Calculations of n→π Transition Energies: Comparisons Between TD-DFT, ADC, CC, CASPT2, and BSE/GW Descriptions

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2017-08, Vol.121 (32), p.6122-6134
• Main Authors: Azarias, Cloé, Habert, Chloé, Budzák, Šimon, Blase, Xavier, Duchemin, Ivan, Jacquemin, Denis
• Format: Article
• Language: English
• Subjects: Condensed Matter; Physics
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.7b05222

Using a large panel of theoretical approaches, namely, CC2, CCSD, CCSDR(3), CC3, ADC(2), ADC(3), CASPT2, time-dependent density functional theory (TD-DFT), and BSE/evGW, the two latter combined with different exchange-correlation functionals, we investigate the lowest singlet transition in 23 n→π* compounds based on the nitroso, thiocarbonyl, carbonyl, and diazo chromophores. First, for 16 small derivatives we compare the transition energies provided by the different wave function approaches to define theoretical best estimates. For this set, it surprisingly turned out that ADC(2) offers a better match with CC3 than ADC(3). Next, we use 10 functionals belonging to the “LYP” and “M06” families and compare the TD-DFT and the BSE/evGW descriptions. The BSE/evGW results are less sensitive than their TD-DFT counterparts to the selected functional, especially in the M06 series. Nevertheless, BSE/evGW delivers larger errors than TD-CAM-B3LYP, which provides extremely accurate results in the present case, especially when the Tamm–Dancoff approximation is applied. In addition, we show that, among the different starting points for BSE/evGW calculations, M06-2X eigenstates stand as the most appropriate. Finally, we confirm that the trends observed on the small compounds pertain in larger molecules.