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Title: Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes

Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔE{sub AB}. Counterpoise-corrected interaction energies ΔE{sub AB} are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A−B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2].more » (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [E{sub MP2/CBS}] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔE{sub CC-MP}, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔE{sub AB} with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting deviation from the computational reference of less than 1 kcal mol{sup −1}. The zero-point vibrational energy corrected estimates Δ(E{sub AB}+ZPE), obtained with the three functionals and the 6-31G(d) and N07T basis sets, are compared with experimental D{sub 0} measures, when available. In particular, this comparison is finally extended to the naphthalene and coronene dimers and to three π−π associations of different PAHs (R, made by 10, 16, or 24 C atoms) and P (80 C atoms)« less
Authors:
; ; ;  [1] ;  [2] ;  [3] ;  [4]
  1. Dipartimento di Chimica, Università di Torino, Corso Massimo D’Azeglio 48, I-10125 Torino (Italy)
  2. Scuola Normale Superiore, Piazza dei Cavalieri 7, I-56126, Pisa (Italy)
  3. Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università di Napoli “Federico II,” Via Cintia, 80126 Napoli (Italy)
  4. Dipartimento di Scienze Chimiche, Università di Napoli “Federico II,” Complesso Universitario di Monte Sant’Angelo, Via Cintia, I-80126 Napoli (Italy)
Publication Date:
OSTI Identifier:
22253231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 24; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETYLENE; BENZENE; DENSITY FUNCTIONAL METHOD; ETHYLENE; INTERACTIONS; PERTURBATION THEORY; POLYCYCLIC AROMATIC HYDROCARBONS; STABILITY; VAN DER WAALS FORCES; VINYL RADICALS