HHundreds of catalytic methods are developed each year to meet the demand for high-purity chiral compounds. The computational design of enantioselective organocatalysts remains a significant challenge, as catalysts are typically...
Hydrated transition
metal ions are prototypical systems that can
be used to model properties of transition metals in complex chemical
environments. These seemingly simple systems present challenges for
computational chemistry and are thus crucial in evaluations of quantum
chemical methods for spin-state and redox energetics. In this work,
we explore the applicability of the domain-based pair natural orbital
implementation of coupled cluster (DLPNO-CC) theory to the calculation
of ionization energies and redox potentials for hydrated ions of all
first transition row (3d) metals in the 2+/3+ oxidation states, in
connection with various solvation approaches. In terms of model definition,
we investigate the construction of a minimally explicitly hydrated
quantum cluster with a first and second hydration layer. We report
on the convergence with respect to the coupled cluster expansion and
the PNO space, as well as on the role of perturbative triple excitations.
A recent implementation of the conductor-like polarizable continuum
model (CPCM) for the DLPNO-CC approach is employed to determine self-consistent
redox potentials at the coupled cluster level. Our results establish
conditions for the convergence of DLPNO-CCSD(T) energetics and stress
the absolute necessity to explicitly consider the second solvation
sphere even when CPCM is used. The achievable accuracy for redox potentials
of a practical DLPNO-based approach is, on average, 0.13 V. Furthermore,
multilayer approaches that combine a higher-level DLPNO-CCSD(T) description
of the first solvation sphere with a lower-level description of the
second solvation layer are investigated. The present work establishes
optimal and transferable methodological choices for employing DLPNO-based
coupled cluster theory, the associated CPCM implementation, and cost-efficient
multilayer derivatives of the approach for open-shell transition metal
systems in complex environments.
Experimental results on optically controlled non-equilibrium solvation dynamics show their dependence on excitation wavelength, l .ex However, the renowned Onsager regression hypothesis and Smoluchowski equation-based approach fail to explain such dependance. Failure of this theory prompted us to develop a novel theory by projecting the dynamics in a higherdimensional space onto a one-dimensional energy gap space, where the effect of l ex is included explicitly. We have then derived hierarchical equations of moments in time domain for an anharmonic potential based on the new kinetic equation derived here in the energy gap space to evaluate the non-equilibrium solvation time correlation function (NSTCF). The new methodlogy presented here also removes the difficulties in perturbative approaches to evaluate the NSTCF in a condensed phase. We have also shown that the NSTCF is independent of excitation wavelength for harmonic potential but dependent on the same for anharmonic potential, which is in accord with experimental observation. However, Onsager's regression hypothesis-based prediction for the NSTCF is independent of excitation wavelength for all kinds of potentials. More importantly, the calculated results of NSTCF is in excellent agreement with the experimental results where the Onsager regression hypothesis-based prediction fails.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.