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Abstract:

The NMR spin coupling parameters, 1J(N1H) 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 △σ(15N) is -25.2 ppm, in good agreement with the experimental value of -22.6 ppm © 2009 American Chemical Society.

Registro:

Documento: Artículo
Título:NMR chemical shielding and spin-spin coupling constants of liquid NH 3: A systematic investigation using the sequential QM/MM method
Autor:Gester, R.M.; Georg, H.C.; Canuto, S.; Cristina Caputo, M.; Provasi, P.F.
Filiación:Instituto de Física, Universidade de São Paulo, CP 66318, 05315-970, São Paulo, SP, Brazil
Instituto de Física, Universidade Federal de Goiás, CP 131, 74001-970, Goiânia, GO, Brazil
Department of Physics, University of Buenos Aires, Ciudad Universitaria, 1400 - Buenos Aires, Argentina
I-MIT (CONICET), Department of Physics, Northeastern University, Av. Libertad 5500, W 3404 AAS - Corrientes, Argentina
Palabras clave:Ammonia; Chemical shift; Computer simulation; Density functional theory; Deuterium; Molecules; Monte Carlo methods; Nuclear magnetic resonance; Shielding; Spin dynamics; Time varying systems; Vapors; Ammonia molecules; Chemical shielding; Density functional theory calculations; Deuterated liquids; Electronic polarization; Experimental values; Geometry relaxation; Hydrogen bonded molecules; Iterative procedures; Lennard-Jones potential; Liquid ammonia; Liquid chemicals; Monte Carlo Simulation; Pure solvents; QM/MM method; Solvent molecules; Spin couplings; Spin-spin coupling constants; Systematic investigations; Theoretical models; Theoretical result; Liquids
Año:2009
Volumen:113
Número:52
Página de inicio:14936
Página de fin:14942
DOI: http://dx.doi.org/10.1021/jp9050484
Título revista:Journal of Physical Chemistry A
Título revista abreviado:J Phys Chem A
ISSN:10895639
CODEN:JPCAF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v113_n52_p14936_Gester

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Citas:

---------- APA ----------
Gester, R.M., Georg, H.C., Canuto, S., Cristina Caputo, M. & Provasi, P.F. (2009) . NMR chemical shielding and spin-spin coupling constants of liquid NH 3: A systematic investigation using the sequential QM/MM method. Journal of Physical Chemistry A, 113(52), 14936-14942.
http://dx.doi.org/10.1021/jp9050484
---------- CHICAGO ----------
Gester, R.M., Georg, H.C., Canuto, S., Cristina Caputo, M., Provasi, P.F. "NMR chemical shielding and spin-spin coupling constants of liquid NH 3: A systematic investigation using the sequential QM/MM method" . Journal of Physical Chemistry A 113, no. 52 (2009) : 14936-14942.
http://dx.doi.org/10.1021/jp9050484
---------- MLA ----------
Gester, R.M., Georg, H.C., Canuto, S., Cristina Caputo, M., Provasi, P.F. "NMR chemical shielding and spin-spin coupling constants of liquid NH 3: A systematic investigation using the sequential QM/MM method" . Journal of Physical Chemistry A, vol. 113, no. 52, 2009, pp. 14936-14942.
http://dx.doi.org/10.1021/jp9050484
---------- VANCOUVER ----------
Gester, R.M., Georg, H.C., Canuto, S., Cristina Caputo, M., Provasi, P.F. NMR chemical shielding and spin-spin coupling constants of liquid NH 3: A systematic investigation using the sequential QM/MM method. J Phys Chem A. 2009;113(52):14936-14942.
http://dx.doi.org/10.1021/jp9050484