Electronic Transition Energies: A Study of the Performance of a Large Range of Single Reference Density Functional and Wave Function Methods on Valence and Rydberg States Compared to Experiment

Marco Caricato; Gary W Trucks; Michael J Frisch; Kenneth B Wiberg

doi:10.1021/ct9005129

Electronic Transition Energies: A Study of the Performance of a Large Range of Single Reference Density Functional and Wave Function Methods on Valence and Rydberg States Compared to Experiment

J Chem Theory Comput. 2010 Feb 9;6(2):370-83. doi: 10.1021/ct9005129. Epub 2010 Jan 22.

Authors

Marco Caricato¹, Gary W Trucks¹, Michael J Frisch¹, Kenneth B Wiberg¹

Affiliation

¹ Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06511 and Gaussian, Inc., 340 Quinnipiac. St Bldg. 40,Wallingford, Connecticut 06492.

PMID: 26617296
DOI: 10.1021/ct9005129

Abstract

This work reports a comparison among wave function and DFT single reference methods for vertical electronic transition energy calculations toward singlet states, valence and Rydberg in nature. A series of 11 small organic molecules are used as test cases, where accurate experimental data in gas phase are available. We compared CIS, RPA, CIS(D), EOM-CCSD, and 28 multipurpose density functionals of the type LSDA, GGA, M-GGA, H-GGA, HM-GGA and with separated short and long-range exchange. The list of functionals is obviously not complete, but it spans more than 20 years of DFT development and includes functionals which are commonly used in the computation of a variety of molecular properties. Large differences in the results were found between the various functionals. The aim of this work is therefore to shed some light on the performance of the plethora of functionals available and compare them with some traditional wave function based methods on a molecular property of large interest as the transition energy.