Solvent Dependent Nuclear Magnetic Resonance Molecular Parameters Based on a Polarization Consistent Screened Range Separated Hybrid Density Functional Theory Framework

Begam, Khadiza; Cohen, Lilian; Goobes, Gil; Dunietz, Barry D.

doi:10.1021/acs.jctc.2c00275

Cited by 2 publications

(1 citation statement)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The accuracy of DFT predicted nuclear shieldings and agreement with experimental data in solution is often improved by including solvent effect. Dunietz et al 51 developed an improved approach, based on a polarization consistent screened range separated hybrid DFT framework for prediction of NMR parameters in solution. Lipparini et al, 52 computed nuclear shieldings at the CASSCF level of theory using GIAO approach and Cholesky decomposition.…”

Section: Progress In Theoretical Methodologymentioning

confidence: 99%

Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

View full text Add to dashboard Cite

This chapter continues earlier reviews of essential works on theoretical issues of nuclear magnetic shieldings published from 1 January to 31 December 2022. As previously, the chapter concentrates on theoretical calculations of nuclear shielding parameters and/or chemical shifts in case of free molecules in the gas phase and solution, and in some cases in the solid state using a periodic formulation. The nuclear shieldings in solution are mainly calculated using inexpensive polarizable continuum model of solvent (PCM). The use of discrete solvent molecules (in particular water and other polar solvents), which is essential for correct description of hydrogen bonding, is often omitted by numerous authors. Most calculations use a relatively simple and fast, but reliable density functional theory (DFT) combined with gauge-including atomic orbital (GIAO) approach. On the other hand, reports on prediction of nuclear magnetic shielding parameters using high level theoretical methods combined with large and flexible basis sets are not so common due to the enormous computational cost. In addition, correction of raw theoretical nuclear magnetic shieldings due to ro-vibration (zero-point vibration correction, ZPVC) and temperature corrections (TC), as well as implicit and explicit solvent effects and relativistic corrections are not often reported.

show abstract

Section: Progress In Theoretical Methodologymentioning

confidence: 99%

Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

View full text Add to dashboard Cite

show abstract

Polarization consistent dielectric screening in polarizable continuum model calculations of solvation energies

Khatri,

Dunietz

2023

The Journal of Chemical Physics

View full text Add to dashboard Cite

A polarization consistent framework, where dielectric screening is affected consistently in polarizable continuum model (PCM) calculations, is employed for the study of solvation energies. The computational framework combines a screened range-separated-hybrid functional (SRSH) with PCM calculations, SRSH-PCM, where dielectric screening is imposed in both PCM self-consistent reaction field (SCRF) iterations and the electronic structure Hamiltonian. We begin by demonstrating the impact of modifying the Hamiltonian to include such dielectric screening in SCRF iterations by considering the solutions of electrostatically embedded Hartree–Fock (HF) exact exchange equations. Long-range screened HF-PCM calculations are shown to capture properly the linear dependence of gap energy of frontier orbitals on the inverse of the dielectric constant, whereas unscreened HF-PCM orbital energies are fallaciously semi-constant with respect to the dielectric constant and, therefore, inconsistent with the ionization energy gaps. Similar trends affect density functional theory (DFT) calculations that aim to achieve predictive quality. Importantly, the dielectric screened calculations are shown to significantly affect DFT- and HF PCM-based solvation energies, where screened solvation energies are smaller compared to the unscreened values. Importantly, SRSH-PCM, therefore, appears to reduce the tendency of DFT-PCM to overestimate solvation energies, where we find the effect to increase with the dielectric constant and the polarity of the molecular solute, trends that enhance the quality of DFT-PCM calculations of solvation energy. Understanding the relationship of dielectric screening in the Hamiltonian and DFT-PCM calculations can ultimately benefit on-going efforts for the design of predictive and parameter free descriptions of solvation energies.

show abstract

Solvent Dependent Nuclear Magnetic Resonance Molecular Parameters Based on a Polarization Consistent Screened Range Separated Hybrid Density Functional Theory Framework

Cited by 2 publications

References 60 publications

Theory and computation of nuclear shielding

Theory and computation of nuclear shielding

Polarization consistent dielectric screening in polarizable continuum model calculations of solvation energies

Contact Info

Product

Resources

About