A theoretical study of the electronic spectra of pyridine and phosphabenzene

Lorentzon, Johan; Fülscher, Markus P.; Roos, Björn O.

doi:10.1007/s002140050113

Cited by 18 publications

(54 citation statements)

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“…Both PBE and PBEh predict the HOMO to be an n-orbital and the HOMO-1 and HOMO-2 to be π-orbitals. The n-π-π ordering is in agreement with high level wave-function and Green's function based calculations [113][114][115]122 and PES experiments. 97,[100][101][102] The PBE spectrum appears compressed with respect to experiment, yet the spacing between the n HOMO and the π HOMO-1 is too large.…”

Section: 100supporting

confidence: 81%

“…51,59 Another advantage of these systems is that they are well-characterized experimentally [93][94][95][96][97][98][99][100][101][102][103][104][105][106][107][108] and well-studied theoretically by high-level wavefunction and Green's function methods. 93,104,[109][110][111][112][113][114][115][116][117][118][119][120][121][122] We calculate the electronic structure of benzene, pyridine, and the diazines using: (i) semi-local and hybrid DFT (ii) G 0 W 0 , (iii) ev-scGW, (iv) scGW 0 , (v) scGW, and (vi) G 0 W 0 combined with the second-order exchange self-energy (2OX), as an attempt to go beyond the GW approximation. We compare our results to gas phase photoemission spectroscopy (PES) experiments and to reference calculations.…”

Section: Introductionmentioning

confidence: 99%

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Benchmark ofGWmethods for azabenzenes

et al. 2012

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Many-body perturbation theory in the GW approximation is a useful method for describing electronic properties associated with charged excitations. A hierarchy of GW methods exists, starting from non-self-consistent G 0 W 0 , through partial self-consistency in the eigenvalues (evscGW) and in the Green's function (scGW 0 ), to fully self-consistent GW (scGW). Here, we assess the performance of these methods for benzene, pyridine, and the diazines. The quasiparticle spectra are compared to photoemission spectroscopy (PES) experiments with respect to all measured particle removal energies and the ordering of the frontier orbitals. We find that the accuracy of the calculated spectra does not match the expectations based on their level of selfconsistency. In particular, for certain starting points G 0 W 0 and scGW 0 provide spectra in better agreement with the PES than scGW.

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Section: 100supporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Benchmark ofGWmethods for azabenzenes

et al. 2012

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“…To address this issue, in Table V we list the results for the four lowest vertical ionization energies obtained in the present work using different computational approaches, as well as those from previous studies. 35,40,42,46 As can be seen, the difficulty arises mainly from the large variation in the estimates for the nitrogen LP orbital, 7a 1 (σ N LP ), whose ionization energy depends strongly on the method used. At the highest level of theory (EOM-IP-CCSDT) employed in the present work, the 7a 1 (σ N LP ) 1 state is predicted to lie vertically below the 1a 2 (π) 1 state by 0.12 eV.…”

Section: 1mentioning

confidence: 99%

“…The CASPT2 results of Lorentzon et al 46 (unavailable for More information can be gained from the density difference plots comparing the total correlated electron density in the electronic ground state of neutral pyridine and its cationic states. Since total densities cannot be obtained in the ADC approach, they were evaluated using the CCD method for both the initial and final states (Figure 2).…”

Section: 1mentioning

confidence: 99%

“…Yang et al 45 used the direct static exchange approach, which takes cross-section effects into account, to investigate the photoelectron spectra of pyridine and some of its derivatives. Lorentzon et al 46 computed the lowest ionization potentials using second-order complete-active space perturbation theory (CASPT2). Walker et al 40 studied a large number of cationic states spanning the entire outervalence energy domain using multi-reference configuration interaction methods with singly and doubly excited configurations (MRD-CI).…”

Section: Introductionmentioning

confidence: 99%

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Ionization of pyridine: Interplay of orbital relaxation and electron correlation

Trofimov

Holland

Powis

et al. 2017

The Journal of Chemical Physics

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The valence shell ionization spectrum of pyridine was studied using the third-order algebraicdiagrammatic construction [ADC(3)] approximation scheme for the one-particle Green's function and the outer-valence Green's function (OVGF) method. The results were used to interpret angle resolved photoelectron spectra recorded with synchrotron radiation in the photon energy range of 17 -120 eV. The lowest four states of the pyridine radical cation, and CCSD (coupled-cluster singles and doubles) methods, and the harmonic vibrational frequencies were obtained at the MP2 level of theory for the lowest three cation states. The results were used to estimate the adiabatic 0-0 ionization energies, which were then compared to the available experimental and theoretical data. Photoelectron anisotropy parameters and photoionization partial cross-sections, derived from the experimental spectra, were compared to predictions obtained with the continuum multiple scattering approach.3

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Theoretical Calculations on Vibrational Frequencies and Absorption Spectra of S₁ and S₂ States of Pyridine

Hayashi

Shiu

et al. 2003

J Chinese Chemical Soc

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Three harmonic potential‐energy surfaces of 1A1, 1B1, and 1B2 singlet states of pyridine have been obtained by using ab initio method. Geometric properties and force fields of these states have been determined with the complete‐active‐space self‐consistent‐field (CASSCF) theoretical method. Vibrational frequencies of two excited states have been assigned on the basis of the potential energy distribution from normal mode analysis. The resulting properties are used to simulate the experimental absorption spectrum. From the spectral simulation the totally symmetric vibrations with large Huang‐Rhys factors have been identified as ν12 and ν6a modes in the 1B1 state; ν1 and ν12 modes in the 1B2 state, indicating that these modes have strong vibronic coupling between ground and excited states.

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A theoretical study of the electronic spectra of pyridine and phosphabenzene

Cited by 18 publications

References 0 publications

Benchmark ofGWmethods for azabenzenes

Benchmark ofGWmethods for azabenzenes

Ionization of pyridine: Interplay of orbital relaxation and electron correlation

Theoretical Calculations on Vibrational Frequencies and Absorption Spectra of S₁ and S₂ States of Pyridine

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A theoretical study of the electronic spectra of pyridine and phosphabenzene

Cited by 18 publications

References 0 publications

Benchmark ofGWmethods for azabenzenes

Benchmark ofGWmethods for azabenzenes

Ionization of pyridine: Interplay of orbital relaxation and electron correlation

Theoretical Calculations on Vibrational Frequencies and Absorption Spectra of S1 and S2 States of Pyridine

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Theoretical Calculations on Vibrational Frequencies and Absorption Spectra of S₁ and S₂ States of Pyridine