), mean polarizability (α) and total static hyperpolarizability (β) of NFN molecule have been collected in
Compounds | εH eV | εL eV | εL-εH eV | Χ eV | µ eV | η eV | S eV | ω eV |
---|---|---|---|---|---|---|---|---|
Nicotine | −5.53130 | −0.50232 | 5.02898 | 3.01681 | −3.01681 | 2.51449 | 0.19884 | 1.80973 |
NFN | −5.10625 | −4.24310 | 0.86315 | 4.6746 | −4.6746 | 0.43157 | 1.15856 | 25.3167 |
NFN B3LYP/3-21G* | ||
---|---|---|
HF | DFT | |
Polarizability | ||
αxx | −155.47 | −152.78 |
αxy | −0.1832 | 0.7354 |
αyy | −138.14 | −135.77 |
αyz | −1.8238 | −1.6824 |
αzz | −142.18 | −139.05 |
αxz | −0.2229 | −0.2637 |
<α> | −145.248 | −142.531 |
∆α | 16.3888 | 15.9228 |
Hyperpolarizability | ||
βxxx | −477.81 | −436.029 |
βxxy | 5.3589 | 5.6610 |
βxyy | −102.195 | −96.058 |
βyyy | 68.40 | 59.6920 |
βxxz | −6.2840 | −6.8692 |
βxyz | −0.2452 | −0.4498 |
βyyz | 8.6440 | 7.9138 |
βxzz | −48.076 | −40.999 |
βyzz | −7.7217 | −8.3533 |
βzzz | 3.5169 | 2.4564 |
βTotal | 631.570 | 575.924 |
The HOMO and LUMO energy were calculated by B3LYP/3-21G* method. The HOMO represents the ability to donate an electron, LUMO as an electron acceptor represents the ability to obtain an electron. The difference between HOMO and LUMO orbital is called as energy gap that is an important stability for structures. This electronic absorption corresponds to the transition from the ground to the first excited state and is mainly described by one electron excitation from the highest occupied molecular or orbital (LUMO) both the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are the main orbital take part in chemical stability. Therefore, while the energy of the HOMO is directly related to the ionization potential, LUMO energy is directly related to the electron affinity is shown in
On the basis of fully optimized ground-state structure, DFT/B3LYP/3-21G* calculations have been used to determine the low-lying excited states of fullerene. The theoretical results involving the vertical excitation energies, oscillator strength (f) and wavelength are carried out using the Gaussian 09 program. Electronic transition determined from excited-state calculations are listed in
Mulliken atomic charge calculation has an important role in the application of quantum chemical calculation of molecular system because of atomic charge effect dipole moment, molecular polarizability, electronic structure and more a lot of properties of molecular systems. The atomic charge values were obtained by the Mulliken population analysis [
HF | DFT | |||||
---|---|---|---|---|---|---|
Excitation | Wavelength (nm) | Oscillator Strength (f) | Energy (eV) | Wavelength (nm) | Oscillator Strength (f) | Energy (eV) |
Excited State 1 75 → 88 78 → 87 79 → 81 79 → 82 | 661.79 | 0.0056 | 1.8735 | 1507.07 | 0.0014 | 0.8227 |
Excited State 2 74 → 87 77 → 82 77 → 88 79 → 84 80 → 81 80 → 82 | 458.53 | 0.0314 | 2.7039 | 1056.31 | 0.0364 | 1.1738 |
