Basis set and correlation effects in the calculation of accurate gas phase dimerization energies of two M+2 to give M2+4 (M = S, Se)

Jenkins, H. Donald Brooke; Jitariu, Luminiţa C.; Krossing, Ingo; Passmore, Jack; Suontamo, Reijo

doi:10.1002/(sici)1096-987x(200002)21:3<218::aid-jcc5>3.0.co;2-b

Cited by 24 publications

(38 citation statements)

References 34 publications

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“…Using the hybrid HF-DFT levels of theory (B3LYP and B3PW91), low values of the dimerization energy were obtained even with reasonably small basis sets [e.g., 254 kJ/mol with B3PW91/6-311G(2df)]. To understand the wide range of calculated dimerization energies, we initiated a systematic study of basis set and correlation effects on the ionization potential of S 2 and the gas-phase dimerization of M 2 + to give M 4 2+ (M = S, Se), which is published elsewhere. , The problem was finally solved by employing the computationally very expensive CCSD(T)/cc-pV5Z level and also by the compound methods CBS-Q and Gaussian-2 which are reported to be the most accurate available within Gaussian 94 21 and employ MP4 and QCISD(T) as the highest levels of theory. From these calculations we concluded an average gas-phase dimerization energy of two S 2 + to give S 4 2+ of 258 ± 9 kJ/mol .…”

Section: Resultsmentioning

confidence: 99%

“…Consequently we initiated a systematic study of correlation and basis set effects of these reactions and showed that it is mandatory to use sophisticated methods and large basis sets to obtain thermochemically accurate values . From the analysis of our recent results, we concluded that one level of theory [e.g. CBS-Q or B3PW91/6-311+G(3df)//B3PW91/6-311+G*] described the system adequately at lowest computational cost.…”

Section: Introductionmentioning

confidence: 96%

“…We therefore undertook a new theoretical study of the M 2 + / M 4 2+ (M = S, Se) system, and found dimerization energies varying widely at different levels of theory. Consequently we initiated a systematic study of correlation and basis set effects of these reactions and showed that it is mandatory to use sophisticated methods and large basis sets to obtain thermochemically accurate values . From the analysis of our recent results, we concluded that one level of theory [e.g.…”

Section: Introductionmentioning

confidence: 99%

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Preference of np_π−np_π Bonding (n = 3, 4) over Purely σ-Bonded Species in M₄²⁺ (M = S, Se): Geometries, Bonding, and Energetics of Several M₄²⁺ Isomers^,

Krossing

Passmore

1999

Inorg. Chem.

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The dimerization energies of 2M 2 + to give M 4 2+ (M ) S, Se) were calculated as input into thermodynamic Born-Fajans-Haber cycle calculations to determine the relative stabilities of salts of these mono-and dications in the solid state. Computed dimerization energies showed a strong dependence on the basis set and correlated method utilized. Coupled cluster calculations, compound methods or hybrid HF/DFT methods employing large basis sets [CCSD(T)/cc-pV5Z, CBS-Q or B3PW91/6-311+G(3df)//B3PW91/6-311+G*] had to be used and showed an average dimerization energy of 258 (199) kJ/mol for sulfur (selenium). Square planar M 4 2+ (M ) S, Se) was fully optimized (B3LYP, B3PW91), and the calculated vibrational spectra of M 4 2+ were then compared to averaged experimental data to derive scaling factors. The structure, bonding, and energetics of seven starting geometries of the M 4 2+ (M ) S, Se) dication were computed (B3PW91), as well as AIM and NBO analyses of these species. The global minimum of the examined sulfur (selenium) species is the planar, 6π-aromatic D 4h symmetric square, which is 76 (106) and 155 (115) kJ/mol more stable than a D 2h symmetric π*-π*-bonded rectangular (S 2 + ) 2 [(Se 2 + ) 2 ] dimer and a classical, σ-bonded, butterfly-shaped isomer, respectively. This supports the thesis that the observed geometries of the homopolyatomic cations of groups 16 and 17 and related species maximize positive charge delocalization, resulting in thermodynamically stable np π -np π (n g 3) and π*-π* bonds. The formation of chain-like (Te 4 2+ ) n , polymeric Te 8 4+ , and square planar Te 4 2+ is accounted for semiquantitatively. The published, experimental enthalpy of formation of gasous S 4 + (1131 kJ/mol) was computationally shown to be due to a fragmentation of S 6 to give S 4 + and S 2 , confirming earlier photoionization studies. An enthalpy of formation of 972 kJ/mol was then established for the gaseous S 4 + cation, 159 kJ/mol lower than the erroneously assigned published experimental value.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

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Preference of np_π−np_π Bonding (n = 3, 4) over Purely σ-Bonded Species in M₄²⁺ (M = S, Se): Geometries, Bonding, and Energetics of Several M₄²⁺ Isomers^,

Krossing

Passmore

1999

Inorg. Chem.

