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Register a new userHybrid RHF/MP2 geometry optimizations with the Effective Fragment Molecular Orbital Method
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Added by
Anders S. Christensen
Publication date
2013
fields
Physics
and research's language is
English
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The frozen domain effective fragment molecular orbital method is extended to allow for the treatment of a single fragment at the MP2 level of theory. The approach is applied to the conversion of chorismate to prephenate by chorismate mutase, where the substrate is treated at the MP2 level of theory while the rest of the system is treated at the RHF level. MP2 geometry optimization is found to lower the barrier by up to 3.5 kcal/mol compared to RHF optimzations and ONIOM energy refinement and leads to a smoother convergence with respect to the basis set for the reaction profile. For double zeta basis sets the increase in CPU time relative to RHF is roughly a factor of two.
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The computational investigation of photochemical processes often entails the calculation of excited state geometries, energies, and energy gradients. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically protons, quantum mechanically on the same level as the electrons, thereby including the associated nuclear quantum effects and non-Born-Oppenheimer behavior into quantum chemistry calculations. The multicomponent density functional theory (NEO-DFT) and time-dependent DFT (NEO-TDDFT) methods allow efficient calculations of ground and excited states, respectively. Herein, the analytical gradients are derived and implemented for the NEO-TDDFT method and the associated Tamm-Dancoff approximation (NEO-TDA). The programmable equations for these analytical gradients, as well as the NEO-DFT analytical Hessian, are provided. The NEO approach includes the anharmonic zero-point energy and density delocalization associated with the quantum protons, as well as vibronic mixing, in geometry optimizations and energy calculations of ground and excited states. The harmonic zero-point energy associated with the other nuclei can be computed via the NEO Hessian. This approach is used to compute the 0-0 adiabatic excitation energies for a set of nine small molecules with all protons quantized, exhibiting slight improvement over the conventional electronic approach. Geometry optimizations of two excited state intramolecular proton transfer systems are performed with one and two quantized protons, respectively. The NEO calculations for these systems produce electronically excited state geometries with stronger intramolecular hydrogen bonds and similar relative stabilities compared to conventional electronic methods. This work provides the foundation for nonadiabatic dynamics simulations of fundamental processes such as photoinduced proton transfer and proton-coupled electron transfer.
Perdew-Zunger self-interaction correction (PZ-SIC) offers a route to remove self-interaction errors on an orbital-by-orbital basis. A recent formulation of PZ-SIC by Pederson, Ruzsinszky and Perdew proposes restricting the unitary transformation to localized orbitals called Fermi-Lowdin orbitals. This formulation, called the FLOSIC method, simplifies PZ-SIC calculations and was implemented self-consistently using a Jacobi-like (FLOSIC-Jacobi) iteration scheme. In this work we implement the FLOSIC approach using the Krieger-Li-Iafrate (KLI) approximation to the optimized effective potential (OEP). We compare the results of present FLOSIC-KLI approach with FLOSIC-Jacobi scheme for atomic energies, atomization energies, ionization energies, barrier heights, polarizability of chains of hydrogen molecules etc. to validate the FLOSIC-KLI approach. The FLOSIC-KLI approach, which is within the realm of Kohn-Sham theory, predicts smaller energy gaps between frontier orbitals due to the lowering of eigenvalues of the lowest unoccupied orbitals. Results show that atomic energies, atomization energies, ionization energy as an absolute of highest occupied orbital eigenvalue, and polarizability of chains of hydrogen molecules between the two methods agree within 2%. Finally the FLOSIC-KLI approach is used to determine the vertical ionization energies of water clusters.
Recent synthetic studies on the organic molecules tetracene and pentacene have found certain dimers and oligomers to exhibit an intense absorption in the visible region of the spectrum which is not present in the monomer or many previously-studied dimers. In this article we combine experimental synthesis with electronic structure theory and spectral computation to show that this absorption arises from an otherwise dark charge-transfer excitation borrowing intensity from an intense UV excitation. Further, by characterizing the role of relevant monomer molecular orbitals, we arrive at a design principle that allows us to predict the presence or absence of an additional absorption based on the bonding geometry of the dimer. We find this rule correctly explains the spectra of a wide range of acene derivatives and solves an unexplained structure-spectrum phenomenon first observed seventy years ago. These results pave the way for the design of highly absorbent chromophores with applications ranging from photovoltaics to liquid crystals.
Using the effective rotational Hamiltonian method, we have conducted an analysis of the D218O ground and the first excited vibration state rotational energy levels. The analysis was based on the effective Hamiltonians represented in several forms: the Watson Hamiltonian, the Hamiltonian expressed in terms of Pade-Borel approximants, and the Hamiltonian in terms of generating function expansions. The rotational and centrifugal constants have been determined from the fitting, which describe the rotational energy levels with an accuracy close to that of the experimental data. The predictive performance of the model with respect to highly excited rotational states has been evaluated against the global variation calculations. The radii of convergence of the effective rotation Hamiltonian series have been determined.
Density functional theory (DFT) and beyond-DFT methods are often used in combination with photoelectron spectroscopy to obtain physical insights into the electronic structure of molecules and solids. The Kohn-Sham eigenvalues are not electron removal energies except for the highest occupied orbital. The eigenvalues of the highest occupied molecular orbitals often underestimate the electron removal or ionization energies due to the self-interaction (SI) errors in approximate density functionals. In this work, we adapt and implement the density-consistent effective potential(DCEP) method of Kohut, Ryabinkin, and Staroverov to obtain SI corrected local effective potentials from the SI corrected Fermi-Lowdin orbitals and density in the FLOSIC scheme. The implementation is used to obtain the density of states (photoelectron spectra) and HOMO-LUMO gaps for a set of molecules and polyacenes. Good agreement with experimental values is obtained compared to a range of SI uncorrected density functional approximations.
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