Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds

The nuclear magnetic shieldings of Si, Ge, and Sn in MH4−nYn (M = Si, Ge, Sn; Y = F, Cl, Br, I and n = 1–4) molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autor principal: Maldonado, A.F
Otros Autores: Aucar, G.A, Melo, Juan Ignacio
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: Springer Verlag 2014
Acceso en línea:Registro en Scopus
DOI
Handle
Registro en la Biblioteca Digital
Aporte de:Registro referencial: Solicitar el recurso aquí
LEADER 08827caa a22009977a 4500
001 PAPER-14525
003 AR-BaUEN
005 20250724111511.0
008 190411s2014 xx ||||fo|||| 00| 0 eng|d
024 7 |2 scopus  |a 2-s2.0-84919936054 
024 7 |2 cas  |a germanium, 7440-56-4; hydrogen, 12385-13-6, 1333-74-0; iodine, 7553-56-2; lead, 7439-92-1, 13966-28-4; proton, 12408-02-5, 12586-59-3; silicon, 7440-21-3; tin, 14314-35-3, 7440-31-5 
030 |a JMMOF 
040 |a Scopus  |b spa  |c AR-BaUEN  |d AR-BaUEN 
100 1 |a Maldonado, A.F. 
245 1 0 |a Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4−nYn (n = 0–4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds 
260 |b Springer Verlag  |c 2014 
270 1 0 |m Melo, J.I.; Dpto. Fisica, Facultad de Ciencias Exactas y Naturales, Univ. Buenos Aires and IFIBA-ConicetArgentina 
504 |a Edlund, U., Lejon, T., Pyykkö, P., Venkatachalam, T.K., Buncel, E., (1987) J Am Chem Soc, 109, p. 5982. , COI: 1:CAS:528:DyaL2sXltlCgu7o%3D 
504 |a Pyykkö, P., Görling, A., Rösch, N., (1987) Mol Phys, 61, p. 195 
504 |a Kaupp, M., Malkina, O.L., Malkin, V.G., Pyykkö, P., (1998) Chem Eur J, 4, p. 118. , COI: 1:CAS:528:DyaK1cXmtlCmtg%3D%3D 
504 |a Melo, J.I., Ruiz deAzúa, M.C., Giribet, C.G., Aucar, G.A., Provasi, P.F., (2004) J Chem Phys, 121, p. 6798. , COI: 1:CAS:528:DC%2BD2cXotVKmsb8%3D 
504 |a Kaupp, M., Schwerdtfeger, P., Relativistic effects on NMR chemical shifts (Chapter 9) (2004) Relativistic electronic structure theory, part 2: Applications, 2, pp. 552-597. , Elsevier, Amsterdam: 
504 |a Lantto, P., Romero, R.H., Gomez, S.S., Aucar, G.A., Vaara, J., (2006) J Chem Phys, 125, p. 184113 
504 |a Vaara, J., (2007) Phys Chem Chem Phys, 9, p. 5399. , COI: 1:CAS:528:DC%2BD2sXhtFCgsr7L 
504 |a Maldonado, A.F., Aucar, G.A., (2009) Phys Chem Chem Phys, 11, p. 5615. , COI: 1:CAS:528:DC%2BD1MXotFWmsLk%3D 
504 |a Autschbach, J., Zheng, S., (2009) Annu Rep NMR Spectrosc, 67, p. 1. , COI: 1:CAS:528:DC%2BD1MXhsFaru7fP 
504 |a Kantola, A.M., Lantto, P., Vaara, J., Jokisaari, J., (2010) Phys Chem Chem Phys, 12, p. 2679. , COI: 1:CAS:528:DC%2BC3cXislWktr8%3D 
504 |a Arcisauskaite, V., Melo, J.I., Hemmingsen, L., Sauer, S.P.A., (2011) J Chem Phys, 135, p. 044306 
504 |a Roukala, J., Maldonado, A.F., Vaara, J., Aucar, G.A., Lantto, P., (2011) Phys Chem Chem Phys, 13, p. 21016. , COI: 1:CAS:528:DC%2BC3MXhsFaiurfN 
504 |a Melo, J.I., Maldonado, A.F., Aucar, G.A., (2012) J Chem Phys, 137, p. 214319 
504 |a Melo, J.I., Maldonado, A.F., Aucar, G.A., (2011) Theor Chem Accounts, 129, p. 483. , COI: 1:CAS:528:DC%2BC3MXmtVGktbs%3D 
504 |a Melo, J.I., Ruiz deAzúa, M.C., Giribet, C.G., Aucar, G.A., Romero, R.H., (2003) J Chem Phys, 118, p. 471. , COI: 1:CAS:528:DC%2BD38XpvVejurY%3D 
504 |a Manninen, P., Lantto, P., Vaara, J., Ruud, K., (2003) J Chem Phys, 119, p. 2623. , COI: 1:CAS:528:DC%2BD3sXlsFKgtr8%3D 
504 |a Manninen, P., Ruud, K., Lantto, P., Vaara, J., (2005) J Chem Phys, 122, p. 114107 
504 |a Rodriguez-Fortez, A., Alemany, P., Ziegler, T., (1999) J Phys Chem A, 103, p. 8288 
504 |a Maldonado, A.F., Aucar, G.A., (2014) J Phys Chem A 
504 |a Gomez, S.S., Maldonado, A.F., Aucar, G.A., (2005) J Chem Phys, 123, p. 214108 
504 |a Visscher, L., Enevoldsen, T., Saue, T., Jensen, H.J.A., Oddershede, J., (1999) J Comput Chem, 20, p. 1262. , COI: 1:CAS:528:DyaK1MXlt1GhsL0%3D 
