Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory

Gray, Montgomery; Herbert, John M.

doi:10.1063/5.0059364

Title: Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory

Journal Article · Thu Jul 15 00:00:00 UTC 2021 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0059364 · OSTI ID:1833484

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The Ohio State Univ., Columbus, OH (United States); The Ohio State University
The Ohio State Univ., Columbus, OH (United States)

Long considered a failure, second-order symmetry-adapted perturbation theory (SAPT) based on Kohn–Sham orbitals, or SAPT0(KS), can be resurrected for semiquantitative purposes using long-range corrected density functionals whose asymptotic behavior is adjusted separately for each monomer. Here, as in other contexts, correct asymptotic behavior can be enforced via “optimal tuning” based on the ionization energy theorem of density functional theory, but the tuning procedure is tedious, expensive for large systems, and comes with a troubling dependence on system size. Here, we show that essentially identical results are obtained using a fast, convenient, and automated tuning procedure based on the size of the exchange hole. In conjunction with “extended” (X)SAPT methods that improve the description of dispersion, this procedure achieves benchmark-quality interaction energies, along with the usual SAPT energy decomposition, without the hassle of system-specific tuning.

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Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008550

OSTI ID:: 1833484

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 3 Vol. 155; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (75)

Charge-Transfer Excitations: A Challenge for Time-Dependent Density Functional Theory That Has Been Met Kümmel, Stephan Advanced Energy Materials, Vol. 7, Issue 16 https://doi.org/10.1002/aenm.201700440	journal	May 2017
Fully ab initio protein-ligand interaction energies with dispersion corrected density functional theory Antony, Jens; Grimme, Stefan Journal of Computational Chemistry, Vol. 33, Issue 21 https://doi.org/10.1002/jcc.23004	journal	May 2012
Nine questions on energy decomposition analysis Andrés, Juan; Ayers, Paul W.; Boto, Roberto A. Journal of Computational Chemistry, Vol. 40, Issue 26 https://doi.org/10.1002/jcc.26003	journal	June 2019
Symmetry‐adapted perturbation theory based on density functional theory for noncovalent interactions Jansen, Georg Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 2 https://doi.org/10.1002/wcms.1164	journal	August 2013
Recent developments in symmetry‐adapted perturbation theory Patkowski, Konrad WIREs Computational Molecular Science, Vol. 10, Issue 3 https://doi.org/10.1002/wcms.1452	journal	November 2019
Wavefunction methods for noncovalent interactions: Noncovalent interactions Hohenstein, Edward G.; Sherrill, C. David Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.84	journal	July 2011
Symmetry-adapted perturbation theory of intermolecular forces: Symmetry-adapted perturbation theory Szalewicz, Krzysztof Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.86	journal	August 2011
Intermolecular Interactions via Perturbation Theory: From Diatoms to Biomolecules Szalewicz, Krzysztof; Patkowski, Konrad; Jeziorski, Bogumil Intermolecular Forces and Clusters II https://doi.org/10.1007/430_004	book	October 2005
Efficient Monomer-Based Quantum Chemistry Methods for Molecular and Ionic Clusters Jacobson, Leif D.; Richard, Ryan M.; Lao, Ka Un Annual Reports in Computational Chemistry https://doi.org/10.1016/b978-0-444-62672-1.00002-9	book	January 2013
Efficient calculation of coupled Kohn–Sham dynamic susceptibility functions and dispersion energies with density fitting Bukowski, Robert; Podeszwa, Rafał; Szalewicz, Krzysztof Chemical Physics Letters, Vol. 414, Issue 1-3 https://doi.org/10.1016/j.cplett.2005.08.048	journal	October 2005
