Search results for "Atomic electron transition"
showing 7 items of 57 documents
Theoretical characterization of the lowest-energy absorption band of pyrrole
2002
The lowest-energy band of the electronic spectrum of pyrrole has been studied with vibrational resolution by using multiconfigurational second-order perturbation theory (CASPT2) and its multistate extension (MS–CASPT2) in conjunction with large atomic natural orbital-type basis sets including Rydberg functions. The obtained results provide a consistent picture of the recorded spectrum in the energy region 5.5–6.5 eV and confirm that the bulk of the intensity of the band arises from a ππ∗ intravalence transition, in contradiction to recent theoretical claims. Computed band origins for the 3s,3p Rydberg electronic transitions are in agreement with the available experimental data, although new…
Spin transition in heptanuclear star-shaped iron(III)–antimony(V) NCS- and CN-bridged compounds
2009
Abstract The precursor [FeIII(L)Cl] (LH2 = N,N′-bis(2′-hydroxy-benzyliden)-1,6-diamino-3-azahexane) has been prepared and Mossbauer spectroscopy assigned a high-spin (S = 5/2) state at room temperature. The precursor is combined with the bridging units [SbV(X)6]− (X = CN−, NCS−) to yield star-shaped heptanuclear clusters [(LFeIII–X)6SbV]Cl5. The star-shaped compounds are in general high-spin systems at room temperature. On cooling to 20 K some of the iron(III) centers switch to the low-spin state as indicated by Mossbauer spectroscopy, i.e. multiple electronic transitions. While the cyano-bridged complex performs a multiple spin transition the thiocyanate-compound shows no significant popul…
Red- and Blue-Shifts in Oligo(1,4-phenyleneethynylene)s Having Terminal Donor−Acceptor Substitutions
2004
Four series of oligo(1,4-phenyleneethynylene)s (OPEs), 1−4 (a−d), each having a terminal dialkylamino group as their electron donor, were prepared by applying Sonogashira−Hagihara reactions and a protecting group strategy. To study the influence that the push−pull effect has on the long-wavelength absorption, three of the four series of OPEs contain terminal acceptor groups (CN, CHO, NO2). Extending the conjugation (increasing the number of repeat units, n) lowers the energy E(n) of the electron transition in the purely donor-substituted series 1a−4a (bathochromic shift). This effect is superimposed in the push−pull series 1−4 (b−d) by the effect of the intramolecular charge transfer (ICT),…
Konvergenz von Absorption und Fluoreszenz bei gekreuzt konjugierten Oligomeren aus Chalkon-Bausteinen
1999
The absorption and fluorescence spectra of two series of chalcone oligomers (1a–d) and (2a–d) are reported. Due to small or vanishing orbital coefficients (HMO calculation) within the cross-conjugated systems, the bathochromic shifts caused by the extension of the chains are modest. The effective conjugation lengths amount to 6 and 14 chalcone building blocks in the absorptions of the series 1 and 2. The convergence of the fluorescence bands is already reached in 1d and 2d with 4 and 8 enone units, respectively. Besides the uniform or alternate arrangement of the chalcone building blocks, the positions of the propoxy substituents show a considerable influence on the electronic transitions p…
The Nonanuclear [Mo(IV) {(CN)Fe(III)(3-ethoxy-saldptn)}8]Cl4 Complex Compound Exhibits Multiple Spin Transitions Observed by Mössbauer Spectroscopy
2004
The pentadentate ligand 3-EO-5LH2 = 3-ethoxy-saldptn = N,N′-bis(3-ethoxy-1-hydroxy-2-benzyliden)-1,7-diamino-4-azaheptane has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the corresponding 3-ethoxy-salicyaldehyde. 3-EO-5LH2 is a sterical extention to 5LH2. Its complexation with Fe(III) gave the high-spin (S = 5/2) complex of [Fe(III)(3-EO-5L)Cl]. This precursor was combined with [Mo(CN)8]4− and a blue nonanuclear cluster [Mo(IV){(CN)Fe(III)(3-EO-5L)}8]Cl4 resulted. This starshaped nonanuclear compound is a high-spin system at room temperature. On cooling to 10 K some of the eight iron(III) centers switched to the low-spin state as proven by Mossbauer spec…
Effect of N-substitution in multinuclear complexes allows interplay between magnetic states and multistability investigated by Mössbauer spectroscopy
2006
A series of pentadentate ligands N-X-5LH2 (X=H, Methyl, Benzyl)=N-X-saldptn (4-X-N,N′-bis(l-hydroxy-2-benzylidene)-1,7-diamino-4-azaheptane) has been prepared by a Schiff base condensation between 1,7-diamino-4-X-azaheptane and salicylaldehyde. Complexation with Fe(III) yields a series of high-spin (S=5/2) complexes of [FeIII(N-X-5L)Cl]. Such precursors were combined with [Mo(CN)8]4− and a series of blue nonanuclear cluster compounds [MoIV(CN)FeIII(N-X-5L)8]Cl4 resulted. Such star-shaped nonanuclear compounds are high-spin systems at room temperature. On cooling to 10K some of the iron(III) centers switched to the low-spin state as proven by Mossbauer spectra, i.e. multiple electronic trans…
Electronic Spectra of 2,2‘-Bithiophene and 2,2‘:5‘,2‘ ‘-Terthiophene Radical Cations: A Theoretical Analysis
2001
Analysis of the electronic spectra of 2,2‘-bithiophene and 2,2‘:5‘,2‘ ‘-terthiophene radical cations has been performed by using multiconfigurational second-order perturbation theory (CASPT2). Atomic natural orbital (ANO) type basis sets of split valence quality, including polarization functions on all heavy atoms, have been used. In agreement with experimental data, in the energy range below the lowest optically allowed transition of the respective neutral system, theoretical results predict two main absorption bands for both cations. The 22Au and 32Au states computed at 1.94 and 2.80 eV, respectively, are related to the corresponding band maxima recorded for bithiophene cation. The 12B1 s…