• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1274-1274
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• 2001

An anharmonicity is a fundamental quantity shaping the potential for stretching OH vibration in phenol and its derivatives. The phenomenon is examined both by experimental and theoretical methods. FT-IR and NIR spectra of series of phenols derivatives were measured in the range of fundamental and first two Overtones of $_{s}(OH)$ Vibrations in $CCl_4$ solutions. The electronic influence of substituents on the analyzed frequencies is discussed and correlated with $pK_{a}$ parameters. Ab initio MP2/6-31G(d,p) and B3LYP/6-31G(g,p) calculations of the potential for proton movement in OH group were performed. Equilibrium structures were also determined. The frequencies of fundamental and overtones were calculated by Numerov-type procedure. The results of calculations are compared with the experimental data. The best linear correlations were obtained for the results of MP2/6-31G(d,p) calculations. It was shown that some structural parameters are especially sensitive on substitution. The linear correlations were found between those parameters and spectroscopic data. The results of calculation are compared with available crystallographic data.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3249-3252
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• 2013

We have explored the potential energy surface for the isomerization of the aniline (AN) radical cation to the 2-, 3-, and 4-methylpyridine (picoline, MP) radical cations using G3 model calculations. The isomerization may occur through the 1H-azepine (7-aza-cycloheptatriene) radical cation. A quantitative kinetic analysis has been performed using the Rice-Ramsperger-Kassel-Marcus theory, based on the potential energy surface. The result shows that isomerization between $AN^{+\bullet}$ and each $MP^{+\bullet}$ hardly occurs before their dissociations.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3718-3722
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• 2010

Theoretical investigations are carried out on the title reaction by means of ab-initio and DFT methods. The optimized geometries, frequencies and minimum energy path are obtained at UB3LYP/6-311G(d,p) level. Single point energy calculations are performed at MP2 and MP4 levels of theory. Energetics are further refined by calculating the energy of the species with a modified Gaussian-2 method, G2M(CC,MP2). The rate constant of the reaction is calculated using Canonical Transition State Theory (CTST) utilizing the ab-initio data obtained during the present study and is found to be $5.47{\times}10^{-12}\;cm^3\;molecule^{-1}s^{-1}$ at 298 K and 1 atm.

• Bulletin of the Korean Chemical Society
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• v.25 no.2
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• pp.260-262
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• 2004

In agreement with the results of previous MP2 calculations by Sauers, B3LYP, CASSCF, and CASPT2 calculations on the parent 2-carbena-1,3-dioxolane show that it fragments to ethylene plus $CO_2$ by a concerted pathway with only a small energy barrier. Not only is fragmentation via stepwise C-O bond cleavage computed to be a much higher energy pathway, but the singlet diradical that would be an intermediate along such a reaction path is not even computed to be a local minimum on the potential energy surface.

• Journal of the Korean Chemical Society
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• v.50 no.3
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• pp.203-207
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• 2006

Ab initio calculations of the structure and the binding energies of K+(C2H5OH)n, (n=1~5) complexes were carried out with MP2/ full gen 6d and MP2/ 6-311G** methods. The stable structures of the complexes with n=2 to 5 were linear, trigonal, tetrahedral and trigonal bipyramid respectively. The binding energies of complexes were increased with the number of ligands, but the incremental binding energies were decreased. These results agreed well with the results of K+ complexes with other solvents.

• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1955-1961
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• 2012

In this work, the reactions of carbamyl and thiocarbamyl halides with $NH_3$ were studied in the gas phase at the MP2(FC)/6-31+G(d) level of theory. Single point calculations were performed at the QCISD/6-311+G(3df,2p) to refine the energetics. The reaction mechanisms were also studied in aqueous solution. The structures were fully optimized at the CPCM-MP2(FC)/6-31+G(d) and refined by a single point CPCM-QCISD/6-311+G(3df,2p) calculations. The reaction mechanisms for the title compounds were compared with those for the acetyl and thioacetyl halides. The lower reactivity of carbamyl (and thiocarbamyl) groups was explained by comparing the C=O and C=S ${\pi}$-bond strengths as well as resonance contributions in the ground state.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.882-890
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• 2000

