Density Functional Theory Mechanistic Study of Ni-Catalyzed Reductive Alkyne–Alkyne Cyclodimerization: Oxidative Cyclization versus Outer-Sphere Proton Transfer

2020 ◽  
Vol 22 (6) ◽  
pp. 2454-2459 ◽  
Author(s):  
Xiaojian Ren ◽  
Yu Lu ◽  
Gang Lu ◽  
Zhi-Xiang Wang
Keyword(s):  
Density Functional Theory ◽  
Proton Transfer ◽  
Density Functional ◽  
Outer Sphere ◽  
Oxidative Cyclization ◽  
Mechanistic Study ◽  
Functional Theory

scholarly journals Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation

Micromachines ◽  
2021 ◽  
Vol 12 (6) ◽  
pp. 679
Author(s):  
Pouya Partovi-Azar ◽  
Daniel Sebastiani
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Proton Transfer ◽  
Density Functional ◽  
Photochemical Reactions ◽  
Transfer Energy ◽  
Functional Theory ◽  
Effective Potentials ◽  
Proton Dissociation ◽  
Dissociation Curves

Recently, a new method [P. Partovi-Azar and D. Sebastiani, J. Chem. Phys. 152, 064101 (2020)] was proposed to increase the efficiency of proton transfer energy calculations in density functional theory by using the T1 state with additional optimized effective potentials instead of calculations at S1. In this work, we focus on proton transfer from six prototypical photoacids to neighboring water molecules and show that the reference proton dissociation curves obtained at S1 states using time-dependent density functional theory can be reproduced with a reasonable accuracy by performing T1 calculations at density functional theory level with only one additional effective potential for the acidic hydrogens. We also find that the extra effective potentials for the acidic hydrogens neither change the nature of the T1 state nor the structural properties of solvent molecules upon transfer from the acids. The presented method is not only beneficial for theoretical studies on excited state proton transfer, but we believe that it would also be useful for studying other excited state photochemical reactions.

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