Excited State 3 74 → 85 77 → 84 78 → 81 78 → 82 79 → 81 79 → 87 80 → 84 | 380.21 | 0.0021 | 3.2610 | 651.98 | 0.0000 | 1.9017 |
The Fukui Function (FF) of a molecule provides information on the reactivity. The atom with the highest Fukui function value is highly reactive when compared to the other atoms in the molecule. These values represent the qualitative description of reactivity of different atoms in the molecule. The Fukui Function successfully predicts relative reactivity for most chemical systems and as such it provides a method for understanding and categorizing chemical reactions. The use of the Fukui Function for the selectivity of the nicotine molecule for nucleophilic and electrophilic attracts has been made with special emphasis to the dependence of the Fukui values on the basis to B3LYP/3-21G* level of theory. Ayers and Parr [
ATOM | CHARGES | |
---|---|---|
DFT | HF | |
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 N18 C19 H20 H21 H22 H23 H24 N25 C26 C27 C28 C29 H30 H31 H32 H33 H34 H35 H36 | 0.197975 −0.132399 0.051453 −0.093132 0.067261 −0.102881 −0.125630 −0.034270 −0.071621 −0.113094 −0.096077 −0.065258 0.219385 −0.072306 −0.148998 −0.246228 0.178749 −0.857865 −0.100270 0.307530 0.219484 0.224976 0.286579 0.242774 −0.457726 −0.388548 −0.395855 −0.233856 −0.1418690 0.199874 0.199877 0.203037 0.204392 0.214170 0.202767 0.172618 | 0.289952 −0.189103 −0.022161 0.052123 −0.078313 0.007909 −0.396749 0.054490 −0.042288 0.008468 −0.046427 0.071413 0.336054 −0.204861 0.143168 −0.1341124 0.267552 −1.044565 −0.030929 0.390279 0.286861 0.283967 0.347006 0.269603 −0.636131 −0.431101 −0.445328 −0.214962 −0.382682 0.223487 0.217643 0.226773 0.226490 0.236353 0.225489 0.176919 |
corresponds to the number of electrons in the molecule. N + 1 corresponds to an anion, with an electron added to the LUMO of the neutral molecule. N − 1 correspondingly is the cation with an electron removed from the HOMO of the neutral. All calculations are done at the ground-state geometry. These functions can be condensed to the nuclei by using an atomic charge partitioning scheme, such as Mulliken population analysis:
Local softness and electrophilicity indices are calculated using (4)
where +, −, and 0 signs show nucleophilic, electrophilic, and radical attack, respectively. Redistribution of the electrons on the f+ species the atomic charges of each atom are slightly increased (
Atom Number | |||||||||
---|---|---|---|---|---|---|---|---|---|
C1 | −0.01776 | 0.011441 | 0.07251 | −0.0035 | 0.002274 | 0.014418 | −0.032 | 0.0207 | 0.1312 |
C2 | 0.032434 | 0.026946 | −0.0414 | 0.00644 | 0.005357 | −0.00824 | 0.0586 | 0.0487 | −0.075 |
C3 | −0.01825 | 0.484883 | −0.1591 | −0.0036 | 0.09641 | −0.03163 | −0.033 | 0.8775 | −0.287 |
C4 | 0.028453 | −0.02433 | −0.2354 | 0.00565 | −0.00483 | −0.04681 | 0.0514 | −0.044 | −0.426 |
