Journal ArticleDOI
``Troublesome'' Vibrations of Aromatic Molecules in Second-Order Möller-Plesset and Density Functional Theory Calculations: Infrared Spectra of Phenol and Phenol-OD Revisited
Danuta Michalska,Wiktor Zierkiewicz,Dariusz C. Bieńko,Walter Wojciechowski,Thérèse Zeegers-Huyskens +4 more
TLDR
In this article, the Fourier transform infrared (FT-IR) spectra of phenol and phenol-OD have been measured in carbon tetrachloride and cyclohexane solutions, in the frequency range 3700−400 cm-1, and the experimental integrated infrared intensities are reported.Abstract:
The infrared spectra of phenol and phenol-OD are thoroughly reinvestigated, to resolve the contradictory assignment of some vibrations. The harmonic frequencies, integrated IR intensities, and potential energy distribution (PED) have been calculated by the B3LYP method with the 6-311++G(df,pd) basis set. The Fourier transform infrared (FT-IR) spectra of phenol and phenol-OD have been measured in carbon tetrachloride and cyclohexane solutions, in the frequency range 3700−400 cm-1, and the experimental integrated infrared intensities are reported. On the basis of the results obtained, the detailed assignment of all the fundamental modes of Ph-OH and Ph-OD are presented. The study demonstrates that density functional B3LYP is clearly superior to the ab initio Hartree−Fock (HF) and second-order Moller−Plesset (MP2) methods in reliable prediction of the vibrational spectra of phenol. In particular, it is shown that scaling of the B3LYP-calculated frequencies of the CH and OH(OD) stretching vibrations by the sc...read more
Citations
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Journal ArticleDOI
The prediction of Raman spectra of platinum(II) anticancer drugs by density functional theory
TL;DR: Theoretical calculations of the Raman intensities and the simulated Raman spectra of platinum(II) complexes were presented in this article, where the clear-cut assignment of the Pt-ligand vibrations in the analyzed compounds has been made on the basis of the calculated potential energy distribution.
Journal ArticleDOI
FT-Raman and FT-IR spectra, vibrational assignments and density functional studies of 5-bromo-2-nitropyridine.
TL;DR: A detailed interpretations of the infrared and Raman spectra of 5-bromo-2-nitropyridine is reported on the basis of the calculated potential energy distribution (PED).
Journal ArticleDOI
Electronic structures, vibrational spectra, and revised assignment of aniline and its radical cation: Theoretical study
TL;DR: In this article, a detailed analysis of the aniline radical cation was performed by using the unrestricted density functional (UB3LYP) and second-order Moller-Plesset (UMP2) methods with the extended 6-311++G(df,pd) basis set.
Journal ArticleDOI
Direct detection of products from the pyrolysis of 2-phenethyl phenyl ether
Mark W. Jarvis,John W. Daily,Hans-Heinrich Carstensen,Anthony M. Dean,Shantanu Sharma,David C. Dayton,David J. Robichaud,Mark R. Nimlos +7 more
TL;DR: The pyrolysis of 2-phenethyl phenyl ether in a hyperthermal nozzle was studied to determine the importance of concerted and homolytic unimolecular decomposition pathways and suggest that the concerted retro-ene and Maccoll reactions are dominant at low temperatures (below 1000 °C), whereas the contribution of the C(6)H(5)C(2)H
Journal ArticleDOI
Ab initio characterization of the conical intersections involved in the photochemistry of phenol.
TL;DR: For benzene, a "channel three" radiationless decay mechanism associated with a prefulvenic conical intersection, CI(pref), was found to exist in phenol, and the OH torsion was finding to be by far the strongest coupling mode in each case.
References
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Journal ArticleDOI
Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
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Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
TL;DR: In this article, a contract Gaussian basis set (6•311G) was developed by optimizing exponents and coefficients at the Mo/ller-Plesset (MP) second-order level for the ground states of first-row atoms.
Journal ArticleDOI
Note on an Approximation Treatment for Many-Electron Systems
Chr. Møller,Milton S. Plesset +1 more
TL;DR: In this article, a perturbation theory for treating a system of n electrons in which the Hartree-Fock solution appears as the zero-order approximation was developed, and it was shown by this development that the first order correction for the energy and the charge density of the system is zero.
Journal ArticleDOI
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
TL;DR: In this paper, a modified basis set of supplementary diffuse s and p functions, multiple polarization functions (double and triple sets of d functions), and higher angular momentum polarization functions were defined for use with the 6.31G and 6.311G basis sets.