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“…Although the lattice enthalpy of the A 2+ [(B − ) 2 ] salt O 4 2+ [A] 2 − is roughly three times larger than that of the A + B − salt, the formation of two units of solid O 2 + [AsF 6 ] − is favored by 615 kJ mol −1 over O 4 2+ [AsF 6 ] 2 − (Scheme ) 168. Owing to the larger S–S separation in S 4 2+ (201 pm) and the stronger SS single bonds172 Δ H diss (g) is exothermic173 by only 258 kJ mol −1 . Therefore in the solid state the higher lattice enthalpy contribution of the A 2+ [(B − ) 2 ] salt dominates and the formation of S 4 2+ [(AsF 6 − ) 2 ] is favored by 238 kJ mol −1 .…”

Section: A Rationalization Of the Special Properties Of Salts Of Wmentioning

confidence: 99%

Noncoordinating Anions—Fact or Fiction? A Survey of Likely Candidates

2004

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Is there anything resembling a truly noncoordinating anion? Would it not be great to be able to prepare any crazy, beautiful, or simply useful cationic species that one has in mind, or has detected by mass spectroscopy? In condensed phases the target cation has to be partnered with a suitable counteranion. This is the moment when difficulties arise and many wonderful ideas end in the sink owing to coordination or decomposition of the anion. However, maybe these counteranion problems can be overcome by one of the new weakly coordinating anions (WCAs). Herein is an overview on the available candidates in the quest for the least coordinating anion and a summary of new applications, available starting materials, and general strategies to introduce a WCA into a system. Some of the unusual properties of WCA salts such as high solubility in low dielectric media, pseudo gas-phase conditions in condensed phases, and the stabilization of weakly bound and low-charged complexes are rationalized on thermodynamic grounds. Limits of the WCAs, that is, anion coordination and decomposition, are shown and a quantum chemical analysis of all types of WCAs is presented which allows the choice of a particular WCA to be based on quantitative data from a wide range of different anions.

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“…Wegen der größeren S‐S‐Abstände in S 4 2+ (201 pm) und der stärkeren S‐S‐Einfachbindungen172 ist Δ H diss. (g) in diesem Kreisprozess nur zu etwa 258 kJ mol −1 exotherm 173. Daher überwiegt im Festkörper die höhere Gitterenergie des A 2+ (B − ) 2 ‐Salzes, und die Bildung von S 4 2+ ([AsF 6 ] − ) 2 ist um etwa 238 kJ mol −1 begünstigt.…”

Section: Thermodynamische Betrachtung Der Besonderen Eigenschaftenunclassified

Nichtkoordinierende Anionen – Traum oder Wirklichkeit? Eine Übersicht zu möglichen Kandidaten

2004

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Gibt es so etwas wie ein wirklich nichtkoordinierendes Anion? Wäre es nicht großartig, jede verrückte, schöne oder einfach nur nützliche kationische Spezies herstellen zu können, sei es, weil sie einen gerade interessiert oder weil man sie vielleicht schon einmal im Massenspektrum entdeckt hat? Um dieses Ziel in kondensierter Phase zu erreichen, müssen die Zielkationen mit einem geeigneten Gegenion versehen werden – dies ist der Moment, bei dem häufig Schwierigkeiten auftreten und viele gute Ideen wegen einer Koordination oder Zersetzung des Anions im Abguss enden. Zur Lösung des Problems bietet sich womöglich eines der neuen schwach koordinierenden Anionen (WCAs) an, die Gegenstand dieses Aufsatzes sind. Vorgestellt werden neue Entwicklungen, Anwendungen, Ausgangsmaterialien und allgemeine Strategien zur Einführung von WCAs in ein System. Einige der ungewöhnlichen Eigenschaften von WCA‐Salzen wie hohe Löslichkeit in unpolaren Medien, Pseudo‐Gasphasenbedingungen in der kondensierten Phase oder die Stabilisierung von schwach gebundenen und niedrig geladenen Komplexen werden anhand thermodynamischer Betrachtungen plausibel gemacht. Die Grenzen bei der Verwendung von WCAs – durch Koordination und Zersetzung – werden aufgezeigt, und eine quantenchemische Analyse der WCA‐Typen wird vorgestellt. Dies ermöglicht es, die Entscheidung für ein spezielles WCA auf der Basis von harten quantitativen Daten aus einer Vielzahl von Anionen zu gründen.

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Basis set and correlation effects in the calculation of accurate gas phase dimerization energies of two M+2 to give M2+4 (M = S, Se)

Cited by 24 publications

References 34 publications

Preference of np_π−np_π Bonding (n = 3, 4) over Purely σ-Bonded Species in M₄²⁺ (M = S, Se): Geometries, Bonding, and Energetics of Several M₄²⁺ Isomers^,

Preference of np_π−np_π Bonding (n = 3, 4) over Purely σ-Bonded Species in M₄²⁺ (M = S, Se): Geometries, Bonding, and Energetics of Several M₄²⁺ Isomers^,

Noncoordinating Anions—Fact or Fiction? A Survey of Likely Candidates

Nichtkoordinierende Anionen – Traum oder Wirklichkeit? Eine Übersicht zu möglichen Kandidaten

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Basis set and correlation effects in the calculation of accurate gas phase dimerization energies of two M+2 to give M2+4 (M = S, Se)

Cited by 24 publications

References 34 publications

Preference of npπ−npπ Bonding (n = 3, 4) over Purely σ-Bonded Species in M42+ (M = S, Se): Geometries, Bonding, and Energetics of Several M42+ Isomers,

Preference of npπ−npπ Bonding (n = 3, 4) over Purely σ-Bonded Species in M42+ (M = S, Se): Geometries, Bonding, and Energetics of Several M42+ Isomers,

Noncoordinating Anions—Fact or Fiction? A Survey of Likely Candidates

Nichtkoordinierende Anionen – Traum oder Wirklichkeit? Eine Übersicht zu möglichen Kandidaten

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Product

Resources

About

Preference of np_π−np_π Bonding (n = 3, 4) over Purely σ-Bonded Species in M₄²⁺ (M = S, Se): Geometries, Bonding, and Energetics of Several M₄²⁺ Isomers^,

Preference of np_π−np_π Bonding (n = 3, 4) over Purely σ-Bonded Species in M₄²⁺ (M = S, Se): Geometries, Bonding, and Energetics of Several M₄²⁺ Isomers^,