C5 | −0.01811 | 0.091076 | 0.06466 | −0.0036 | 0.01810 | 0.01285 | −0.032 | 0.1648 | 0.1170 |
N6 | 0.287293 | 0.428028 | −0.5354 | 0.05712 | 0.08510 | −0.10646 | 0.5199 | 0.7746 | −0.968 |
C7 | −0.03006 | −0.00660 | −0.1045 | −0.0059 | −0.00131 | −0.02079 | −0.054 | −0.011 | −0.189 |
H8 | 0.004645 | −0.00414 | 0.23298 | 0.00092 | −0.00082 | 0.04632 | 0.0084 | −0.007 | 0.4216 |
H9 | 0.002456 | −0.02694 | 0.19943 | 0.00048 | −0.00535 | 0.03965 | 0.0044 | −0.048 | 0.3609 |
H10 | 0.003318 | −0.00160 | 0.18764 | 0.00065 | −0.00031 | 0.037310 | 0.0060 | −0.002 | 0.3395 |
H11 | 0.005871 | −0.00876 | 0.21071 | 0.00116 | −0.00174 | 0.04189 | 0.0106 | −0.015 | 0.3813 |
H12 | 0.014426 | 0.006525 | 0.22819 | 0.00286 | 0.001297 | 0.04537 | 0.0261 | 0.0118 | 0.4129 |
N13 | 0.574047 | 0.001451 | −0.4785 | 0.11414 | 0.000288 | −0.09514 | 1.0388 | 0.0026 | −0.865 |
C14 | 0.071002 | 0.001881 | −0.3822 | 0.01411 | 0.00374 | −0.07599 | 0.1284 | 0.0034 | −0.691 |
C15 | 0.04187 | −0.00033 | −0.3988 | 0.00832 | −0.00006 | −0.07931 | 0.0757 | −0.005 | −0.721 |
C16 | −0.02738 | 0.002620 | −0.2259 | −0.0054 | 0.00052 | −0.04492 | −0.049 | 0.0047 | −0.408 |
C17 | −0.02501 | 0.00575 | −0.4128 | −0.0049 | 0.00114 | −0.08208 | −0.045 | 0.0104 | −0.747 |
H18 | 0.000342 | 0.00181 | 0.19232 | −0.0006 | 0.00035 | 0.038240 | 0.0006 | 0.0032 | 0.3480 |
H19 | −0.00300 | −0.00019 | 0.20087 | −0.0005 | −0.00003 | 0.03994 | −0.005 | −0.003 | 0.3635 |
H20 | −0.00101 | 0.00081 | 0.19538 | −0.00020 | −0.00016 | 0.03884 | −0.001 | −0.001 | 0.3535 |
H21 | −0.00149 | 0.000067 | 0.19734 | −0.00029 | 0.00001 | 0.03923 | −0.002 | 0.0001 | 0.3571 |
H22 | 0.014494 | 0.00048 | 0.20524 | −0.00028 | 0.00009 | 0.04080 | 0.0262 | 0.0008 | 0.3714 |
H23 | 0.000293 | −0.00003 | 0.19479 | −0.00005 | −0.00005 | 0.03873 | 0.0005 | −0.005 | 0.3525 |
H24 | 0.048812 | −0.00050 | 0.17199 | 0.00970 | −0.00009 | 0.03419 | 0.0883 | 0.0009 | 0.3112 |
H25 | 0.004551 | 0.00656 | 0.2200 | 0.00090 | 0.001304 | 0.043744 | 0.0082 | 0.0118 | 0.3981 |
H26 | 0.007791 | 0.002097 | 0.2004 | 0.00154 | 0.000416 | 0.03984 | 0.0140 | 0.0037 | 0.3626 |
that this atom is nucleophilic attack, while for electrophilic attack, H23 are found to be the most active atoms. The calculated Fukui’s functions for all the inhibitors are presented in
Natural Bond Orbital Analysis was originally developed as a way of quantifying resonance structure contributions to molecules. NBO analysis is carried out by examining all possible interactions between “filled” (donor) Lewis-type NBOs and “empty” (acceptor) non-Lewis NBOs, and estimating their energetic importance of 2nd-order perturbation theory. NBO analysis is an essential tool for studying intra and intermolecular bonding and interaction among bonds, and also provides a convenient basis for charge transfer or conjugative interaction in molecular systems. NBO analysis has been performed on NFN molecule using Gaussian 03 package at the B3LYP/3-21G* level in order to understand various second order interactions between electron donors and electron acceptors. In the NBO analysis [
