Abstrakt
A method for ab initio calculation of NMR parameters including the effects due to molecular dynamics (MD) will be introduced [1]. The Ad-MD method employs QM-calculated adiabatic dependence of an NMR parameter on molecular geometry and MD-calculated probability distribution of respective geometrical parameters.
One adiabatic NMR surface can be used for Ad-MD calculation in a polymer assuming chemical equivalence of polymer units that possess particular dynamical behaviors. Hence, well-benchmarked adiabatic dependence of a spectral parameter like NMR shift (δ) and/or indirect spin-spin coupling (J-coupling) can be used repetitively for their dynamical averaging in a polymer practically at the cost of MD calculation.
Ad-MD method enables rapid and reliable comparison of different MD force fields and/or adiabatic NMR surfaces (e.g. Karplus equations) in direct relation with measure NMR spectra which may be utilized in development of a novel force fields.
Performance of Ad-MD method will be illustrated on dynamical averaging of 31P NMR shift (δ31P) in the Dickerson-Drew DNA [1]. Respective adiabatic δ31P-surface was benchmarked in model phosphates with distinctively different structure and dynamics previously [2,3]. 1.
J. Fukal, M.
Buděšínský, M. Zgarbová, J. Šebera, O.
Páv, P. Jurečka, V.
Sychrovský, J Comput Chem., 2022, 43, 132-143. 2. J.
Fukal, O. Páv, M.
Buděšínský, J. Šebera, V. Sychrovský, Phys.
Chem. Chem.
Phys., 2017, 19, 31830-31841. 3. J.
Fukal, O. Páv, M.
Buděšínský, I. Rosenberg, J. Šebera, V.
Sychrovský, Phys. Chem.
Chem. Phys., 2019, 21, 9924-9934