Spin-Scaled Range-Separated Double-Hybrid Density Functional Theory for Excited States

Overview

Journal J Chem Theory Comput

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2021 Jun 21

PMID 34152771

Citations 11

Authors

David Mester

Mihaly Kallay

Affiliations

Soon will be listed here.

Abstract

Our recently presented range-separated (RS) double-hybrid (DH) time-dependent density functional approach [ 927 (2021)] is combined with spin-scaling techniques. The proposed spin-component-scaled (SCS) and scaled-opposite-spin (SOS) variants are thoroughly tested for almost 500 excitations including the most challenging types. This comprehensive study provides useful information not only about the new approaches but also about the most prominent methods in the DH class. The benchmark calculations confirm the robustness of the RS-DH ansatz, while several tendencies and deficiencies are pointed out for the existing functionals. Our results show that the SCS variant consistently improves the results, while the SOS variant preserves the benefits of the original RS-DH method reducing its computational expenses. It is also demonstrated that, besides our approaches, only the nonempirical functionals provide balanced performance for general applications, while particular methods are only suggested for certain types of excitations.

Citing Articles

Overview of Developments in the MRCC Program System.

Mester D, Nagy P, Csoka J, Gyevi-Nagy L, Szabo P, Horvath R J Phys Chem A. 2025; 129(8):2086-2107.

PMID: 39957179 PMC: 11874011. DOI: 10.1021/acs.jpca.4c07807.

Noncovalently bound excited-state dimers: a perspective on current time-dependent density functional theory approaches applied to aromatic excimer models.

Hancock A, Goerigk L RSC Adv. 2023; 13(51):35964-35984.

PMID: 38090083 PMC: 10712016. DOI: 10.1039/d3ra07381e.

Performance Tests of the Second-Order Approximate Internally Contracted Multireference Coupled-Cluster Singles and Doubles Method icMRCC2.

Zielinski P, Black J, Kohn A J Chem Theory Comput. 2023; 19(23):8671-8688.

PMID: 37991987 PMC: 10720349. DOI: 10.1021/acs.jctc.3c00969.

Vertical Ionization Potentials and Electron Affinities at the Double-Hybrid Density Functional Level.

Mester D, Kallay M J Chem Theory Comput. 2023; 19(13):3982-3995.

PMID: 37326360 PMC: 10339736. DOI: 10.1021/acs.jctc.3c00363.

Assessing Recent Time-Dependent Double-Hybrid Density Functionals on Doublet-Doublet Excitations.

Van Dijk J, Casanova-Paez M, Goerigk L ACS Phys Chem Au. 2023; 2(5):407-416.

PMID: 36855692 PMC: 9955292. DOI: 10.1021/acsphyschemau.2c00014.

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