Natural Charge-Transfer Analysis: Eliminating Spurious Charge-Transfer States in Time-Dependent Density Functional Theory via Diabatization, with Application to Projection-Based Embedding

Carter-Fenk, Kevin D.; Mundy, Christopher J.; Herbert, John M.

doi:10.1021/acs.jctc.1c00412

Title: Natural Charge-Transfer Analysis: Eliminating Spurious Charge-Transfer States in Time-Dependent Density Functional Theory via Diabatization, with Application to Projection-Based Embedding

Journal Article · Tue Jul 13 00:00:00 EDT 2021 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.1c00412· OSTI ID:1819935

Carter-Fenk, Kevin D. ^[1]; Mundy, Christopher J. ^[2]; Herbert, John M. ^[1]

Ohio State University
BATTELLE (PACIFIC NW LAB)

For many types of vertical excitation energies, linear-response time-dependent density functional theory (LR-TDDFT) offers a useful degree of accuracy combined with unrivaled computational efficiency, although charge-transfer excitation energies are often systematically and dramatically underestimated, especially for large systems and those that contain explicit solvent. As a result, low energy electronic spectra of solution-phase chromophores often contain tens to hundreds of spurious charge-transfer states, making LR-TDDFT needlessly expensive in bulk solution. More nefariously, intensity borrowing by the low-energy charge-transfer states can affect intensities of the valence excitations even if those excitation energies are accurate. At higher excitation energies, it is difficult to distinguish spurious CT states from genuine charge-transfer-to-solvent (CTTS) excitations. In this work, we introduce an automated diabatization scheme that enables fast and effective screening of the CTTS acceptor space in bulk solution. Our procedure introduces the concept of “natural charge-transfer orbitals”, which provide a means to isolate characteristic pairs of orbitals that are most likely to participate in a CTTS excitation. The projection of these orbitals onto solvent-centered virtual orbitals provides a criterion for defining the most important solvent molecules in a given excitation. We apply this method to analyze an ab initio molecular dynamics (MD) trajectory of I-(aq) and report the lowest-energy CTTS band in the absorption spectrum. Our results are in excellent agreement with experimental measurements for bulk I-(aq), and only one-third of the water molecules in the I-(H2O)96 simulation cell need to be described with LR-TDDFT in order to obtain excitation energies that are converged to < 0.1 eV. The tools introduced herein will improve the accuracy, efficiency, and usability of LR-TDDFT in solution-phase environments

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1819935

Report Number(s):: PNNL-SA-161769

Journal Information:: Journal of Chemical Theory and Computation, Vol. 17, Issue 7

Country of Publication:: United States

Language:: English

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