Electronic spectra and structure of nitroanilines

Millefiori, S.; Favini, G.; Millefiori, A.; Grasso, Domenico

doi:10.1016/0584-8539(77)80143-8

Cited by 81 publications

(84 citation statements)

References 12 publications

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“…Ultraviolet and X-ray photoelectron (pe) spectroscopy have proved that on H-bond formation the molecular orbital (MO) localized on the proton-acceptor atom is stabilized, while the MO localized on the proton-donor atom moves in the opposite direction (1). These results are supported by theoretical calculations (2).…”

Section: Introductionsupporting

confidence: 77%

Spectroscopic and electrochemical properties of intramolecularly hydrogen-bonded compounds. Ortho-hydroxyazobenzenes

Millefiori¹,

Millefiori²

1981

Can. J. Chem.

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SALVATORE MILLEFIORI and ARCANGELO MILLEFIORI. Can. J. Chem. 59,821 (1981) The gas-phase uv photoelectron spectra and the half-wave polarographic reduction potentials in acetonitrile solutions of a series of 2-hydroxy-5-methylazobenzene have been determined. The first three IP's and the E,,, values were linearly correlated withof ando constants, respectively. E,,, can also be linearly related to the energy ofthe lowest unoccupied molecular orbital. Effectsofthe intramolecular hydrogen bonding on the pe spectra and on the polarographic reduction of the title compounds were evaluated by comparing the experimental findings in 2-hydroxy-5-methylazobenzene, 2-methoxy-5-methylazobenzene, and phydroxyazobenzene. On H-bond formation, the antibonding combination of the two nitrogen lone-pairs, n-, and the oxygen lonepair is ionized at a slightly higher energy and at a lower energy, respectively, than in the non H-bonded compound. The first x-ionization band is slightly lowered in energy in the non H-bonded structure, probably owing to a normal substituent effect. These features are not maintained in the 4'-nitro derivative, where the band encompassing then -ionization remains at the same potential in both structures, while the first x band in the non H-bonded compound moves toward higher IP. Spectral differences between the bonded and nonbonded structures are the result of a balance of substituent effects, and of both hydrogen bond and orbital interactions. The solution electron affinity of the studied compounds increases on H-bond formation by an amount comparable with the experimental strength of the H-bonding. INDOIS-CI calculations are in qualitative agreement with the experimental results. [Traduit par le journal]

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Section: Introductionsupporting

confidence: 77%

Spectroscopic and electrochemical properties of intramolecularly hydrogen-bonded compounds. Ortho-hydroxyazobenzenes

Millefiori¹,

Millefiori²

1981

Can. J. Chem.

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“…The gas-phase dipole moment of the PNA molecule at the B2GP-PLYP/apvdz//PBE-D3/apvdz level is 7.07 D, which is ∼0.8 D above the experimental data for PNA in liquid benzene (6.29 D). 38 The average dipole moment of PNA in scCO 2 is presently estimated as 8.6 ± 2 D.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Probing Lewis Acid–Base Interactions with Born–Oppenheimer Molecular Dynamics: The Electronic Absorption Spectrum ofp-Nitroaniline in Supercritical CO₂

et al. 2015

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The structure and dynamics of p-nitroaniline (PNA) in supercritical CO2 (scCO2) at T = 315 K and ρ = 0.81 g cm(-3) are investigated by carrying out Born-Oppenheimer molecular dynamics, and the electronic absorption spectrum in scCO2 is determined by time dependent density functional theory. The structure of the PNA-scCO2 solution illustrates the role played by Lewis acid-base (LA-LB) interactions. In comparison with isolated PNA, the ν(N-O) symmetric and asymmetric stretching modes of PNA in scCO2 are red-shifted by -17 and -29 cm(-1), respectively. The maximum of the charge transfer (CT) absorption band of PNA in scSCO2 is at 3.9 eV, and the predicted red-shift of the π → π* electronic transition relative to the isolated gas-phase PNA molecule reproduces the experimental value of -0.35 eV. An analysis of the relationship between geometry distortions and excitation energies of PNA in scCO2 shows that the π → π* CT transition is very sensitive to changes of the N-O bond distance, strongly indicating a correlation between vibrational and electronic solvatochromism driven by LA-LB interactions. Despite the importance of LA-LB interactions to explain the solvation of PNA in scCO2, the red-shift of the CT band is mainly determined by electrostatic interactions.

