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Low-lying Electronic States (low-lying + electronic_states)
Selected AbstractsTheoretical studies on high-valent manganese porphyrins: Toward a deeper understanding of the energetics, electron distributions, and structural features of the reactive intermediates of enzymatic and synthetic manganese-catalyzed oxidative processesISRAEL JOURNAL OF CHEMISTRY, Issue 1 2000Abhik Ghosh We present here a relatively comprehensive theoretical study, based on nonlocal density functional theory calculations, of the energetics, electron distributions, and structural features of the low-lying electronic states of various high-valent intermediates of manganese porphyrins. Two classes of molecules have been examined: (a) compounds with the general formula [(P)MnX2]0 (P = porphyrin; X = F, Cl, PF6) and (b) high-valent manganese-oxo species. For [(P)Mn(PF6)2]0, the calculations reveal a number of nearly equienergetic quartet and sextet states as the lowest states, consistent with experimental results on a comparable species, [(TMP)Mn(ClO4)2]0 (TMP = tetramesitylporphyrin). In contrast, [(P)MnCl2]0 and [(P)MnF2]0 have a single well-defined S = 3/2 Mn(IV) ground state, again in agreement with experiment, with the three unpaired spins largely concentrated (>90%) on the manganese atom. Manganese(IV)-oxo porphyrins have an S = 3/2 ground state, with the three unpaired spins distributed approximately 2.3:0.7 between the manganese and oxygen atoms. The metal-to-oxygen spin delocalization, as measured by the oxygen spin population, for MnIV = O porphyrins is less than, but still qualitatively similar to, that in analogous iron(IV)-oxo intermediates, indicating that the MnIV = O bond is significantly weaker than the FeIV = O bond in an analogous molecule. Thus, the optimized metal,oxygen bond distances are 1.654 and 1.674 Å for (P)FeIV(O)(Py) and (P)MnIV(O)(Py), respectively (Py = pyridine). This is consistent with the experimental observation that MnIV = O stretching frequencies are over 10% lower than FeIV = O stretching frequencies for analogous compounds. For [(P)Mn(O)(PF6)]0, [(P)Mn(O)(Py)]+, and [(P)Mn(O)(F)]0, the ground states clearly correspond to a (dxy)2 Mn(V) configuration and the short Mn,O distances of 1.541, 1.546, and 1.561 Å for the three compounds, respectively, reflect the formal triple bond character of the Mn,O interaction. Interestingly, the corresponding Mn(IV)-oxo porphyrin cation radical states are calculated to be a few tenths of an electrovolt higher than the Mn(V) ground states, suggesting that the Mn(IV)-oxo porphyrin cation radicals are not likely to exist as ground-state species. [source] A combined ab initio and Franck-Condon factor simulation study on the photodetachment spectrum of ScO2,JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2009Edmond P. F. Lee Abstract Restricted-spin coupled-cluster single-double plus perturbative triple excitation {RCCSD(T)} potential energy functions (PEFs) of the 2B2 state of ScO2 and the 1A1 state of ScO2, were computed, employing the augmented correlation-consistent polarized-weighted core-valence quadruple-zeta (aug-cc-pwCVQZ) basis set for Sc and augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set for O, and with the outer core Sc 3s23p6 electrons being explicitly correlated. Franck-Condon factors, which include allowance for Duschinsky rotation and anharmonicity, were calculated using the computed RCCSD(T) PEFs, and were used to simulate the first photodetachment band of ScO2,. The simulated spectrum matches well with the corresponding experimental 355 nm photodetachment spectrum of Wu and Wang, J Phys Chem A 1998, 102, 9129, confirming the assignment of the photodetachment spectrum and the reliability of the RCCSD(T) PEFs used. Further calculations on low-lying electronic states of ScO2 gave adiabatic relative electronic energies (Te's) of, and vertical excitation energies (Tv's) to, the 2A1, 2B1, and 2A2 states of ScO2 (from the 2B2 state of ScO2), as well as electron affinities (EAs) and vertical detachment energies (VDEs) to these neutral states from the 1A1 state of ScO2,. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009 [source] Extensive theoretical studies on the low-lying electronic states of indium monochloride cation, InCl+JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 1 2005Wenli Zou Abstract The global potential energy curves for the 14 low-lying doublet and quartet ,-S states of InCl+ are calculated at the scalar relativistic MR-CISD+Q (multireference configuration interaction with single and double excitations, and Davidson's correction) level of theory. Spin-orbit coupling is accounted for via the state interaction approach with the full Breit,Pauli Hamiltonian, which leads to 30 , states. The computed spectroscopic constants of nine bound ,-S states and 17 bound , states are in good agreement with the available experimental data. The transition dipole moments and Franck,Condon factors of selected transitions are also calculated, from which the corresponding radiative lifetimes are derived. © 2004 Wiley Periodicals, Inc. J Comput Chem 26: 106,113, 2005 [source] Parallelization of multireference perturbation calculations with GAMESSJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2001Hiroaki Umeda Abstract The quasi-degenerate multireference second-order perturbation theory (MRMP2) routines in the GAMESS suite of program codes have been parallelized using a distributed data interface (DDI). Two typical kinds of molecules were chosen for examination of parallelization speedup using one to eight PCs gathered as a cluster and connected by Fast Ethernet. The first example, in which total energies of several low-lying electronic states have been obtained for niobium monohydride, give parallelization speedup of 7.15 when eight PCs were used as a cluster. The second example is the ground-state total energy for a medium sized molecule, 4a,4b,8a,9a-tetrahydro-pyridino[1,,2,-4,3]imidazo-lidino[1,5-a]pyridine. When distributed memory is employed, the parallelization speedup improves to 6.84 for the MRMP2 calculations when an eight-PC cluster is used. These results demonstrate that our efforts to achieve the parallelization of MRMP2 routines have been successful. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1243,1251, 2001 [source] Theoretical Study of the Reactions M++CH3F (M=Ge, As, Se, Sb)CHEMPHYSCHEM, Issue 9 2010Oscar Méndez Abstract CASSCF,MRMP2 calculations have been carried out to analyze the reactions of the methyl fluoride molecule with the atomic ions Ge+, As+, Se+ and Sb+. For these interactions, potential energy curves for the low-lying electronic states were calculated for different approaching modes of the fragments. Particularly, those channels leading to CH and CF oxidative addition products, H2FCMH+ and H3CMF+, respectively were explored, as well as the paths which evolve to the abstraction (MF++CH3) and the elimination (CH2M++HF) asymptotes. For the reaction Ge++CH3F the only favorable channel leads to fluorine abstraction by the ion. As+ and Sb+ can react with CH3F along pathways yielding stable addition products. However, a viable path joining the oxidative addition product H3CMF+ with the elimination asymptote CH2M++HF was found for the reaction of the fluorocarbon compound with As+. No favorable channels were detected for the interaction of fluoromethane with Se+. The results discussed herein allow rationalizing some of the experimental data found for these interactions through gas-phase mass spectrometry. [source] | ||||||||||