Bond (A-B) | Occupancy | EDA (%) | EDB (%) | NBO | S (%) | P (%) |
---|---|---|---|---|---|---|
BD(1)C1-C2 | 1.97426 | 51.76 | 48.24 | 0.7195sp1.72 + 0.6975sp1.26 | 36.72, 44.19 | 63.28, 55.81 |
BD(1)C1-C12 | 1.94763 | 50.37 | 49.63 | 0.7097sp2.08 + 0.7045sp1.10 | 32.50, 47.61 | 67.50, 52.39 |
BD(1)C1-N18 | 1.95812 | 31.94 | 68.06 | 0.5652sp4.83 + 0.8250sp2.21 | 17.16, 31.11 | 82.84, 68.89 |
BD(1)C2-C7 | 1.96547 | 49.39 | 50.61 | 0.7028sp1.44+ 0.7114sp1.18 | 41.01, 45.78 | 58.99, 54.22 |
BD(1)C3-C4 | 1.98504 | 49.66 | 50.34 | 0.7047sp1.41 + 0.7095sp1.32 | 41.49, 43.17 | 58.51, 56.83 |
BD(1)C3-C8 | 1.96330 | 49.82 | 50.18 | 0.7058sp1.35+ 0.7084sp1.34 | 42.60, 42.76 | 57.40, 57.24 |
BD(1)C4-C9 | 1.95981 | 50.64 | 49.36 | 0.7116sp1.29 + 0.7026sp1.45 | 43.75, 40.81 | 40.81, 59.19 |
BD(1)C5-C6 | 1.98223 | 50.42 | 49.58 | 0.7101sp1.27 +0.7041sp1.32 | 44.13, 43.06 | 55.87, 56.94 |
BD(1)C5-C10 | 1.96016 | 50.05 | 49.95 | 0.7074sp1.31 + 0.7068sp1.40 | 43.34, 41.64 | 56.66, 58.36 |
BD(1)C6-C11 | 1.95785 | 51.71 | 48.29 | 0.7191sp1.08 + 0.6949sp1.68 | 48.07, 37.32 | 51.93, 62.68 |
BD(1)C7-C8 | 1.98923 | 49.28 | 50.72 | 0.7020sp1.31 + 0.7122sp1.28 | 42.22, 43.93 | 57.78, 56.07 |
BD(1)C9-C10 | 1.98616 | 50.15 | 49.85 | 0.7082sp1.35 + 0.7060sp1.40 | 42.96, 57.04 | 41.69, 58.31 |
BD(1)C11-C12 | 1.98686 | 50.19 | 49.81 | 0.7085sp1.26 + 0.7057sp1.38 | 44.25, 42.07 | 55.75, 57.93 |
BD(1)C13-C14 | 1.97796 | 48.71 | 51.29 | 0.6979sp1.67 + 0.7162sp2.00 | 37.52, 33.30 | 62.48, 66.70 |
BD(1)C13-N18 | 1.98466 | 35.62 | 64.38 | 0.5968sp2.68 + 0.8024sp2.04 | 27.17, 32.87 | 72.83, 67.13 |
BD(1)C13-H20 | 1.98034 | 65.14 | 34.86 | 0.8071sp1.83 + 0.5904sp0.00 | 35.36, 100.0 | 64.64 |
BD(1)C14-C15 | 1.97543 | 51.02 | 48.98 | 0.7143sp1.92 + 0.6999sp1.90 | 34.28, 34.43 | 65.72, 65.57 |
BD(1)C14-C19 | 1.97418 | 51.36 | 48.64 | 0.7166sp2.09 + 0.6974sp2.66 | 32.38, 27.34 | 67.62, 72.66 |
BD(1)C15-C16 | 1.98006 | 50.06 | 49.94 | 0.7075sp1.89 + 0.7067sp1.89 | 34.56, 34.59 | 65.44, 65.41 |
BD(1)C15-H21 | 1.98220 | 63.18 | 36.82 | 0.7948sp2.22 + 0.6068sp0.00 | 31.01, 100.0 | 28.99 |
BD(1)C16-C17 | 1.98303 | 50.12 | 49.88 | 0.7080sp1.95 + 0.7062sp1.61 | 33.86, 38.24 | 66.14, 61.76 |
BD(1)C16-H22 | 1.98086 | 63.44 | 36.56 | 0.7965sp2.17 + 0.6047sp0.00 | 31.57, 100.0 | 68.43 |
BD(1)C17-N18 | 1.98700 | 35.59 | 64.41 | 0.5966sp2.70 + 0.8026sp1.82 | 27.00, 35.44 | 73.00, 64.56 |
BD(1)C17-H23 | 1.97830 | 64.31 | 35.69 | 0.8020sp1.87 + 0.5974sp0.00 | 34.80, 100.0 | 65.20 |
BD(1)C19-H24 | 1.96561 | 63.82 | 36.18 | 0.7989sp2.99 + 0.6015sp0.00 | 25.05, 100.0 | 74.95 |
BD(1)C19-N25 | 1.98009 | 40.77 | 59.23 | 0.6385sp3.73 + 0.7696sp2.58 | 21.13, 27.97 | 78.87, 72.03 |
