A theoretical study of SnF2+, SnCl2+, and SnO2+ and their experimental search


Autoria(s): Batista, Ana Paula de Lima; Lima, Jose Carlos Barreto de; Franzreb, Klaus; Ornellas, Fernando R.
Contribuinte(s)

UNIVERSIDADE DE SÃO PAULO

Data(s)

11/09/2013

11/09/2013

21/10/2012

Resumo

We present a detailed theoretical study of the stability of the gas-phase diatomic dications SnF2+, SnCl2+, and SnO2+ using ab initio computer calculations. The ground states of SnF2+, SnCl2+, and SnO2+ are thermodynamically stable, respectively, with dissociation energies of 0.45, 0.30, and 0.42 eV. Whereas SnF2+ dissociates into Sn2+ + F, the long range behaviour of the potential energy curves of SnCl2+ and SnO2+ is repulsive and wide barrier heights due to avoided crossing act as a kind of effective dissociation energy. Their equilibrium internuclear distances are 4.855, 5.201, and 4.852 a(0), respectively. The double ionisation energies (T-e) to form SnF2+, SnCl2+, and SnO2+ from their respective neutral parents are 25.87, 23.71, and 25.97 eV. We combine our theoretical work with the experimental results of a search for these doubly positively charged diatomic molecules in the gas phase. SnO2+ and SnF2+ have been observed for prolonged oxygen (O-16(-)) ion beam sputtering of a tin metal foil and of tin (II) fluoride (SnF2) powder, respectively, for ion flight times of about 10(-5) s through a magnetic-sector mass spectrometer. In addition, SnCl2+ has been detected for O-16(-) ion surface bombardment of stannous (tin (II)) chloride (SnCl2) powder. To our knowledge, SnF2+ is a novel gas-phase molecule, whereas SnCl2+ had been detected previously by electron-impact ionization mass spectrometry, and SnO2+ had been observed before by spark source mass spectrometry as well as by atom probe mass spectrometry. We are not aware of any previous theoretical studies of these molecular systems. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4758475]

National Science Foundation at Arizona State University

National Science Foundation at Arizona State University [NSF EAR 0622775, EAR 0948878]

Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP)

Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP)

Coordenacao de Pessoal de Nivel Superior (CAPES) of Brazil

Coordenacao de Pessoal de Nivel Superior (CAPES) of Brazil

Conselho Nacional de Desenvolvimento Cientifico e Tecnologico of Brazil (CNPq)

Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) of Brazil

Identificador

JOURNAL OF CHEMICAL PHYSICS, MELVILLE, v. 137, n. 15, p. 135-138, OCT 21, 2012

0021-9606

http://www.producao.usp.br/handle/BDPI/33260

10.1063/1.4758475

http://dx.doi.org/10.1063/1.4758475

Idioma(s)

eng

Publicador

AMER INST PHYSICS

MELVILLE

Relação

JOURNAL OF CHEMICAL PHYSICS

Direitos

restrictedAccess

Copyright AMER INST PHYSICS

Palavras-Chave #AB INITIO CALCULATIONS #DISSOCIATION ENERGIES #ENERGY LEVEL CROSSING #GROUND STATES #IONISATION #ION-SURFACE IMPACT #MASS SPECTRA #POSITIVE IONS #POTENTIAL ENERGY SURFACES #THERMODYNAMICS #TIN COMPOUNDS #POTENTIAL-ENERGY CURVES #CONFIGURATION-INTERACTION CALCULATIONS #CORRELATED MOLECULAR CALCULATIONS #PHASE DIATOMIC TRICATIONS #TIN MONOXIDE MOLECULE #MULTIPLY-CHARGED IONS #GAUSSIAN-BASIS SETS #GAS-PHASE #SPECTROSCOPIC PROPERTIES #ELECTRONIC STATES #PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
Tipo

article

original article

publishedVersion