Analytical gradients for nuclear-electronic orbital multistate density functional theory: Geometry optimizations and reaction paths

Hydrogen tunneling plays a critical role in many biologically and chemically important processes. The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) method was developed to describe hydrogen transfer systems. In this approach, the transferring proton is treated quantum mechanically on the same level as the electrons within multicomponent DFT, and a nonorthogonal configuration interaction scheme is used to produce delocalized vibronic states from localized vibronic states. The NEO-MSDFT method has been shown to provide accurate hydrogen tunneling splittings for fixed molecular systems. Herein, the NEO-MSDFT analytical gradients for both ground and excited vibronic states are derived and implemented. The analytical gradients and semi-numerical Hessians are used to optimize and characterize equilibrium and transition state geometries and to generate minimum energy paths (MEPs), for proton transfer in the deprotonated acetylene dimer and malonaldehyde. The barriers along the resulting MEPs are lower when the transferring proton is quantized because the NEO-MSDFT method inherently includes the zero-point energy of the transferring proton. Analysis of the proton densities along the MEPs illustrates that the proton density can exhibit symmetric or asymmetric bilobal character associated with symmetric or slightly asymmetric double-well potential energy surfaces and hydrogen tunneling. Analysis of the contributions to the intrinsic reaction coordinate reveals that changes in the C-O bond lengths drive proton transfer in malonaldehyde. This work provides the foundation for future reaction path studies and direct nonadiabatic dynamics simulations of a wide range of hydrogen transfer reactions. Published under an exclusive license by AIP Publishing.

Automated summary

This study develops a nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) method to describe hydrogen transfer systems. The method is shown to accurately predict hydrogen tunneling splittings. The analytical gradients derived in this study are used to optimize geometries and generate reaction paths for proton transfer reactions. The results demonstrate that quantizing the transferring proton can lower the barrier of the reaction and the proton density and C-O bond lengths play important roles.