Electronic spectrum of thiophen and some deuterated thiophens

Lonardo, G. Di; Galloni, G.; Trombetti, A.; Zauli, C.

doi:10.1039/f29726802009

Cited by 41 publications

(22 citation statements)

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“…The gas phase UV absorption spectrum of thiophene in the lowest valence state ͑an A-band located at 5.5 eV͒ has a long vibrational progression with the lowest absorption at 41 595 cm −1 ͑5. [8][9][10] The gas phase UV absorption spectrum confirms the valence nature of the strong bands at 5.5 and 7.0 eV. [8][9][10] The gas phase UV absorption spectrum confirms the valence nature of the strong bands at 5.5 and 7.0 eV.…”

Section: A Resonance Raman Spectroscopic and Casscf Investigation Of mentioning

confidence: 61%

A resonance Raman spectroscopic and CASSCF investigation of the Franck–Condon region structural dynamics and conical intersections of thiophene

Zheng

Wang

et al. 2010

The Journal of Chemical Physics

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Resonance Raman spectra were acquired for thiophene in cyclohexane solution with 239.5 and 266 nm excitation wavelengths that were in resonance with ∼240 nm first intense absorption band. The spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion mostly along the reaction coordinates of six totally symmetry modes and three nontotally symmetry modes. The appearance of the nontotally symmetry modes, the C-S antisymmetry stretch +C-C=C bend mode ν(21)(B(2)) at 754 cm(-1) and the H(7)C(3)-C(4)H(8) twist ν(9)(A(2)) at 906 cm(-1), suggests the existence of two different types of vibronic-couplings or curve-crossings among the excited states in the Franck-Condon region. The electronic transition energies, the excited state structures, and the conical intersection points (1)B(1)/(1)A(1) and (1)B(2)/(1)A(1) between 2 (1)A(1) and 1 (1)B(2) or 1 (1)B(1) potential energy surfaces of thiophene were determined by using complete active space self-consistent field theory computations. These computational results were correlated with the Franck-Condon region structural dynamics of thiophene. The ring opening photodissociation reaction pathway through cleavage of one of the C-S bonds and via the conical intersection point (1)B(1)/(1)A(1) was revealed to be the predominant ultrafast reaction channel for thiophene in the lowest singlet excited state potential energy hypersurface, while the internal conversion pathway via the conical intersection point (1)B(2)/(1)A(1) was found to be the minor decay channel in the lowest singlet excited state potential energy hypersurface.

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Section: A Resonance Raman Spectroscopic and Casscf Investigation Of mentioning

confidence: 61%

A resonance Raman spectroscopic and CASSCF investigation of the Franck–Condon region structural dynamics and conical intersections of thiophene

Zheng

Wang

et al. 2010

The Journal of Chemical Physics

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“…The energies of the states identified in our EELS spectra are indicated with a. Previous results are from: calculations, Salzmann et al, 44 Kleinschmidt et al, Holland et al, 46 Nakatsuji et al 47 and Merchán et al 48 (both CASSCF and PT2 results are presented); experiments, Moodie et al, 51 Zauli et al, 52 Flicker et al, 43 van Veen et al, 53 Asmis, 13 Haberkern et al 42 and Veszpremi et al 54 The…”

Section: Scattering Modelmentioning

confidence: 84%

Shape and Core-Excited Resonances in Thiophene

et al. 2018

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We present a comprehensive study of resonance formation in electron collisions with thiophene. Detailed calculations have been performed using the ab initio R-matrix method. Absolute differential cross sections for electron impact excitation up to 18 eV and for two scattering angles, 90 and 135°, have been measured. Agreement between the calculated and measured experimental cross sections is very good. Three shape resonances previously described, two of π* character and one σ*, as well as a number of resonances of core-excited or mixed character are identified and characterized in the calculations. The measured cross sections provide experimental confirmation for a number of the core-excited resonances. The link between these resonances and prior DEA experiments is discussed.

