NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method
The NMR spin coupling parameters, ¹J(N,H) and ²J(H,H), and the chemical shielding, σ(15N), of liquid ammonia are studied from a combined and sequential QM/MM methodology. Monte Carlo simulations are performed to generate statistically uncorrelated configurations that are submitted to density functio...
| Autores: | , , , , |
|---|---|
| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2009 |
| País: | Argentina |
| Recursos: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/24732 |
| Acesso em linha: | http://hdl.handle.net/11336/24732 |
| Access Level: | acceso abierto |
| Palavra-chave: | Solvent Effect Chemical Shielding Spin Spin Coupling Constant https://purl.org/becyt/ford/1.3 https://purl.org/becyt/ford/1 |
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Argentina |
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| dc.title.none.fl_str_mv |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method |
| title |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method |
| spellingShingle |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method Gester, Rodrigo M. Solvent Effect Chemical Shielding Spin Spin Coupling Constant https://purl.org/becyt/ford/1.3 https://purl.org/becyt/ford/1 |
| title_short |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method |
| title_full |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method |
| title_fullStr |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method |
| title_full_unstemmed |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method |
| title_sort |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method |
| dc.creator.none.fl_str_mv |
Gester, Rodrigo M. Georg, Herbert C. Canuto, Sylvio Caputo, Maria Cristina Provasi, Patricio Federico |
| author |
Gester, Rodrigo M. |
| author_facet |
Gester, Rodrigo M. Georg, Herbert C. Canuto, Sylvio Caputo, Maria Cristina Provasi, Patricio Federico |
| author_role |
author |
| author2 |
Georg, Herbert C. Canuto, Sylvio Caputo, Maria Cristina Provasi, Patricio Federico |
| author2_role |
author author author author |
| dc.subject.none.fl_str_mv |
Solvent Effect Chemical Shielding Spin Spin Coupling Constant https://purl.org/becyt/ford/1.3 https://purl.org/becyt/ford/1 |
| topic |
Solvent Effect Chemical Shielding Spin Spin Coupling Constant https://purl.org/becyt/ford/1.3 https://purl.org/becyt/ford/1 |
| description |
The NMR spin coupling parameters, ¹J(N,H) and ²J(H,H), and the chemical shielding, σ(15N), of liquid ammonia are studied from a combined and sequential QM/MM methodology. Monte Carlo simulations are performed to generate statistically uncorrelated configurations that are submitted to density functional theory calculations. Two different Lennard−Jones potentials are used in the liquid simulations. Electronic polarization is included in these two potentials via an iterative procedure with and without geometry relaxation, and the influence on the calculated properties are analyzed. B3LYP/aug-cc-pVTZ-J calculations were used to compute the ¹J(N,H) constants in the interval of −67.8 to −63.9 Hz, depending on the theoretical model used. These can be compared with the experimental results of −61.6 Hz. For the ²J(H,H) coupling the theoretical results vary between −10.6 to −13.01 Hz. The indirect experimental result derived from partially deuterated liquid is −11.1 Hz. Inclusion of explicit hydrogen bonded molecules gives a small but important contribution. The vapor-to-liquid shifts are also considered. This shift is calculated to be negligible for ¹J(N,H) in agreement with experiment. This is rationalized as a cancellation of the geometry relaxation and pure solvent effects. For the chemical shielding, σ(15N) calculations at the B3LYP/aug-pcS-3 show that the vapor-to-liquid chemical shift requires the explicit use of solvent molecules. Considering only one ammonia molecule in an electrostatic embedding gives a wrong sign for the chemical shift that is corrected only with the use of explicit additional molecules. The best result calculated for the vapor to liquid chemical shift Δσ(15N) is −25.2 ppm, in good agreement with the experimental value of −22.6 ppm. |
| publishDate |
2009 |
| dc.date.none.fl_str_mv |
2009-09 |