504 |a Jameson, C.J., (1998) Multinuclear NMR, , Plenum, New York: 
504 |a Kaupp, M., Kaupp, M., Bühl, M., Malkin, V.G., Interpretation of NMR chemical shifts (Chapter 18) (2004) Calculation of NMR and EPR parameters: theory and applications, pp. 293-306. , Wiley-VCH, Weinheim: 
504 |a Fukawa, S., Hada, M., Fukuda, R., Tanaka, S., Nakatsuji, H., (2001) J Comput Chem, 22, p. 528. , COI: 1:CAS:528:DC%2BD3MXisVSnur8%3D 
504 |a Aucar, G.A., Romero, R.H., Maldonado, A.F., (2010) Int Rev Phys Chem, 29, p. 1. , COI: 1:CAS:528:DC%2BC3cXjt1yhu78%3D 
504 |a Saue, T., Visscher, L., Bast, R., Jensen, H.J.A., Dyall, K.G., Ekstrom, U., Eliav, E., Yamamoto, S., (2010) DIRAC10, , http://dirac.chem.sdu.dk, University of Southern Denmark, Odense: 
504 |a Kagakkai, N.B., (1984) Kagaku benran, , 3rd edn. Maruzen, Tokyo 
504 |a Sadlej, A.J., (1991) Theor Chim Acta, 79, p. 123. , COI: 1:CAS:528:DyaK3MXktlGrurs%3D 
504 |a Maldonado, A.F., Gimenez, C.A., Aucar, G.A., (2012) Chem Phys, 395, p. 75. , COI: 1:CAS:528:DC%2BC38XitF2ksLk%3D 
504 |a Maldonado, A.F., Gimenez, C.A., Aucar, G.A., (2012) J Chem Phys, 136, p. 224110 
504 |a Aidas, K., Angeli, C., Bak, K.L., Bakken, V., Bast, R., Boman, L., Christiansen, O., gren, H., The Dalton quantum chemistry program system (2013) WIREs Comput Mol Sci, 4, pp. 269-284 
504 |a Kaneko, H., Hada, M., Nakajima, T., Nakatsuji, H., (1996) Chem Phys Lett, 261, p. 1. , COI: 1:CAS:528:DyaK28XlvFKnsbw%3D 
506 |2 openaire  |e Política editorial 
520 3 |a The nuclear magnetic shieldings of Si, Ge, and Sn in MH4−nYn (M = Si, Ge, Sn; Y = F, Cl, Br, I and n = 1–4) molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the “heavy atom effect on vicinal heavy atom” (HAVHA), in more detail. We found that the main electronic mechanism is the spin–orbit or σp T(3) correction, although other corrections such as σp S(1) and σp S(3) are also important. Finally, we analyzed proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine. © 2014, Springer-Verlag Berlin Heidelberg.  |l eng 
593 |a Physics Department, Natural and Exact Science Faculty, Northeastern University of Argentina, Corrientes, Argentina 
593 |a Institute of Modelling and Innovation on Technology, IMIT, Corrientes, Argentina 
593 |a Dpto. Fisica, Facultad de Ciencias Exactas y Naturales, Univ. Buenos Aires and IFIBA-Conicet, Buenos Aires, Argentina 
690 1 0 |a LRESC 
690 1 0 |a NMR 
690 1 0 |a POLARIZATION PROPAGATORS 
690 1 0 |a RELATIVISTIC EFFECTS 
690 1 0 |a GERMANIUM 
690 1 0 |a HALOGEN 
690 1 0 |a HYDROGEN 
690 1 0 |a IODINE 
690 1 0 |a LEAD 
690 1 0 |a LIGAND 
690 1 0 |a PROTON 
690 1 0 |a SILICON 
690 1 0 |a TIN 
690 1 0 |a ARTICLE 
690 1 0 |a ATOM 
690 1 0 |a ELECTRON 
690 1 0 |a EXCITATION 
690 1 0 |a MAGNETIC FIELD 
690 1 0 |a MAGNETISM 
690 1 0 |a NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 
690 1 0 |a POLARIZATION 
690 1 0 |a PROTON NUCLEAR MAGNETIC RESONANCE 
700 1 |a Aucar, G.A. 
700 1 |a Melo, Juan Ignacio 
773 0 |d Springer Verlag, 2014  |g v. 20  |k n. 9  |p J. Mol. Model.  |x 16102940  |t Journal of Molecular Modeling 
856 4 1 |u https://www.scopus.com/inward/record.uri?eid=2-s2.0-84919936054&doi=10.1007%2fs00894-014-2417-z&partnerID=40&md5=f4066bcf287953271bae0443831e0f81  |y Registro en Scopus 
856 4 0 |u https://doi.org/10.1007/s00894-014-2417-z  |y DOI 
856 4 0 |u https://hdl.handle.net/20.500.12110/paper_16102940_v20_n9_p_Maldonado  |y Handle 
856 4 0 |u https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_16102940_v20_n9_p_Maldonado  |y Registro en la Biblioteca Digital 
961 |a paper_16102940_v20_n9_p_Maldonado  |b paper  |c PE 
962 |a info:eu-repo/semantics/article  |a info:ar-repo/semantics/artículo  |b info:eu-repo/semantics/publishedVersion 
999 |c 75478