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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/47176
Ver los metadatos del registro completo
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 |