Proton transfer or hemibonding? The structure and stability of radical cation clusters

Do, Hainam; Besley, Nicholas A.

doi:10.1039/c3cp52922c

Cited by 42 publications

(40 citation statements)

References 39 publications

(133 reference statements)

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“…Essentially the same conclusion has also been reported by Do and Besley for (H 2 S) n + ( n = 2–4) by searching the isomers through the Basin–Hopping approach and subsequent structural optimization at the CCSD(T)/aug-cc-pVDZ level of theory. 12 In our computations, the UMP2 method yields an S 2 value with a small average deviation of 0.021 compared to the exact value (0.75), and the spin contamination is not serious. Furthermore, the simulated spectra calculated using the UMP2 method show better agreement with the experimental spectra than those calculated using UB2PLYPD (details are shown in Tables SI-2 and SI-3 in ESI†).…”

Section: Resultsmentioning

confidence: 55%

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Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H₂S)_n⁺ clusters in the gas phase

Wang

Fujii

2017

Chem. Sci.

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Section: Resultsmentioning

confidence: 55%

“…The experimental observations are consistent with the favorability of the hemi-bonded ion core over the proton-transferred ion core in (H 2 S) n + as predicted by recent theoretical calculations. 12 …”

Section: Introductionmentioning

confidence: 99%

Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H₂S)_n⁺ clusters in the gas phase

Wang

Fujii

2017

Chem. Sci.

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“…These clusters can undergo a proton transfer reaction, yielding a cationic molecule and a radical; the resulting monomers might form an isomeric complex [3]. Mainly cationic clusters of chalcogen or halogen atoms have been the subject of such studies [4][5][6][7][8][9][10], while dimers formed by pnicogen atoms have been less reported. The [XH 3 -XH 3 ] Á?…”

Section: Introductionmentioning

confidence: 98%

A computational study on [(PH2X)2]·+ homodimers involving intermolecular two-center three-electron bonds

2015

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A computational study at CCSD(T) theoretical level has been carried out on radical cation [(PH 2 X) 2 ] Á? homodimers. Four stable minima configurations have been found for seven substituted phosphine derivatives, X = H, CH 3 , CCH, NC, OH, F and Cl. The most stable minimum presents an intermolecular two-center three-electron PÁÁÁP bond except for X = CCH. The other three minima correspond to an alternative PÁÁÁP pnicogen bonded complex, to a PÁÁÁX contact and the last one to the complex resulting from a proton transfer, PH 3 X ? :PHX Á . The complexes obtained have been compared with those of the corresponding neutral ones, (PH 2 X) 2 , and the analogous protonated ones, PH 3 X ? :PH 2 X, recently described in the literature. The spin and charge densities of the complexes have been examined. The electronic characteristics of the complexes have been analyzed with the NBO and AIM methods. The results obtained for the spin density, charge and NBO are coherent for all the complexes.

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“…The structures corresponding to the global minimum for the (H 2 O) 7 and (H 2 O) 3 (CH 3 OH) 4 clusters are illustrated in Figure 7, which shows the structures to be similar with the methyl groups of methanol occupying the sites of free hydrogens in the (H 2 O) 7 cluster. Other studies have considered radical cation clusters including water [258,259] with a combination of DFT and MP2 methods. Low-energy structures that correspond to different characteristic structural motifs can be identified.…”

Section: Basin Hopping For Low-lying Minima Of Clustersmentioning

confidence: 99%

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

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2,698

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A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and openshell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr 2 dimer, exploring zeolitecatalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.Keywords quantum chemistry, software, electronic structure theory, density functional theory, electron correlation, computational modelling, Q-Chem Disciplines Chemistry CommentsThis article is from Molecular Physics: An International Journal at the Interface Between Chemistry and Physics 113 (2015): 184, doi:10.1080/00268976.2014. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. Authors 185A summary of the technical advances that are incorporated in the fourth major release of the Q-CHEM quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly corre...

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Proton transfer or hemibonding? The structure and stability of radical cation clusters

Abstract: The basin hopping search algorithm in conjunction with second-order Møller-Plesset perturbation theory is used to determine the lowest energy structures of the radical cation clusters (NH 3 ) n

Cited by 42 publications

References 39 publications

Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H₂S)_n⁺ clusters in the gas phase

Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H₂S)_n⁺ clusters in the gas phase

A computational study on [(PH2X)2]·+ homodimers involving intermolecular two-center three-electron bonds

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

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Proton transfer or hemibonding? The structure and stability of radical cation clusters

Abstract: The basin hopping search algorithm in conjunction with second-order Møller-Plesset perturbation theory is used to determine the lowest energy structures of the radical cation clusters (NH 3 ) n

Cited by 42 publications

References 39 publications

Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H2S)n+ clusters in the gas phase

Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H2S)n+ clusters in the gas phase

A computational study on [(PH2X)2]·+ homodimers involving intermolecular two-center three-electron bonds

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Contact Info

Product

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Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H₂S)_n⁺ clusters in the gas phase

Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H₂S)_n⁺ clusters in the gas phase