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Spectroscopy and Photochemistry; General Theory
Variational Formulation of the Generalized Many-Body Expansion with Self-Consistent Charge Embedding: Simple and Correct Analytic Energy Gradient for Fragment-Based ab Initio Molecular Dynamics Jie Liu, Bhaskar Rana, Kuan-Yu Liu, and John M. Herbert J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.9b01214 • Publication Date (Web): 06 Jun 2019 Downloaded from http://pubs.acs.org on June 7, 2019
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The Journal of Physical Chemistry Letters
Variational Formulation of the Generalized Many-Body Expansion with Self-Consistent Charge Embedding: Simple and Correct Analytic Energy Gradient for Fragment-Based ab Initio Molecular Dynamics Jie Liu,∗ Bhaskar Rana, Kuan-Yu Liu, and John M. Herbert† Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210 (Dated: June 5, 2019) The many-body expansion (MBE) and its extension to overlapping fragments, the generalized (G)MBE, constitute the theoretical basis for most fragment-based approaches for large-scale quantum chemistry. We reformulate the GMBE for use with embedding charges determined selfconsistently from the fragment wave functions, in a manner that preserves the variational nature of the underlying self-consistent field method. As a result, the analytic gradient retains the simple “sum of fragment gradients” form that is often assumed in practice, sometimes incorrectly. This obviates (without approximation) the need to solve coupled-perturbed equations, and we demonstrate stable, fragment-based ab initio molecular dynamics simulations using this technique. Energy conservation fails when charge-response contributions to the Fock matrix are neglected, even while geometry optimizations and vibrational frequency calculations may yet be accurate. Stable simulations can be recovered by means of straightforward modifications introduced here, providing a general paradigm for fragment-based ab initio molecular dynamics.
∗ Present
address: Hefei National Laboratory of Physical Science at the Microscale, University of Science and Technology of China, Anhui 230026, China †
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The Journal of Physical Chemistry Letters
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energy
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The Journal of Physical Chemistry Letters
3 Fragment methods1–3 provide a practical and intuitive means to reduce the computational scaling of ab initio quantum chemistry. The common idea amongst these methods is decomposition of a large (super)system into smaller subsystems. Numerous subsystem electronic structure calculations, which are trivially parallelizable, are then used to approximate the total energy or other properties of the supersystem. An appealing application of these methods is ab initio molecular dynamics (AIMD) of liquid water, where fragment-based approaches have recently been used to perform simulations at correlated wave function levels of theory.4–7 In an attempt to improve accuracy by capturing many-body polarization, fragment methods often embed the subsystem calculations in a classical electrostatic representation of the entire supersystem, using atomic point charges derived from the fragment wave functions.8–14 In principle these embedding charges should be iteratively updated in order to reflect changes in the fragment wave functions,8–11 however self-consistency significantly complicates the formulation of analytic energy gradients by introducing response terms that describe how the embedding charges respond to changes in the wave functions.9,10 In practice these response terms are often neglected,8,11,13,15–18 meaning that the putative fragment-based analytic gradient is formally incorrect insofar as it is not the derivative of the corresponding fragment-based energy expression. It has been argued that these terms are numerically small,13 and their neglect has been justified a posteriori by noting that fragmentbased geometry optimizations and harmonic frequency calculations accurately approximate supersystem results.13,15–17,19–21 There do exist fragment-based methods for which correct analytic gradients have been reported with self-consistent electrostatic embedding.9,10,22–25 However, these methods are formulated in such a way that the embedding compromises the variational nature of the underlying self-consistent field (SCF) method, and therefore a correct analytic gradient therefore requires solution of coupled-perturbed equations, which is ordinarily not required for SCF first derivatives.26 A notable example is the fragment molecular orbital (FMO) method,27–31 the most widely-used fragment-based approach. First proposed in 1999,32 with an approximate analytic gradient reported soon thereafter,33 various pieces of the gradient were developed subsequently,34–38 until finally in 2011 the exact analytic gradient was reported.22–24 Notably, inclusion of the response terms is found to improve energy conservation in
AIMD simulations.39 That said, the long delay in reporting the exact analytic gradient for FMO is a testament to its complexity, and motivates our attempt to simply the formalism. In the present work, we introduce an alternative to FMO that satisfies a variational principle and therefore obviates the need to solve coupled-perturbed equations, without sacrificing a rigorously correct energy gradient. Most fragment-based approaches, including FMO, rely at some level upon a many-body expansion (MBE) of the supersystem energy:40,41 X X X E= EA + ∆EAB + ∆EABC + · · · . A
A