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“…Finally, the ES of thiophene, which is one of the most important building block in organic electronic devices, were the subject of previous theoretical investigations, 33,[204][205][206]210,211 that unveiled a series of transitions that were not yet characterized in the available measurements. 186,190,[206][207][208][209][210] To the best of our knowledge, the present work is the first to report CC calculations obtained with (iterative) triples and therefore constitutes the most accurate estimates to date. Indeed, all the transitions listed in Tables 6 and S6 are characterized by a largely dominant single excitation character, with %T 1 above 90% except for the two 1 A 1 transitions for which %T 1 = 88% and 87%, respectively.…”

Section: Five-membered Ringsmentioning

confidence: 85%

A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Medium Size Molecules

Loos

Lipparini²,

Boggio‐Pasqua³

et al. 2019

Preprint

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Following our previous work focussing on compounds containing up to 3 non-hydrogen atoms [J. Chem. Theory Comput. 14 (2018) [4360][4361][4362][4363][4364][4365][4366][4367][4368][4369][4370][4371][4372][4373][4374][4375][4376][4377][4378][4379], we present here highly-accurate vertical transition energies obtained for 27 molecules encompassing 4, 5, and 6 non-hydrogen atoms: equation-of-motion coupled cluster theory up to the highest technically possible excitation order for these systems (CC3, EOM-CCSDT, and EOM-CCSDTQ), selected configuration interaction 1 arXiv:1912.04173v2 [physics.chem-ph] 31 Jan 2020 (SCI) calculations (with tens of millions of determinants in the reference space), as well as the multiconfigurational n-electron valence state perturbation theory (NEVPT2) method. All these approaches are applied in combination with diffuse-containing atomic basis sets. For all transitions, we report at least CC3/aug-cc-pVQZ vertical excitation energies as well as CC3/aug-cc-pVTZ oscillator strengths for each dipole-allowed transition. We show that CC3 almost systematically delivers transition energies in agreement with higher-level methods with a typical deviation of ±0.04 eV, except for transitions with a dominant double excitation character where the error is much larger. The present contribution gathers a large, diverse and accurate set of more than 200 highly-accurate transition energies for states of various natures (valence, Rydberg, singlet, triplet, n → π , π → π , . . . ). We use this series of theoretical best estimates to benchmark a series of popular methods for excited state calculations: CIS(D), ADC(2), CC2, STEOM-CCSD, EOM-CCSD, CCSDR(3), CCSDT-3, CC3, as well as NEVPT2. The results of these benchmarks are compared to the available literature data.Although these conclusions agree well with earlier studies, 69-71 they obviously only hold for single excitations, i.e., transitions with %T 1 in the 80-100% range. Therefore, we also recently proposed a set of 20 TBE for transitions exhibiting a significant double-excitation character (i.e., with %T 1 typically below 80%). 72 Unsurprisingly, our results clearly evidenced that the error in CC methods is intimately related to the %T 1 value. For example, for the ES with a significant yet not dominant double excitation character [such as the infamous A g ES of butadiene (%T 1 = 75%)] CC methods including triples deliver rather accurate estimates (MAE of 0.11 eV with CC3 and 0.06 eV with CCSDT), surprisingly outperforming second-order multi-reference schemes such as CASPT2 or the generally robust n-electron valence state perturbation theory (NEVPT2). In contrast, for ES with a dominant double excitation character, e.g., the low-lying (n, n) → (π , π ) excitation in nitrosomethane (%T 1 = 2%), single-reference methods (not including quadruples) have been found to be unsuitable with MAEs of 0.86 and 0.42 eV for CC3 and CCSDT, respectively. In this case, multiconfigurational methods are in practice required to obtain accurate results. 72 A clear limit of ...

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Electronic spectrum of thiophen and some deuterated thiophens

Cited by 41 publications

References 0 publications

A resonance Raman spectroscopic and CASSCF investigation of the Franck–Condon region structural dynamics and conical intersections of thiophene

A resonance Raman spectroscopic and CASSCF investigation of the Franck–Condon region structural dynamics and conical intersections of thiophene

Shape and Core-Excited Resonances in Thiophene

A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Medium Size Molecules

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