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“…These conditions are largely fulfilled for mono-and di-substituted nitroaromatics, for which experimental gas-phase and solvent excitation energies are available. [37][38][39][40] In addition, we have recorded gas-phase and solvent spectra for the prototypical aromatic compounds pyridine (Py), benzofuran (Bf), coumarin (Cm) and nitrobenzene (NB).…”

Section: B Considerations For Excited Statesmentioning

confidence: 99%

Experimental Benchmark Data and Systematic Evaluation of Two a Posteriori, Polarizable-Continuum Corrections for Vertical Excitation Energies in Solution

Mewes¹,

You

Wormit³

et al. 2015

J. Phys. Chem. A

142

232

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We report the implementation and evaluation of a perturbative, density-based correction scheme for vertical excitation energies calculated in the framework of a polarizable continuum model (PCM). Because the proposed first-order correction terms depend solely on the zeroth-order excited-state density, a transfer of the approach to any configuration interaction-type excited-state method is straightforward. Employing the algebraic-diagrammatic construction (ADC) scheme of up to third order as well as time-dependent density-functional theory (TD-DFT), we demonstrate and evaluate the approach. For this purpose, we assembled a set of experimental benchmark data for solvatochromism in molecules (xBDSM) containing 44 gas-phase to solvent shifts for 17 molecules. These data are compared to solvent shifts calculated at the ADC(1), ADC(2), ADC(3/2), and TD-DFT/LRC-ωPBE levels of theory in combination with state-specific as well as linear-response type PCM-based correction schemes. Some unexpected trends and differences between TD-DFT, the levels of ADC, and variants of the PCM are observed and discussed. The most accurate combinations reproduce experimental solvent shifts resulting from the bulk electrostatic interaction with maximum errors in the order of 50 meV and a mean absolute deviation of 20-30 meV for the xBDSM set.

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Electronic spectra and structure of nitroanilines

Cited by 81 publications

References 12 publications

Spectroscopic and electrochemical properties of intramolecularly hydrogen-bonded compounds. Ortho-hydroxyazobenzenes

Spectroscopic and electrochemical properties of intramolecularly hydrogen-bonded compounds. Ortho-hydroxyazobenzenes

Probing Lewis Acid–Base Interactions with Born–Oppenheimer Molecular Dynamics: The Electronic Absorption Spectrum ofp-Nitroaniline in Supercritical CO₂

Experimental Benchmark Data and Systematic Evaluation of Two a Posteriori, Polarizable-Continuum Corrections for Vertical Excitation Energies in Solution

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Electronic spectra and structure of nitroanilines

Cited by 81 publications

References 12 publications

Spectroscopic and electrochemical properties of intramolecularly hydrogen-bonded compounds. Ortho-hydroxyazobenzenes

Spectroscopic and electrochemical properties of intramolecularly hydrogen-bonded compounds. Ortho-hydroxyazobenzenes

Probing Lewis Acid–Base Interactions with Born–Oppenheimer Molecular Dynamics: The Electronic Absorption Spectrum ofp-Nitroaniline in Supercritical CO2

Experimental Benchmark Data and Systematic Evaluation of Two a Posteriori, Polarizable-Continuum Corrections for Vertical Excitation Energies in Solution

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Probing Lewis Acid–Base Interactions with Born–Oppenheimer Molecular Dynamics: The Electronic Absorption Spectrum ofp-Nitroaniline in Supercritical CO₂