Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds

Detalhes bibliográficos
Autor(a) principal: Bitencourt, Ana Carla Peixoto
Data de Publicação: 2008
Outros Autores: Ragni, Mirco, Maciel, Glauciete Sarmento, Aquilanti, Vincenzo, Prudente, Frederico Vasconcellos
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UFBA
Texto Completo: http://www.repositorio.ufba.br/ri/handle/ri/6014
Resumo: p. 1-9
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spelling Bitencourt, Ana Carla PeixotoRagni, MircoMaciel, Glauciete SarmentoAquilanti, VincenzoPrudente, Frederico VasconcellosBitencourt, Ana Carla PeixotoRagni, MircoMaciel, Glauciete SarmentoAquilanti, VincenzoPrudente, Frederico Vasconcellos2012-05-31T12:28:54Z2012-05-31T12:28:54Z20080021-9606http://www.repositorio.ufba.br/ri/handle/ri/6014v. 49, n. 44p. 1-9In view of the particular attention recently devoted to hindered rotations, we have tested reduced kinetic energy operators to study the torsional mode around the O–O bond for H2O2 and for a series of its derivatives (HOOCl, HOOCN, HOOF, HOONO, HOOMe, HOOEt, MeOOMe, ClOOCl, FOOCl, FOOF, and FOONO), for which we had previously determined potential energy profiles along the dihedral ROOR′ angle [R,R′ = H,F,Cl,CN,NO,Me ( = CH3), Et ( = C2H5)]. We have calculated level distributions as a function of temperature and partition functions for all systems. Specifically, for the H2O2 system we have used two procedures for the reduction in the kinetic energy operator to that of a rigid-rotor-like one and the calculated partition functions are compared with previous work. Quantum partition functions are evaluated both by quantum level state sums and by simple classical approximations. A semiclassical approach, using a linear approximation of the classical path and a quadratic Feynman–Hibbs approximation of Feynman path integral, introduced in previous work and here applied to the torsional mode, is shown to greatly improve the classical approximations. Further improvement is obtained by the explicit introduction of the dependence of the moment of inertia from the torsional angle. These results permit one to discuss the characteristic time for chirality changes for the investigated molecules either by quantum mechanical tunneling (dominating at low temperatures) or by transition state theory (expected to provide an estimate of racemization rates in the high energy limit).Submitted by JURANDI DE SOUZA SILVA (jssufba@hotmail.com) on 2012-05-31T12:28:54Z No. of bitstreams: 1 C__Documents and Settings_rep...t.default_Cache_9_32_A9163d01.pdf: 460336 bytes, checksum: 180533d2963bc9ffa966a83c00011765 (MD5)Made available in DSpace on 2012-05-31T12:28:54Z (GMT). No. of bitstreams: 1 C__Documents and Settings_rep...t.default_Cache_9_32_A9163d01.pdf: 460336 bytes, checksum: 180533d2963bc9ffa966a83c00011765 (MD5) Previous issue date: 2008http://dx.doi.org/10.1063/1.2992554reponame:Repositório Institucional da UFBAinstname:Universidade Federal da Bahia (UFBA)instacron:UFBALevel distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bondsTetrahedron Lettersinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleenginfo:eu-repo/semantics/openAccessORIGINALC__Documents and Settings_rep...t.default_Cache_9_32_A9163d01.pdfC__Documents and Settings_rep...t.default_Cache_9_32_A9163d01.pdfapplication/pdf460336https://repositorio.ufba.br/bitstream/ri/6014/1/C__Documents%20and%20Settings_rep...t.default_Cache_9_32_A9163d01.pdf180533d2963bc9ffa966a83c00011765MD51LICENSElicense.txtlicense.txttext/plain1762https://repositorio.ufba.br/bitstream/ri/6014/2/license.txt1b89a9a0548218172d7c829f87a0eab9MD52TEXTC__Documents and Settings_rep...t.default_Cache_9_32_A9163d01.pdf.txtC__Documents and Settings_rep...t.default_Cache_9_32_A9163d01.pdf.txtExtracted texttext/plain40737https://repositorio.ufba.br/bitstream/ri/6014/3/C__Documents%20and%20Settings_rep...t.default_Cache_9_32_A9163d01.pdf.txt4bb39dd496845fa7be61846d2b714d3fMD53ri/60142022-07-05 14:03:48.356oai:repositorio.ufba.br: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Repositório InstitucionalPUBhttp://192.188.11.11:8080/oai/requestopendoar:19322022-07-05T17:03:48Repositório Institucional da UFBA - Universidade Federal da Bahia (UFBA)false
dc.title.pt_BR.fl_str_mv Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
dc.title.alternative.pt_BR.fl_str_mv Tetrahedron Letters
title Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
spellingShingle Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
Bitencourt, Ana Carla Peixoto
title_short Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
title_full Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
title_fullStr Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
title_full_unstemmed Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
title_sort Level distributions, partition functions, and rates of chirality changing processes for the torsional mode around O–O bonds
author Bitencourt, Ana Carla Peixoto
author_facet Bitencourt, Ana Carla Peixoto
Ragni, Mirco
Maciel, Glauciete Sarmento
Aquilanti, Vincenzo
Prudente, Frederico Vasconcellos
author_role author
author2 Ragni, Mirco
Maciel, Glauciete Sarmento
Aquilanti, Vincenzo
Prudente, Frederico Vasconcellos
author2_role author
author
author
author
dc.contributor.author.fl_str_mv Bitencourt, Ana Carla Peixoto
Ragni, Mirco
Maciel, Glauciete Sarmento
Aquilanti, Vincenzo
Prudente, Frederico Vasconcellos
Bitencourt, Ana Carla Peixoto
Ragni, Mirco
Maciel, Glauciete Sarmento
Aquilanti, Vincenzo
Prudente, Frederico Vasconcellos
description p. 1-9
publishDate 2008
dc.date.issued.fl_str_mv 2008
dc.date.accessioned.fl_str_mv 2012-05-31T12:28:54Z
dc.date.available.fl_str_mv 2012-05-31T12:28:54Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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dc.identifier.uri.fl_str_mv http://www.repositorio.ufba.br/ri/handle/ri/6014
dc.identifier.issn.none.fl_str_mv 0021-9606
dc.identifier.number.pt_BR.fl_str_mv v. 49, n. 44
identifier_str_mv 0021-9606
v. 49, n. 44
url http://www.repositorio.ufba.br/ri/handle/ri/6014
dc.language.iso.fl_str_mv eng
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dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
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dc.source.pt_BR.fl_str_mv http://dx.doi.org/10.1063/1.2992554
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