Journal ArticleDOI
Electronic Spectra of M(CO)6 (M = Cr, Mo, W) Revisited by a Relativistic TDDFT Approach
Angela Rosa,E. J. Baerends,S. J. A. van Gisbergen,E. van Lenthe,J.A. Groeneveld,J.G. Snijders +5 more
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In this paper, the authors showed that in all members of the series the lowest excited states in the spectra do not correspond to ligand field excitations, as has been accepted in the past, but instead correspond to charge transfer (CT) states.Abstract:
Relativistic time dependent density functional calculations have been performed on the excited states of the M(CO)6 (M = Cr, Mo, W) series. Our results, in agreement with previous density functional1 and ab initio2 calculations on Cr(CO)6, indicate that in all members of the series the lowest excited states in the spectra do not correspond to ligand field (LF) excitations, as has been accepted in the past. Instead they correspond to charge transfer (CT) states. The LF excitations are calculated at much higher energy than suggested by the original assignment by Beach and Gray3 and at different energy along the M(CO)6 series, being much higher in the heavier carbonyls than in Cr(CO)6. These results lead to a definitive reassessment of the role of the LF states in the photochemical dissociation of the metal−CO bonds in the M(CO)6 series, suggesting that the experimentally observed photodissociation of the M−CO bond upon irradiation into the lowest energy bands occurs in the heavier carbonyls, as it does in C...read more
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Chemistry with ADF
G. te Velde,F.M. Bickelhaupt,Evert Jan Baerends,C. Fonseca Guerra,S. J. A. van Gisbergen,J.G. Snijders,T. Ziegler +6 more
TL;DR: The “Activation‐strain TS interaction” (ATS) model of chemical reactivity is reviewed as a conceptual framework for understanding how activation barriers of various types of reaction mechanisms arise and how they may be controlled, for example, in organic chemistry or homogeneous catalysis.
Journal ArticleDOI
Revised Basis Sets for the LANL Effective Core Potentials.
TL;DR: A new contraction of the basis sets associated with the Hay-Wadt relativistic effective core potentials (RECPs) for the main group and transition metal atoms are suggested, more suitable for density functional theory investigations than the previous 'double-ζ' contractions based upon Hartree-Fock atomic results.
Journal ArticleDOI
Electronic structure and spectra of ruthenium diimine complexes by density functional theory and INDO/S. Comparison of the two methods
Serge I. Gorelsky,A. B. P. Lever +1 more
TL;DR: In this article, a comparison of these calculations with those carried out using Zerner's frequently used INDO/S method is described and discussed, and it is shown that for these species, and probably for all non-solvatochromic species in general, INDO-S is a good model reproducing very well the results of the computationally much more demanding but also more reliable TD-DFRT calculations.
Journal ArticleDOI
Theoretical Studies of the Ground and Excited Electronic States in Cyclometalated Phenylpyridine Ir(III) Complexes Using Density Functional Theory
TL;DR: In this article, the ground state and low-lying excited electronic states in the Ir(III) complex Ir(ppy)3, and in the related complexes Ir (ppy)2(acac) and Ir(ppy)-2(bza), are studied using density functional theory techniques.
Journal ArticleDOI
Molecular calculations of excitation energies and (hyper)polarizabilities with a statistical average of orbital model exchange-correlation potentials
TL;DR: In this paper, an approximate Kohn-Sham exchange-correlation potential νxcSAOP is developed with the method of statistical averaging of (model) orbital potentials and is applied to the calculation of excitation energies as well as of static and frequency-dependent multipole polarizabilities and hyperpolarizabilities within time-dependent density functional theory (TDDFT).
References
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Density-functional exchange-energy approximation with correct asymptotic behavior.
TL;DR: This work reports a gradient-corrected exchange-energy functional, containing only one parameter, that fits the exact Hartree-Fock exchange energies of a wide variety of atomic systems with remarkable accuracy, surpassing the performance of previous functionals containing two parameters or more.
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Density-functional approximation for the correlation energy of the inhomogeneous electron gas
TL;DR: Numerical results for atoms, positive ions, and surfaces are close to the exact correlation energies, with major improvements over the original LM approximation for the ions and surfaces.
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Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory
TL;DR: In this paper, the three-parameter Lee-Yang-Parr (B3LYP) functional was used to compute low-lying electronic excitations of N2, ethylene, formaldehyde, pyridine and porphin.
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An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules
TL;DR: In this paper, time-dependent density-functional (TDDFT) methods are applied within the adiabatic approximation to a series of molecules including C70, and they provide an efficient approach for treating frequency-dependent response properties and electronic excitation spectra of large molecules.
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Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold
TL;DR: In this paper, the performance of time-dependent density-functional response theory (TD-DFRT) for the calculation of high-lying bound electronic excitation energies of molecules is evaluated.