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The coupling constant polarizability and hyperpolarizabilty of 1 J (NH) in N ‐methylacetamide, and its application for the multipole spin–spin coupling constant polarizability/reaction field approach to solvation
Author(s) -
Kjær Hanna,
Sauer Stephan P. A.,
Kongsted Jacob
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21897
Subject(s) - polarizability , coupling constant , multipole expansion , quadrupole , chemistry , electric field gradient , ab initio quantum chemistry methods , dipole , solvation , ab initio , atomic physics , molecular physics , computational chemistry , molecule , physics , quantum mechanics , organic chemistry
We present a benchmark study of a combined multipole spin–spin coupling constant (SSCC) polarizability/reaction field (MJP/RF) approach to the calculation of both specific and bulk solvation effects on SSCCs of solvated molecules. The MJP/RF scheme is defined by an expansion of the SSCCs of the solvated molecule in terms of coupling constant dipole and quadrupole polarizabilities and hyperpolarizabilities derived from single molecule ab initio calculations. The solvent electric field and electric field gradient are calculated based on data derived from molecular dynamics (MD) simulations thereby accounting for solute–solvent dynamical effects. The MJP/RF method is benchmarked against polarizable QM/MM calculations for the one‐bond N–H coupling constant in N ‐methylacetamide. The best agreement between the MJP/RF and QM/MM approaches is found by truncating the electric field expansion in the MJP/RF approach at the linear electric field level. In addition, we investigate the sensitivity of the results due to the choice of one‐electron basis set in the ab initio calculations of the coupling constant (hyper‐)polarizabilities and find that they are affected by the basis set in a way similar to the coupling constants themselves. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011