Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)

Autores
Hernández, Federico Javier; Brice, Joseph T.; Leavitt, Christopher M.; Liang, Tao; Raston, Paul L.; Pino, Gustavo Ariel; Douberly, Gary E.
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH–H2O and OH(D2O)n clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH–H2O and OH–D2O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D2O)2, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for “up-up” and “up-down” structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D2O molecules are observed shifted approximately 300 cm−1 to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D2O)3.
Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. University of Georgia; Estados Unidos
Fil: Brice, Joseph T.. University of Georgia; Estados Unidos
Fil: Leavitt, Christopher M.. University of Georgia; Estados Unidos
Fil: Liang, Tao. University of Georgia; Estados Unidos
Fil: Raston, Paul L.. James Madison University. Department of Chemistry and Biochemistry; Estados Unidos
Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Douberly, Gary E.. University of Georgia; Estados Unidos
Materia
OH RADICAL COMPLEX
IR SPECTROSCOPY
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/47176

id CONICETDig_4eda2679d9753346325e4b91e4aaffa3
oai_identifier_str oai:ri.conicet.gov.ar:11336/47176
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)Hernández, Federico JavierBrice, Joseph T.Leavitt, Christopher M.Liang, TaoRaston, Paul L.Pino, Gustavo ArielDouberly, Gary E.OH RADICAL COMPLEXIR SPECTROSCOPYhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH–H2O and OH(D2O)n clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH–H2O and OH–D2O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D2O)2, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for “up-up” and “up-down” structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D2O molecules are observed shifted approximately 300 cm−1 to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D2O)3.Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. University of Georgia; Estados UnidosFil: Brice, Joseph T.. University of Georgia; Estados UnidosFil: Leavitt, Christopher M.. University of Georgia; Estados UnidosFil: Liang, Tao. University of Georgia; Estados UnidosFil: Raston, Paul L.. James Madison University. Department of Chemistry and Biochemistry; Estados UnidosFil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Douberly, Gary E.. University of Georgia; Estados UnidosAmerican Institute of Physics2015-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/47176Hernández, Federico Javier; Brice, Joseph T.; Leavitt, Christopher M.; Liang, Tao; Raston, Paul L.; et al.; Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3); American Institute of Physics; Journal of Chemical Physics; 143; 164304; 11-2015; 1-130021-96061089-7690CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.4933432info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4933432info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:44:43Zoai:ri.conicet.gov.ar:11336/47176instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:44:43.944CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
title Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
spellingShingle Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
Hernández, Federico Javier
OH RADICAL COMPLEX
IR SPECTROSCOPY
title_short Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
title_full Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
title_fullStr Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
title_full_unstemmed Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
title_sort Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3)
dc.creator.none.fl_str_mv Hernández, Federico Javier
Brice, Joseph T.
Leavitt, Christopher M.
Liang, Tao
Raston, Paul L.
Pino, Gustavo Ariel
Douberly, Gary E.
author Hernández, Federico Javier
author_facet Hernández, Federico Javier
Brice, Joseph T.
Leavitt, Christopher M.
Liang, Tao
Raston, Paul L.
Pino, Gustavo Ariel
Douberly, Gary E.
author_role author
author2 Brice, Joseph T.
Leavitt, Christopher M.
Liang, Tao
Raston, Paul L.
Pino, Gustavo Ariel
Douberly, Gary E.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv OH RADICAL COMPLEX
IR SPECTROSCOPY
topic OH RADICAL COMPLEX
IR SPECTROSCOPY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH–H2O and OH(D2O)n clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH–H2O and OH–D2O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D2O)2, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for “up-up” and “up-down” structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D2O molecules are observed shifted approximately 300 cm−1 to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D2O)3.
Fil: Hernández, Federico Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. University of Georgia; Estados Unidos
Fil: Brice, Joseph T.. University of Georgia; Estados Unidos
Fil: Leavitt, Christopher M.. University of Georgia; Estados Unidos
Fil: Liang, Tao. University of Georgia; Estados Unidos
Fil: Raston, Paul L.. James Madison University. Department of Chemistry and Biochemistry; Estados Unidos
Fil: Pino, Gustavo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Douberly, Gary E.. University of Georgia; Estados Unidos
description Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH–H2O and OH(D2O)n clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH–H2O and OH–D2O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D2O)2, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for “up-up” and “up-down” structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D2O molecules are observed shifted approximately 300 cm−1 to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D2O)3.
publishDate 2015
dc.date.none.fl_str_mv 2015-11
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/47176
Hernández, Federico Javier; Brice, Joseph T.; Leavitt, Christopher M.; Liang, Tao; Raston, Paul L.; et al.; Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3); American Institute of Physics; Journal of Chemical Physics; 143; 164304; 11-2015; 1-13
0021-9606
1089-7690
CONICET Digital
CONICET
url http://hdl.handle.net/11336/47176
identifier_str_mv Hernández, Federico Javier; Brice, Joseph T.; Leavitt, Christopher M.; Liang, Tao; Raston, Paul L.; et al.; Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH–H2O and OH(D2O)n (n = 1-3); American Institute of Physics; Journal of Chemical Physics; 143; 164304; 11-2015; 1-13
0021-9606
1089-7690
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/1.4933432
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4933432
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1844613407081234432
score 13.070432