BD(1)C19-C26 | 1.98392 | 50.67 | 49.33 | 0.7118sp2.78 + 0.7024sp3.05 | 26.45, 24.66 | 73.55, 75.34 |
BD(1)N25-C28 | 1.98463 | 60.82 | 39.18 | 0.7799sp2.57 + 0.6259sp3.74 | 21.10, 27.75 | 71.97, 78.90 |
BD(1)N25-C29 | 1.98879 | 60.70 | 39.30 | 0.7791sp2.60 + 0.6269sp3.67 | 27.75, 21.43 | 72.25, 78.57 |
BD(1)C26-C27 | 1.98084 | 50.74 | 49.26 | 0.7123sp2.97 + 0.7019sp3.04 | 25.19, 24.75 | 74.81, 75.25 |
BD(1)C26-H30 | 1.98543 | 62.47 | 37.53 | 0.7904sp2.95 + 0.6127sp0.00 | 25.33, 100.0 | 74.67 |
BD(1)C26-H31 | 1.98605 | 62.18 | 37.82 | 0.7885sp3.04 + 0.6150sp0.00 | 24.77, 100.0 | 75.23 |
BD(1)C27-C28 | 1.99014 | 50.63 | 49.37 | 0.7116sp3.02 + 0.7026sp2.81 | 24.88, 26.26 | 75.12, 73.74 |
BD(1)C27-H32 | 1.98712 | 62.47 | 37.53 | 0.7904sp2.95 + 0.6126sp0.00 | 25.29, 100.0 | 74.71 |
BD(1)C27-H33 | 1.98813 | 62.32 | 37.68 | 0.7895sp3.00 + 0.6138sp0.00 | 25.02, 100.0 | 74.98 |
BD(1)C28-H34 | 1.98738 | 62.28 | 37.72 | 0.7892sp2.89 + 0.6142sp0.00 | 25.70, 100.0 | 74.30 |
BD(1)C28-H35 | 1.98829 | 62.40 | 37.60 | 0.7900sp2.72 + 0.6132sp0.00 | 26.85, 100.0 | 73.15 |
BD(1)C28-H36 | 1.99691 | 60.53 | 39.47 | 0.7780sp2.84 + 0.6283sp0.00 | 26.05, 100.0 | 73.95 |
BD(1)C29-H37 | 1.99112 | 61.83 | 38.17 | 0.7863sp2.79 + 0.6178sp0.00 | 26.36,100.0 | 73.64 |
BD(1)C29-H38 | 1.99147 | 62.11 | 37.89 | 0.7881sp2.82 + 0.6155sp0.00 | 26.17,100.0 | 73.83 |
LP(1) C8 | 0.80654 | - | - | sp99.99 | 0.08 | 99.92 |
LP(1) N25 | 1.89205 | - | - | Sp5.18 | 16.19 | 83.81 |
Donor NBO (i) | Acceptor NBO (j) | E(2) kcal/mol | E(j) - E (i) (a.u.) | F (i, j) a.u. |
---|---|---|---|---|
BD(1) C1-C2 | BD*(1) C1-C12 | 1.69 | 1.25 | 0.041 |
BD(1) C1-C2 | BD*(1) C7-C8 | 1.13 | 1.28 | 0.034 |
BD(1) C1-C2 | BD*(1) C13-N18 | 2.48 | 1.13 | 0.041 |
BD(1) C1-C12 | BD*(1) C1-C2 | 2.28 | 1.25 | 0.048 |
BD(1) C1-C12 | BD*(1) C17-N18 | 2.42 | 1.09 | 0.046 |
BD(1) C1-N18 | BD*(1) C11-C12 | 1.58 | 1.27 | 0.040 |
BD(1) C1-N18 | BD*(1) C13-C14 | 2.06 | 1.26 | 0.046 |
BD(1) C2-C7 | BD*(1) C3-C8 | 2.63 | 0.74 | 0.041 |
BD(1) C3-C4 | BD*(1) C7-C8 | 1.30 | 1.28 | 0.036 |
BD(1) C3-C4 | BD*(1) C9-C10 | 1.43 | 1.26 | 0.038 |
BD(1) C3-C8 | BD*(1) C3-C4 | 0.78 | 1.23 | 0.028 |
BD(1) C4-C9 | BD*(1) C9-C10 | 1.08 | 1.24 | 0.033 |
BD(1) C5-C6 | BD*(1) C9-C10 | 1.50 | 1.25 | 0.039 |
BD(1) C5-C6 | BD*(1) C11-C12 | 1.31 | 1.27 | 0.036 |
BD(1) C5-C10 | BD*(1) C9-C10 | 2.22 | 0.77 | 0.039 |
BD(1) C6-C11 | BD*(1) C11-C12 | 1.18 | 1.24 | 0.034 |
BD(1) C7-C8 | BD*(1) C3-C4 | 1.56 | 1.25 | 0.040 |
BD(1) C9-C10 | BD*(1) C5-C6 | 1.47 | 1.24 | 0.038 |
BD(1) C11-C12 | BD*(1) C5-C6 | 1.55 | 1.23 | 0.039 |
BD(1) C13-C14 | BD*(1) C14-C15 | 3.81 | 1.29 | 0.063 |
BD(1) C13-C14 | BD*(1) C14-C19 | 2.11 | 1.14 | 0.044 |
BD(1) C13-N18 | BD*(1) C17-N18 | 2.55 | 1.24 | 0.050 |
BD(1) C13-H20 | BD*(1) C13-C14 | 2.07 | 1.09 | 0.042 |
BD(1) C13-H20 | BD*(1) C14-C15 | 3.51 | 1.10 | 0.055 |
BD(1) C13-H20 | BD*(1) C17-N18 | 3.29 | 0.94 | 0.050 |