Intermolecular forces from asymptotically corrected density functional description of monomers Misquitta, Alston J.; Szalewicz, Krzysztof Chemical Physics Letters, Vol. 357, Issue 3-4 https://doi.org/10.1016/s0009-2614(02)00533-x	journal	May 2002
First-order intermolecular interaction energies from Kohn–Sham orbitals Heßelmann, Andreas; Jansen, Georg Chemical Physics Letters, Vol. 357, Issue 5-6 https://doi.org/10.1016/s0009-2614(02)00538-9	journal	May 2002
Intermolecular induction and exchange-induction energies from coupled-perturbed Kohn–Sham density functional theory Heßelmann, Andreas; Jansen, Georg Chemical Physics Letters, Vol. 362, Issue 3-4 https://doi.org/10.1016/s0009-2614(02)01097-7	journal	August 2002
Chemical content of the kinetic energy density Schmider, H. L.; Becke, A. D. Journal of Molecular Structure: THEOCHEM, Vol. 527, Issue 1-3 https://doi.org/10.1016/s0166-1280(00)00477-2	journal	August 2000
Energy Decomposition Analysis with a Stable Charge-Transfer Term for Interpreting Intermolecular Interactions Lao, Ka Un; Herbert, John M. Journal of Chemical Theory and Computation, Vol. 12, Issue 6 https://doi.org/10.1021/acs.jctc.6b00155	journal	May 2016
Size-Dependence of Nonempirically Tuned DFT Starting Points for G ₀ W ₀ Applied to π-Conjugated Molecular Chains Bois, Juliana; Körzdörfer, Thomas Journal of Chemical Theory and Computation, Vol. 13, Issue 10 https://doi.org/10.1021/acs.jctc.7b00557	journal	September 2017
Atomic Orbital Implementation of Extended Symmetry-Adapted Perturbation Theory (XSAPT) and Benchmark Calculations for Large Supramolecular Complexes Lao, Ka Un; Herbert, John M. Journal of Chemical Theory and Computation, Vol. 14, Issue 6 https://doi.org/10.1021/acs.jctc.8b00058	journal	April 2018
A Simple Correction for Nonadditive Dispersion within Extended Symmetry-Adapted Perturbation Theory (XSAPT) Lao, Ka Un; Herbert, John M. Journal of Chemical Theory and Computation, Vol. 14, Issue 10 https://doi.org/10.1021/acs.jctc.8b00527	journal	August 2018
Charge Separation and Charge Transfer in the Low-Lying Excited States of Pentacene Alam, Bushra; Morrison, Adrian F.; Herbert, John M. The Journal of Physical Chemistry C, Vol. 124, Issue 45 https://doi.org/10.1021/acs.jpcc.0c07932	journal	October 2020
Accurate and Efficient ab Initio Calculations for Supramolecular Complexes: Symmetry-Adapted Perturbation Theory with Many-Body Dispersion Carter-Fenk, Kevin; Lao, Ka Un; Liu, Kuan-Yu The Journal of Physical Chemistry Letters, Vol. 10, Issue 11 https://doi.org/10.1021/acs.jpclett.9b01156	journal	May 2019
Explicit Polarization: A Quantum Mechanical Framework for Developing Next Generation Force Fields Gao, Jiali; Truhlar, Donald G.; Wang, Yingjie Accounts of Chemical Research, Vol. 47, Issue 9 https://doi.org/10.1021/ar5002186	journal	July 2014
Time-Dependent Density-Functional Description of the ¹ L _a State in Polycyclic Aromatic Hydrocarbons: Charge-Transfer Character in Disguise? Richard, Ryan M.; Herbert, John M. Journal of Chemical Theory and Computation, Vol. 7, Issue 5 https://doi.org/10.1021/ct100607w	journal	April 2011
Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions Papajak, Ewa; Zheng, Jingjing; Xu, Xuefei Journal of Chemical Theory and Computation, Vol. 7, Issue 10 https://doi.org/10.1021/ct200106a	journal	August 2011
S66: A Well-balanced Database of Benchmark Interaction Energies Relevant to Biomolecular Structures Řezáč, Jan; Riley, Kevin E.; Hobza, Pavel Journal of Chemical Theory and Computation, Vol. 7, Issue 8 https://doi.org/10.1021/ct2002946	journal	July 2011
Accuracy of Quantum Chemical Methods for Large Noncovalent Complexes Sedlak, Robert; Janowski, Tomasz; Pitoňák, Michal Journal of Chemical Theory and Computation, Vol. 9, Issue 8 https://doi.org/10.1021/ct400036b	journal	July 2013
Application of Diffusion Monte Carlo to Materials Dominated by van der Waals Interactions Benali, Anouar; Shulenburger, Luke; Romero, Nichols A. Journal of Chemical Theory and Computation, Vol. 10, Issue 8 https://doi.org/10.1021/ct5003225	journal	June 2014