Ab initio calculations are carried out on protonation equilibria of 5-memberedheteroaromatic aldehydes (5MHAs;heteroatom Y = NH, O, PH,and S and substituentZ = NH2, OCH3, SCH3, CH3, H, Cl, CHO, CN,NO2) at the $MP2}6-31G*$ level. Naturalbond orbital (NBO) analyses show that the optimal localized natural Lewis structures of the protonated aldehydes,(P), are ortho (C3) protonated (for Y = O, PH and S) and N-pro-tonated (for Y = NH) forms in contrast to the standard structural Lewis formula for aldehydes, (R). The delo-calizability of ${\pilone}-pairon$ the heteroatom $(n{\pi}(Y))$ is in the order Y = NH > O > S > PH. The transmission efficiency of (Z) substituent effects to the carbonyl moiety run parallel to the delocalizability of $n{\pi}(Y)$ for R,but is dominantly influenced by the cationic charge on $C{\alpha}(C{\alpha}+)$ for P, which is in the reverse order of thede-localizability of $n{\pi}(Y).$ The Hammett ${\rho}values$ for variation of Z in the protonation are determined by the dif-ference in the transmission efficiencies between Pand R stateat simple interpretation of their magnitude is not warranted. However,the magnitude of the gas-phase ${\rho}z+$ values decreases as the level ofcomputation is raised from RHF/3-21G* to RHF/6-31G* and to $MP2}6-31G*$ but increases again at the MP4SDQ/6-31G* level. Further decrease occurs when solvent effect (water) is accounted for by the SCRF method. Comparison of the SCRF ${\rho}z+values$ with those determined in the aqueous acid solution for Y = S and CHCH shows inadequacy of accounting for the solvent effects on the ${\rho}values$ by a continuum model. It is noteworthy that semiempirical calculations, especially theAM1 method, give even lower magnitude of the gas-phase ${\rho}values.

• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1267-1271
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• 2002

The conformation dependences of basis set superposition errors (BSSE) for 1,2-difluoroethane (DFE) and 1,2-dimethoxyethane (DME) molecules have been estimated using counterpoise method at the Moller-Plesset second order perturbation (MP2) level of theory with various basis sets, assuming that all BSSE dependences on conformations are due to the change in CC bond. The BSSE on the energy differences between eclipsed and gauche forms of DFE are in the range of 0.2-1.2 kcal/mol and those between local minima, gauche and anti forms, are less than 0.2 kcal/mol. For the larger DME molecule, the BSSE differences between local minima are still less than 0.4 kcal/mol, but may not be ignored compared to the energy differences of 0.2-3.0 kcal/mol between conformers.

• Bulletin of the Korean Chemical Society
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• v.18 no.1
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• pp.27-32
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• 1997

The geometries and energies of the isomers in alkyne complexes MCl(PH3)2(η2-C2H2), M=Rh and Ir, are theoretically investigated using ab initio methods at the Hartree-Fock and up to MP4 level of theory and relativistic effective core potentials for Rh and Ir metals. The optimized structures of Rh complexes, 1-3 at MP2/ECP1 level are in good agreement with the related experimental data. The binding energies of C2H2 to d8-metal fragments are computed to be ∼55 kcal/mol. The vinylidene complexes for Rh and Ir metals are calculated to be much lower in energy than the alkyne complexes. The alkyne-vinylidene rearrangement is possible to proceed exothermically through the intermediate hydrido-alkynyl complexes, 2 or 9. Detailed comparison is given about the geometries and relative energies on Rh and Ir isomers at the various level ab initio calculations with orbital analysis.

• Bulletin of the Korean Chemical Society
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• v.19 no.5
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• pp.557-560
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• 1998

The structures and energies for the intramolecular rearrangement in $d^8-MCl(PH_3)_2$(HC≡CPh), M=Rh and Ir, complexes were studied by ab initio method at the Hartree-Fock and MP2 levels of theory. Three transition states in two pathways were optimized and characterized by frequency calculations. The activation energies for the process of π-type complex 1 to hydrido-alkynyl 2 have been computed to be relatively low 6.97 and 21.33 kcal/mol at MP2 level for Rh and Ir metals, respectively. However, the activation energies for a 1,2-hydrogen shift via t.s.3 have been computed to be high 50.83 and 60.05 kcal/mol for Rh and Ir metals.