TY - JOUR
T1 - Ultrafast Evaluation of Two-Photon Absorption with Simplified Time-Dependent Density Functional Theory
AU - De Wergifosse, Marc
AU - Beaujean, Pierre
AU - Grimme, Stefan
N1 - Funding Information:
This work was supported by the DFG in the framework of the project “Theoretical studies of nonlinear optical properties of fluorescent proteins by novel low-cost quantum chemistry methods” (Nr. 450959503). Some of the calculations were performed on the computers of the Consortium des Équipements de Calcul Intensif, including those of the Technological Platform of High-Performance Computing, for which we gratefully acknowledge the financial support from the FNRS-FRFC, the Walloon Region, and the University of Namur (Convention nos. 2.5020.11, GEQ U.G006.15, 1610468, and RW/GEQ2016). a
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/10/20
Y1 - 2022/10/20
N2 - This work presents the theoretical background to evaluate two-photon absorption (2PA) cross-sections in the framework of simplified time-dependent density functional theory (sTD-DFT). Our new implementation allows the ultrafast evaluation of 2PA cross-sections for large molecules based on a regular DFT ground-state determinant as well as a variant employing our tight-binding sTD-DFT-xTX flavor for very large systems. The method is benchmarked against higher-level calculations for trans-stilbene and typical fluorescent protein chromophores. For eGFP, a quadrupolar chromophore and its branched version, the flavine mono-nucleotide, and the iLOV protein, we compare sTD-DFT 2PA spectra to experimental ones. This includes extension and testing of our all-atom quantum chemistry methodology for the evaluation of 2PA for a system of ∼2000 atoms, providing striking agreement with the experimental spectrum.
AB - This work presents the theoretical background to evaluate two-photon absorption (2PA) cross-sections in the framework of simplified time-dependent density functional theory (sTD-DFT). Our new implementation allows the ultrafast evaluation of 2PA cross-sections for large molecules based on a regular DFT ground-state determinant as well as a variant employing our tight-binding sTD-DFT-xTX flavor for very large systems. The method is benchmarked against higher-level calculations for trans-stilbene and typical fluorescent protein chromophores. For eGFP, a quadrupolar chromophore and its branched version, the flavine mono-nucleotide, and the iLOV protein, we compare sTD-DFT 2PA spectra to experimental ones. This includes extension and testing of our all-atom quantum chemistry methodology for the evaluation of 2PA for a system of ∼2000 atoms, providing striking agreement with the experimental spectrum.
UR - http://www.scopus.com/inward/record.url?scp=85139557948&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.2c02395
DO - 10.1021/acs.jpca.2c02395
M3 - Article
C2 - 36201255
AN - SCOPUS:85139557948
SN - 1089-5639
VL - 126
SP - 7534
EP - 7547
JO - Journal of physical chemistry A
JF - Journal of physical chemistry A
IS - 41
ER -