Oligoacenes: Theoretical Prediction of Open-Shell Singlet Diradical Ground States Bendikov, Michael; Duong, Hieu M.; Starkey, Kyle Journal of the American Chemical Society, Vol. 126, Issue 24 https://doi.org/10.1021/ja048919w	journal	June 2004
Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theory Stein, Tamar; Kronik, Leeor; Baer, Roi Journal of the American Chemical Society, Vol. 131, Issue 8 https://doi.org/10.1021/ja8087482	journal	March 2009
Both Intra- and Interstrand Charge-Transfer Excited States in Aqueous B-DNA Are Present at Energies Comparable To, or Just Above, the ¹ ππ* Excitonic Bright States Lange, Adrian W.; Herbert, John M. Journal of the American Chemical Society, Vol. 131, Issue 11 https://doi.org/10.1021/ja808998q	journal	March 2009
Using Kohn−Sham Orbitals in Symmetry-Adapted Perturbation Theory to Investigate Intermolecular Interactions Williams, Hayes L.; Chabalowski, Cary F. The Journal of Physical Chemistry A, Vol. 105, Issue 3 https://doi.org/10.1021/jp003883p	journal	January 2001
Comment on “Using Kohn−Sham Orbitals in Symmetry-Adapted Perturbation Theory To Investigate Intermolecular Interactions” Jansen, Georg; Hesselmann, Andreas The Journal of Physical Chemistry A, Vol. 105, Issue 49 https://doi.org/10.1021/jp0112774	journal	December 2001
Ab Initio Quantum Chemistry for Protein Structures Kulik, Heather J.; Luehr, Nathan; Ufimtsev, Ivan S. The Journal of Physical Chemistry B, Vol. 116, Issue 41 https://doi.org/10.1021/jp307741u	journal	October 2012
The Charge Transfer Problem in Density Functional Theory Calculations of Aqueously Solvated Molecules Isborn, Christine M.; Mar, Brendan D.; Curchod, Basile F. E. The Journal of Physical Chemistry B, Vol. 117, Issue 40 https://doi.org/10.1021/jp4058274	journal	October 2013
Density-Dependent Onset of the Long-Range Exchange: A Key to Donor–Acceptor Properties Modrzejewski, Marcin; Rajchel, Łukasz; Chalasinski, Grzegorz The Journal of Physical Chemistry A, Vol. 117, Issue 45 https://doi.org/10.1021/jp4088404	journal	November 2013
Optical Spectroscopy of the Bulk and Interfacial Hydrated Electron from Ab Initio Calculations Uhlig, Frank; Herbert, John M.; Coons, Marc P. The Journal of Physical Chemistry A, Vol. 118, Issue 35 https://doi.org/10.1021/jp5004243	journal	March 2014
Impact of Electron Delocalization on the Nature of the Charge-Transfer States in Model Pentacene/C ₆₀ Interfaces: A Density Functional Theory Study Yang, Bing; Yi, Yuanping; Zhang, Cai-Rong The Journal of Physical Chemistry C, Vol. 118, Issue 48 https://doi.org/10.1021/jp5074076	journal	November 2014
Accurate and Efficient Quantum Chemistry Calculations for Noncovalent Interactions in Many-Body Systems: The XSAPT Family of Methods Lao, Ka Un; Herbert, John M. The Journal of Physical Chemistry A, Vol. 119, Issue 2 https://doi.org/10.1021/jp5098603	journal	December 2014
Charge-Transfer Excited States in a π-Stacked Adenine Dimer, As Predicted Using Long-Range-Corrected Time-Dependent Density Functional Theory Lange, Adrian W.; Rohrdanz, Mary A.; Herbert, John M. The Journal of Physical Chemistry B, Vol. 112, Issue 20 https://doi.org/10.1021/jp802058k	journal	May 2008
Accurate Intermolecular Interactions at Dramatically Reduced Cost: XPol+SAPT with Empirical Dispersion Lao, Ka Un; Herbert, John M. The Journal of Physical Chemistry Letters, Vol. 3, Issue 22 https://doi.org/10.1021/jz301015p	journal	October 2012
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Rapid computation of intermolecular interactions in molecular and ionic clusters: self-consistent polarization plus symmetry-adapted perturbation theory Herbert, John M.; Jacobson, Leif D.; Un Lao, Ka Physical Chemistry Chemical Physics, Vol. 14, Issue 21 https://doi.org/10.1039/c2cp24060b	journal	January 2012
Energy decomposition analysis approaches and their evaluation on prototypical protein–drug interaction patterns Phipps, Maximillian J. S.; Fox, Thomas; Tautermann, Christofer S. Chemical Society Reviews, Vol. 44, Issue 10 https://doi.org/10.1039/c4cs00375f	journal	January 2015