BD(1) C14-C15 | BD*(1) C13-C14 | 3.41 | 1.27 | 0.059 |
BD(1) C14-C15 | BD*(1) C13-H20 | 1.45 | 1.19 | 0.037 |
BD(1) C14-C15 | BD*(1) C14-C19 | 2.47 | 1.13 | 0.047 |
BD(1) C14-C15 | BD*(1) C15-C16 | 2.82 | 1.28 | 0.054 |
BD(1) C14-C19 | BD*(1) C13-C14 | 2.54 | 1.19 | 0.049 |
BD(1) C14-C19 | BD*(1) C13-N18 | 2.89 | 1.04 | 0.049 |
BD(1) C14-C19 | BD*(1) C14-C15 | 2.54 | 1.19 | 0.049 |
BD(1) C15-C16 | BD*(1) C14-C15 | 3.13 | 1.28 | 0.056 |
BD(1) C15-C16 | BD*(1) C14-C19 | 3.03 | 1.13 | 0.052 |
BD(1) C15-C16 | BD*(1) C16-C17 | 2.40 | 1.27 | 0.049 |
BD(1) C15-H21 | BD*(1) C13-C14 | 3.29 | 1.09 | 0.053 |
BD(1) C15-H21 | BD*(1) C16-C17 | 2.91 | 1.09 | 0.050 |
BD(1) C16-C17 | BD*(1) C1-N18 | 2.51 | 1.01 | 0.046 |
BD(1) C16-C17 | BD*(1) C15-C16 | 2.79 | 1.29 | 0.054 |
BD(1) C16-H22 | BD*(1) C14-C15 | 2.92 | 1.09 | 0.050 |
BD(1) C16-H22 | BD*(1) C17-N18 | 4.36 | 0.94 | 0.057 |
BD(1) C17-N18 | BD*(1) C13-N18 | 2.80 | 1.26 | 0.053 |
BD(1) C17-H23 | BD*(1) C13-N18 | 3.30 | 0.95 | 0.050 |
BD(1) C17-H23 | BD*(1) C15-C16 | 2.99 | 1.10 | 0.051 |
---|---|---|---|---|
BD(1) C19-H24 | BD*(1) N25-C29 | 2.83 | 0.83 | 0.043 |
BD(1) C19-H24 | BD*(1) C26-H31 | 2.17 | 0.95 | 0.041 |
BD(1) C19-N25 | BD*(1) C28-H35 | 1.64 | 1.16 | 0.039 |
BD(1) C19-C26 | BD*(1) C13-C14 | 2.50 | 1.14 | 0.048 |
BD(1) C19-C26 | BD*(1) C14-C19 | 1.16 | 0.99 | 0.030 |
BD(1) N25-C28 | BD*(1) C14-C19 | 2.61 | 1.07 | 0.047 |
BD(1) N25-C29 | BD*(1) C19-H24 | 1.27 | 1.14 | 0.034 |
BD(1) N25-C29 | BD*(1) C28-H34 | 1.21 | 1.15 | 0.033 |
BD(1) C26-C27 | BD*(1) C14-C19 | 2.23 | 0.97 | 0.042 |
BD(1) C26-H30 | BD*(1) C19-N25 | 2.20 | 0.82 | 0.038 |
BD(1) C26-H31 | BD*(1) C27-H32 | 1.05 | 0.97 | 0.029 |
BD(1) C27-H32 | BD*(1) N25-C28 | 1.55 | 0.81 | 0.032 |
BD(1) C27-H33 | BD*(1) C28-H34 | 1.30 | 0.96 | 0.032 |
BD(1) C28-H34 | BD*(1) N25-C29 | 2.38 | 0.81 | 0.039 |
BD(1) C28-H34 | BD*(1) C27-H33 | 1.62 | 0.96 | 0.035 |
BD(1) C28-H35 | BD*(1) C19-N25 | 1.95 | 0.83 | 0.036 |
BD(1) C28-H35 | BD*(1) C26-C27 | 1.22 | 0.87 | 0.029 |
BD(1) C29-H37 | BD*(1) N25-C28 | 2.33 | 0.82 | 0.039 |
BD(1) C29-H38 | BD*(1) C19-N25 | 3.01 | 0.82 | 0.045 |
LP(1) C8 | BD*(1) C3-C8 | 7.60 | 0.58 | 0.090 |
LP(1) N25 | BD*(1) C19-C26 | 5.71 | 0.61 | 0.053 |
LP(1) N25 | BD*(1) C27-C28 | 5.22 | 0.61 | 0.052 |
LP(1) N25 | BD*(1) C29-H36 | 6.67 | 0.71 | 0.063 |
orbital and occupancy between 0.8 and 1.9 electrons. Several other types of valence data, such as directionality, hybridization and partial charges were analyzed in
The values of some thermodynamic parameters such as zero-point vibrational energy, thermal energy, specific heat capacity, rotational constants, and entropy of nano fullerene with nicotine (NFN) at 298.15 K in ground state are listed in
NFN | ||
---|---|---|
Basis Set | HF/3-21G* | DFT/3-21G* |
Total energy (Thermal), Etotal (kcal/mol) | 207.857 | 194.841 |
Vibrational energy, Evib (kcal/mol) | 206.07 | 193.06 |