| 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/11336/24732 Gester, Rodrigo M.; Georg, Herbert C.; Canuto, Sylvio; Caputo, Maria Cristina; Provasi, Patricio Federico; NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method; American Chemical Society; Journal of Physical Chemistry A; 113; 52; 9-2009; 14936-14942 1089-5639 1520-5215 CONICET Digital CONICET |
| url |
http://hdl.handle.net/11336/24732 |
| identifier_str_mv |
Gester, Rodrigo M.; Georg, Herbert C.; Canuto, Sylvio; Caputo, Maria Cristina; Provasi, Patricio Federico; NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method; American Chemical Society; Journal of Physical Chemistry A; 113; 52; 9-2009; 14936-14942 1089-5639 1520-5215 CONICET Digital CONICET |
| dc.language.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp9050484 info:eu-repo/semantics/altIdentifier/doi/10.1021/jp9050484 |
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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 application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
| publisher.none.fl_str_mv |
American Chemical Society |
| dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
| repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
| _version_ |
1799196168902672384 |
| spelling |
NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM methodGester, Rodrigo M.Georg, Herbert C.Canuto, SylvioCaputo, Maria CristinaProvasi, Patricio FedericoSolvent EffectChemical ShieldingSpin Spin Coupling Constanthttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The NMR spin coupling parameters, ¹J(N,H) and ²J(H,H), and the chemical shielding, σ(15N), of liquid ammonia are studied from a combined and sequential QM/MM methodology. Monte Carlo simulations are performed to generate statistically uncorrelated configurations that are submitted to density functional theory calculations. Two different Lennard−Jones potentials are used in the liquid simulations. Electronic polarization is included in these two potentials via an iterative procedure with and without geometry relaxation, and the influence on the calculated properties are analyzed. B3LYP/aug-cc-pVTZ-J calculations were used to compute the ¹J(N,H) constants in the interval of −67.8 to −63.9 Hz, depending on the theoretical model used. These can be compared with the experimental results of −61.6 Hz. For the ²J(H,H) coupling the theoretical results vary between −10.6 to −13.01 Hz. The indirect experimental result derived from partially deuterated liquid is −11.1 Hz. Inclusion of explicit hydrogen bonded molecules gives a small but important contribution. The vapor-to-liquid shifts are also considered. This shift is calculated to be negligible for ¹J(N,H) in agreement with experiment. This is rationalized as a cancellation of the geometry relaxation and pure solvent effects. For the chemical shielding, σ(15N) calculations at the B3LYP/aug-pcS-3 show that the vapor-to-liquid chemical shift requires the explicit use of solvent molecules. Considering only one ammonia molecule in an electrostatic embedding gives a wrong sign for the chemical shift that is corrected only with the use of explicit additional molecules. The best result calculated for the vapor to liquid chemical shift Δσ(15N) is −25.2 ppm, in good agreement with the experimental value of −22.6 ppm.Fil: Gester, Rodrigo M.. Universidade de Sao Paulo; BrasilFil: Georg, Herbert C.. Universidade Federal de Goiás; Brasil. Universidade de Sao Paulo; BrasilFil: Canuto, Sylvio. Universidade de Sao Paulo; BrasilFil: Caputo, Maria Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Provasi, Patricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Modelado e Innovación Tecnológica. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Modelado e Innovación Tecnológica; ArgentinaAmerican Chemical Society2009-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/24732Gester, Rodrigo M.; Georg, Herbert C.; Canuto, Sylvio; Caputo, Maria Cristina; Provasi, Patricio Federico; NMR chemical shielding and spin-spin coupling constants of liquid NHȝ: a systematic investigation using the sequential QM/MM method; American Chemical Society; Journal of Physical Chemistry A; 113; 52; 9-2009; 14936-149421089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp9050484info:eu-repo/semantics/altIdentifier/doi/10.1021/jp9050484info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T14:17:19Zoai:ri.conicet.gov.ar:11336/24732instacron: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:34982024-05-08 14:17:19.29CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
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15,811543 |