Reinterpreting π-stacking Carter-Fenk, Kevin; Herbert, John M. Physical Chemistry Chemical Physics, Vol. 22, Issue 43 https://doi.org/10.1039/d0cp05039c	journal	January 2020
Shape corrections to exchange-correlation potentials by gradient-regulated seamless connection of model potentials for inner and outer region Grüning, M.; Gritsenko, O. V.; van Gisbergen, S. J. A. The Journal of Chemical Physics, Vol. 114, Issue 2 https://doi.org/10.1063/1.1327260	journal	January 2001
Density-functional theory-symmetry-adapted intermolecular perturbation theory with density fitting: A new efficient method to study intermolecular interaction energies Heßelmann, A.; Jansen, G.; Schütz, M. The Journal of Chemical Physics, Vol. 122, Issue 1 https://doi.org/10.1063/1.1824898	journal	January 2005
Exchange-hole dipole moment and the dispersion interaction Becke, Axel D.; Johnson, Erin R. The Journal of Chemical Physics, Vol. 122, Issue 15 https://doi.org/10.1063/1.1884601	journal	April 2005
Symmetry-adapted perturbation-theory calculations of intermolecular forces employing density-functional description of monomers Misquitta, Alston J.; Szalewicz, Krzysztof The Journal of Chemical Physics, Vol. 122, Issue 21 https://doi.org/10.1063/1.1924593	journal	June 2005
Simultaneous benchmarking of ground- and excited-state properties with long-range-corrected density functional theory Rohrdanz, Mary A.; Herbert, John M. The Journal of Chemical Physics, Vol. 129, Issue 3 https://doi.org/10.1063/1.2954017	journal	July 2008
A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states Rohrdanz, Mary A.; Martins, Katie M.; Herbert, John M. The Journal of Chemical Physics, Vol. 130, Issue 5 https://doi.org/10.1063/1.3073302	journal	February 2009
Property-optimized Gaussian basis sets for molecular response calculations Rappoport, Dmitrij; Furche, Filipp The Journal of Chemical Physics, Vol. 133, Issue 13 https://doi.org/10.1063/1.3484283	journal	October 2010
An efficient, fragment-based electronic structure method for molecular systems: Self-consistent polarization with perturbative two-body exchange and dispersion Jacobson, Leif D.; Herbert, John M. The Journal of Chemical Physics, Vol. 134, Issue 9 https://doi.org/10.1063/1.3560026	journal	March 2011
Long-range corrected hybrid functionals for π-conjugated systems: Dependence of the range-separation parameter on conjugation length Körzdörfer, Thomas; Sears, John S.; Sutton, Christopher The Journal of Chemical Physics, Vol. 135, Issue 20 https://doi.org/10.1063/1.3663856	journal	November 2011
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
A simple measure of electron localization in atomic and molecular systems Becke, A. D.; Edgecombe, K. E. The Journal of Chemical Physics, Vol. 92, Issue 9 https://doi.org/10.1063/1.458517	journal	May 1990
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
Improving virtual Kohn–Sham orbitals and eigenvalues: Application to excitation energies and static polarizabilities Tozer, David J.; Handy, Nicholas C. The Journal of Chemical Physics, Vol. 109, Issue 23 https://doi.org/10.1063/1.477711	journal	December 1998
An improved treatment of empirical dispersion and a many-body energy decomposition scheme for the explicit polarization plus symmetry-adapted perturbation theory (XSAPT) method Lao, Ka Un; Herbert, John M. The Journal of Chemical Physics, Vol. 139, Issue 3 https://doi.org/10.1063/1.4813523	journal	July 2013
Symmetry-adapted perturbation theory with Kohn-Sham orbitals using non-empirically tuned, long-range-corrected density functionals Lao, Ka Un; Herbert, John M. The Journal of Chemical Physics, Vol. 140, Issue 4 https://doi.org/10.1063/1.4862644	journal	January 2014
Long-range correlation energy calculated from coupled atomic response functions Ambrosetti, Alberto; Reilly, Anthony M.; DiStasio, Robert A. The Journal of Chemical Physics, Vol. 140, Issue 18 https://doi.org/10.1063/1.4865104	journal	May 2014
Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies Parker, Trent M.; Burns, Lori A.; Parrish, Robert M. The Journal of Chemical Physics, Vol. 140, Issue 9 https://doi.org/10.1063/1.4867135	journal	March 2014
Erratum: “An improved treatment of empirical dispersion and a many-body energy decomposition scheme for the explicit polarization plus symmetry-adapted perturbation theory (XSAPT) method” [J. Chem. Phys. 139, 034107 (2013)] Lao, Ka Un; Herbert, John M. The Journal of Chemical Physics, Vol. 140, Issue 11 https://doi.org/10.1063/1.4869543	journal	March 2014
Charge-transfer excitations in low-gap systems under the influence of solvation and conformational disorder: Exploring range-separation tuning de Queiroz, Thiago B.; Kümmel, Stephan The Journal of Chemical Physics, Vol. 141, Issue 8 https://doi.org/10.1063/1.4892937	journal	August 2014
Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory Hapka, Michał; Rajchel, Łukasz; Modrzejewski, Marcin The Journal of Chemical Physics, Vol. 141, Issue 13 https://doi.org/10.1063/1.4896608	journal	October 2014
Self-consistent charge embedding at very low cost, with application to symmetry-adapted perturbation theory Liu, Kuan-Yu; Carter-Fenk, Kevin; Herbert, John M. The Journal of Chemical Physics, Vol. 151, Issue 3 https://doi.org/10.1063/1.5111869	journal	July 2019
Coupled cluster benchmarks of large noncovalent complexes: The L7 dataset as well as DNA–ellipticine and buckycatcher–fullerene Ballesteros, Francisco; Dunivan, Shelbie; Lao, Ka Un The Journal of Chemical Physics, Vol. 154, Issue 15 https://doi.org/10.1063/5.0042906	journal	April 2021
Nature of ground and electronic excited states of higher acenes Yang, Yang; Davidson, Ernest R.; Yang, Weitao Proceedings of the National Academy of Sciences, Vol. 113, Issue 35 https://doi.org/10.1073/pnas.1606021113	journal	August 2016
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
Difficulties in applying pure Kohn–Sham density functional theory electronic structure methods to protein molecules Rudberg, Elias Journal of Physics: Condensed Matter, Vol. 24, Issue 7 https://doi.org/10.1088/0953-8984/24/7/072202	journal	January 2012
Electrostatic considerations affecting the calculated HOMO–LUMO gap in protein molecules Lever, Greg; Cole, Daniel J.; Hine, Nicholas D. M. Journal of Physics: Condensed Matter, Vol. 25, Issue 15 https://doi.org/10.1088/0953-8984/25/15/152101	journal	March 2013
Applications of large-scale density functional theory in biology Cole, Daniel J.; Hine, Nicholas D. M. Journal of Physics: Condensed Matter, Vol. 28, Issue 39 https://doi.org/10.1088/0953-8984/28/39/393001	journal	August 2016
Exchange-correlation potential with correct asymptotic behavior van Leeuwen, R.; Baerends, E. J. Physical Review A, Vol. 49, Issue 4 https://doi.org/10.1103/physreva.49.2421	journal	April 1994
Accurate and Efficient Method for Many-Body van der Waals Interactions Tkatchenko, Alexandre; DiStasio, Robert A.; Car, Roberto Physical Review Letters, Vol. 108, Issue 23 https://doi.org/10.1103/physrevlett.108.236402	journal	June 2012
Do Semilocal Density-Functional Approximations Recover Dispersion Energies at Small Intermonomer Separations? Shahbaz, Muhammad; Szalewicz, Krzysztof Physical Review Letters, Vol. 121, Issue 11 https://doi.org/10.1103/physrevlett.121.113402	journal	September 2018
Tuned Range-Separated Hybrids in Density Functional Theory Baer, Roi; Livshits, Ester; Salzner, Ulrike Annual Review of Physical Chemistry, Vol. 61, Issue 1 https://doi.org/10.1146/annurev.physchem.012809.103321	journal	March 2010
A Teenager and his Mother Horowitz, Sandra Journal of Clinical Sleep Medicine, Vol. 10, Issue 12 https://doi.org/10.5664/jcsm.4302	journal	December 2014

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Title: Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory

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