Zero point vibrational energy (kcal/mol) | 195.957 | 181.934 |
Rotational Constants (GHz) | ||
X | 0.5957 | 0.56367 |
Y | 0.1036 | 0.10476 |
Z | 0.09049 | 0.09053 |
Specific heat, Cv (Cal/mol/K) | 72.819 | 79.270 |
Entropy, S (Cal/mol/K) | 144.733 | 150.341 |
Dipole moment, µ (Debye) | ||
µx | −13.9605 | −12.6294 |
µy | 5.1207 | 3.8068 |
µz | 0.3809 | 0.2618 |
µTotal | 14.874 | 13.1933 |
NFN | ||
---|---|---|
Thermodynamic Parameters | HF/3-21G* | DFT/3-21G* |
Zero-point correction (Hartree/Particle) | 0.312279 | 0.289931 |
Thermal correction to Energy | 0.331241 | 0.310499 |
Thermal correction to Enthalpy | 0.332185 | 0.311443 |
Thermal correction to Gibbs Free Energy | 0.263418 | 0.240011 |
195.957 a.u. Whereas the smallest values of ZPVE of B3LYP (NFN) are 181.9345 a.u obtained at B3LYP/ 3-21G*. Dipole moment reflects the molecular charge distribution and is given as a vector in three dimensions. Therefore, it can be used as a descriptor to depict the charge movement across the molecule. Direction of the dipole moment vector in a molecule depends on the centers of positive and negative charges. Dipole moments are strictly determined for neutral molecules. For charged systems, its value depends on the choice of origin and molecular orientation. On the basis of vibration analysis, the statically thermodynamic functions: heat capacity (Cp), entropy (S), and enthalpy changes (H), Gibbs free energy for the title molecule were obtained from the theoretical thermodynamic parameters are listed in
In this work, the optimized geometry of the “nano fullerene interacting with nicotine” molecule has been determined by the method of density functional theory (DFT). On the basis of fully optimized ground-state structure, TDDFT//B3LYP/3-21G* calculations have been used to determine the low-lying excited states of “Nanofullerene interacting with Nicotine.” The hyperpolarizabilities indicate a possible use of these compounds in electro optical applications. The dipole moment of Nicotine is higher than the dipole moment of NFN. We have also discussed global and local reactivity descriptors sites for Nicotine molecules during electrophilic, nucleophilic and radical attack. The charge distribution of nitrogen atom is increasing trend in HF and B3LYP method. These values represent the qualitative description of reactivity of different atoms in the molecule. NBO analysis indicated that the higher second-order perturbation interaction (E2) and the electronic, chemical potential energy (µ) and the HOMO-LUMO gap in Nanofullerene interacting with Nicotine. This compound shows that the stability of the molecules increases because of interaction of nicotine.
S.Dheivamalar,L.Sugi,K.Ambigai, (2016) Density Functional Theory Study of Exohedral Carbon Atoms Effect on Electrophilicity of Nicotine: Comparative Analysis. Computational Chemistry,04,17-31. doi: 10.4236/cc.2016.41003