Electronic spectra from TDDFT and machine learning in chemical space

Ramakrishnan, Raghunathan and Hartmann, Mia and Tapavicza, Enrico and von Lilienfeld, O. Anatole. (2015) Electronic spectra from TDDFT and machine learning in chemical space. Journal of Chemical Physics, 143 (8). 084111.

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Official URL: http://edoc.unibas.ch/43349/

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Due to its favorable computational efficiency, time-dependent (TD) density functional theory (DFT) enables the prediction of electronic spectra in a high-throughput manner across chemical space. Its predictions, however, can be quite inaccurate. We resolve this issue with machine learning models trained on deviations of reference second-order approximate coupled-cluster (CC2) singles and doubles spectra from TDDFT counterparts, or even from DFT gap. We applied this approach to low-lying singlet-singlet vertical electronic spectra of over 20 000 synthetically feasible small organic molecules with up to eight CONF atoms. The prediction errors decay monotonously as a function of training set size. For a training set of 10 000 molecules, CC2 excitation energies can be reproduced to within ±0.1 eV for the remaining molecules. Analysis of our spectral database via chromophore counting suggests that even higher accuracies can be achieved. Based on the evidence collected, we discuss open challenges associated with data-driven modeling of high-lying spectra and transition intensities.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Lilienfeld)
UniBasel Contributors:von Lilienfeld, Anatole
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:AIP Publishing
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:12 Apr 2017 11:39
Deposited On:20 Jun 2016 09:07

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