Resonance Two-Photon Ionization Spectroscopy of the Aniline Dimer

Yeh, Jing-Yue; Shen, T. L.; Nocera, and D. G.; Leroi, G. E.; Suzuka, Iwao; Ozawa, A.; Namuta, Y.

doi:10.1021/jp952415q

Cited by 32 publications

(24 citation statements)

References 26 publications

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“…30,31,60 These two features were attributed to different isomers, and the presence of at least two different isomers was confirmed in subsequent two-color hole-burning spectra. 61 Similar studies using R2PI and zero-kinetic energy (ZEKE) spectroscopy have been reported on substituted benzene dimers, including dimers of fluorobenzene, [62][63][64][65][66][67][68][69] chlorobenzene, 58,70 phenol, aniline, [71][72][73][74] and others. 39,75 Building upon the seminal studies of Bernstein and others, Musgrave and Wright recently reported R2PI spectra of mass-selected toluene homoclusters (Tol) n up to n = 8, 60 and parafluorotoluene clusters (pfTol) n up to n = 11.…”

Section: Introductionsupporting

confidence: 53%

On π-stacking, C-H/π, and halogen bonding interactions in halobenzene clusters: Resonant two-photon ionization studies of chlorobenzene

Muzangwa

Nyambo

Uhler

et al. 2012

The Journal of Chemical Physics

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Noncovalent interactions such as hydrogen bonding, π-π stacking, CH/π interactions, and halogen bonding play crucial roles in a broad spectrum of chemical and biochemical processes, and can exist in cooperation or competition. Here we report studies of the homoclusters of chlorobenzene, a prototypical system where π-π stacking, CH/π interactions, and halogen bonding interactions may all be present. The electronic spectra of chlorobenzene monomer and clusters (Clbz)(n) with n = 1-4 were obtained using resonant 2-photon ionization in the origin region of the S(0)-S(1) (ππ*) state of the monomer. The cluster spectra show in all cases a broad spectrum whose center is redshifted from the monomer absorption. Electronic structure calculations aid in showing that the spectral broadening arises in large part from inhomogeneous sources, including the presence of multiple isomers and Franck-Condon (FC) activity associated with geometrical changes induced by electronic excitation. Calculations at the M06-2x/aug-cc-pVDZ level find in total five minimum energy structures for the dimer, four π-stacked structures, and one T-shaped, and six representative minimum energy structures were found for the trimer. The calculated time-dependent density functional theory spectra using range-separated and meta-GGA hybrid functionals show that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectra, and the calculated absorptions are redshifted with respect to the monomer transition, in agreement with experiment. Due to the significant geometry change in the electronic transition, where for the dimer a transition from a parallel displaced to sandwich structure occurs with a reduced separation of the two monomers, significant FC activity is predicted in low frequency intermolecular modes.

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Section: Introductionsupporting

confidence: 53%

On π-stacking, C-H/π, and halogen bonding interactions in halobenzene clusters: Resonant two-photon ionization studies of chlorobenzene

Muzangwa

Nyambo

Uhler

et al. 2012

The Journal of Chemical Physics

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“…The obtained results are consistent with recent spectroscopic studies in terms of binding energy and geometrical conformation of the dimer. 39,40 Since the 2:1 molar ratio is observed for aniline in the experimental part of the study, the dimer of two guest molecules is introduced into the cavity of γ-CD for a more proper comparison ( Figure 6). The various locations and the complexation energy (E comp ) for the lowest energy orientations are calculated as…”

Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 99%

Selective and Efficient Removal of Volatile Organic Compounds by Channel-type Gamma-Cyclodextrin Assembly through Inclusion Complexation

Çelebioğlu

İpek

Durgun

et al. 2017

Ind. Eng. Chem. Res.

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Cyclodextrins (CD), produced from enzymatic degradation of starch, are a form of biorenewable cyclic oligosaccharide which has an outstanding capability to form inclusion complexes with a variety of molecules including pollutants due to their toroid-shaped molecular structure. In this study, by a simple reprecipitation method, we obtained "channel-type" packing from γ-CD where CD molecules are stacked on top of each other to form long cylindrical channels. The γ-CD "channel-type" crystals have shown very effective removal of organic volatile compounds (VOCs; aniline and toluene) from the surroundings, whereas cage-type γ-CD could not entrap VOCs from the same environment. Encapsulation capability of channel-type γ-CD is at a ∼2:1 and ∼1:1 molar ratio for aniline/CD and toluene/CD, respectively. Thus, channel-type γ-CD crystals have shown higher removal efficiency for aniline compared to toluene. Channel-type γ-CD is also able to remove aniline selectively from surroundings. Additionally, computational modeling studies suggested that single γ-CD cavity can host two molecules of aniline or toluene for the complexation, yet, aniline is more insistent to make a complex with the γ-CD cavity when compared to toluene. We show that channel-type γ-CD can remove VOCs molecules (aniline and toluene) as efficiently as activated carbon. Hence, being a starchbased biorenewable cyclic oligosaccharide in the form of white powder, the use of "channel-type" γ-CD crystals could be a competitive alternative to activated carbon as an adsorbent for the VOC removal/filtering.

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“…The aniline dimer and trimer structures were investigated in the ground and excited states previously. [21][22][23] The N-H site in the amino group of aniline can form a hydrogen bond with a lone pair of the nitrogen atom of another aniline or with the p electrons of its benzene ring. The neutral structure of the aniline dimer shows relative stability for both conformers: the stacked complexes with a N-p type hydrogen bond and N-HÁ Á ÁN bonding with head-to-tail orientation.…”

Section: Introductionmentioning

confidence: 99%

Photodissociation of aniline N–H bonds in clusters of different nature

Poterya

Nachtigallová

Lengyel

et al. 2015

Phys. Chem. Chem. Phys.

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We investigated the solvent effects on the N-H bond photodisociation dynamics of aniline (PhNH2) in clusters using velocity map imaging (VMI). The VMI experiment was accompanied by a time-of-flight mass spectrometry after electron ionization to reveal the cluster nature. The H-fragment images were recorded at 243 nm in various expansion regimes corresponding to different species: isolated molecules; small (PhNH2)N, N ≤ 3, clusters; larger (PhNH2)N, N ≥ 10; small mixed PhNH2·(H2O)N, N ≤ 10, clusters; and individual PhNH2 molecules deposited on large (H2O)N, N̄ = 430. The H-fragment kinetic energy distributions exhibit fast fragments around 0.8 eV (A) assigned previously to a direct dissociation along a repulsive πσ* state potential, and slow statistical fragments peaking near 0.2 eV (B). In the aniline clusters the contribution of fast fragments (A) decreases relatively to (B) with increasing cluster size. A similar effect is observed when aniline is solvated with water molecules. The experimental data are interpreted with ab initio calculations. Cluster structures were calculated with both N-H bonds of an aniline molecule participating in hydrogen bonding, as well as the ones with free N-H bonds. The latter ones yield preferentially the fast fragments as the isolated molecule. For N-H engaged in hydrogen bonding a barrier increased along the N-H coordinate on the dissociative πσ* state potential surface, and also the energy of πσ*/S0 conical intersection increased. Thus the fast dissociation channel was closed stabilizing the molecule in clusters. The population could be funnelled through other conical intersections into the hot ground state which decayed statistically, yielding the slow H-fragments.

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Resonance Two-Photon Ionization Spectroscopy of the Aniline Dimer

Cited by 32 publications

References 26 publications

On π-stacking, C-H/π, and halogen bonding interactions in halobenzene clusters: Resonant two-photon ionization studies of chlorobenzene

On π-stacking, C-H/π, and halogen bonding interactions in halobenzene clusters: Resonant two-photon ionization studies of chlorobenzene

Selective and Efficient Removal of Volatile Organic Compounds by Channel-type Gamma-Cyclodextrin Assembly through Inclusion Complexation

Photodissociation of aniline N–H bonds in clusters of different nature

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