Computing Excited States of Very Large Systems with Range-Separated Hybrid Functionals and the Exact Integral Simplified Time-Dependent Density Functional Theory (XsTD-DFT) DOI
Marc de Wergifosse

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: unknown, P. 12628 - 12635

Published: Dec. 17, 2024

Simplified quantum chemistry (sQC) methods can routinely compute excited states for very large systems in an "all-atom" fashion. They are viable alternatives to regular multiscale schemes. sQC have the advantage of accounting explicitly all environment at a mechanical (QM) level. The treatment charge-transfer is now improved by native implementation range-separated hybrid (RSH) exchange-correlation functionals into eXact integral simplified time-dependent density functional theory (XsTD-DFT). After RSH XsTD-DFT/TDA scheme was benchmarked, XsTD-DFT(/TDA) ultraviolet/visible absorption, circular dichroism (CD), and/or two-photon absorption (2PA) spectra were directly compared results experiments four challenging and increasingly systems: eYFP model system, Λ-shaped multimodular D-π-A-π-D'-π-A-π-D chromophore, mixed donor/acceptor ligand Pd(II) double cage [3BF

Language: Английский

Computational insights into two-photon absorption of centrosymmetric organoboron complexes DOI
Bramantya Bramantya, Borys Ośmiałowski, Robert Zaleśny

et al.

Chemical Physics Letters, Journal Year: 2025, Volume and Issue: unknown, P. 141907 - 141907

Published: Jan. 1, 2025

Language: Английский

Citations

0
Simulations of Two-Photon Absorption Spectra of Fluorescent Dyes: The Impact of Non-Condon Effects DOI Creative Commons
Rudraditya Sarkar, Carmelo Naim, Karan Ahmadzadeh

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Computer simulations play a pivotal role in interpreting experimental two-photon absorption (2PA) spectra. One of the key aspects simulation these spectra is to take into account vibrational fine structure bands electronic This typically done by employing Franck–Condon (FC) term and low-order terms Herzberg–Teller (HT) expansion. In this work, we present systematic study first-order HT effects on vibronic π → π* 2PA 13 common fluorophores. We begin evaluating performance several density functional approximations (DFAs) against second-order coupled cluster singles doubles model (CC2) for reproducing transition moments their first- derivatives with respect normal modes vibration set six donor–acceptor molecules. Our findings reveal that most DFAs produce inaccurate values derivatives, exception LC-BLYP functionals range–separation parameters 0.33 0.47. Although underestimate contribution total intensities bands, they offer reasonable qualitative reproduction reference further explore fluorescent chromophores, finding contributions are secondary FC effects, leading small shifts wavelengths peaks, minimal changes intensities. Additionally, adiabatic Hessian, vertical gradient models assessed. The general agreement among confirms harmonic approximation suitable studying selected

Language: Английский

Citations

0
Two-Photon Absorption Strengths of Small Molecules: Reference CC3 Values and Benchmarks DOI
Carmelo Naim, Robert Zaleśny, Denis Jacquemin

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(20), P. 9093 - 9106

Published: Oct. 7, 2024

We present a large dataset of highly accurate two-photon transition strengths (δTPA) determined for standard small molecules. Our reference values have been calculated using the quadratic response implementation third-order coupled cluster method including iterative triples (Q-CC3). The aug-cc-pVTZ atomic basis set is used molecules with up to five non-hydrogen atoms, while larger are assessed aug-cc-pVDZ; differences due sets discussed. This dataset, encompassing 82 singlet transitions various characters (Rydberg, valence, and double excitations), enables comprehensive benchmark smaller alternative wavefunction methods when Q-CC3 calculations become beyond reach as well time-dependent density functional theory (TD-DFT) approaches. evaluated include equation-of-motion CCSD approximations, Q-CC2, second-order algebraic diagrammatic construction in its intermediate state representation (I-ADC2). In TD-DFT framework, commonly exchange–correlation functionals evaluted. extensive analysis provides quantitative assessment these methods, revealing how different system sizes, intensities, types affect their performances.

Language: Английский

Citations

3
Computational Insights into Two-Photon Absorption of Centrosymmetric Organoboron Complexes DOI
Bramantya Bramantya, Borys Ośmiałowski, Robert Zaleśny

et al.

Published: Jan. 1, 2024

Language: Английский

Citations

0
Computing Excited States of Very Large Systems with Range-Separated Hybrid Functionals and the Exact Integral Simplified Time-Dependent Density Functional Theory (XsTD-DFT) DOI
Marc de Wergifosse

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: unknown, P. 12628 - 12635

Published: Dec. 17, 2024

Simplified quantum chemistry (sQC) methods can routinely compute excited states for very large systems in an "all-atom" fashion. They are viable alternatives to regular multiscale schemes. sQC have the advantage of accounting explicitly all environment at a mechanical (QM) level. The treatment charge-transfer is now improved by native implementation range-separated hybrid (RSH) exchange-correlation functionals into eXact integral simplified time-dependent density functional theory (XsTD-DFT). After RSH XsTD-DFT/TDA scheme was benchmarked, XsTD-DFT(/TDA) ultraviolet/visible absorption, circular dichroism (CD), and/or two-photon absorption (2PA) spectra were directly compared results experiments four challenging and increasingly systems: eYFP model system, Λ-shaped multimodular D-π-A-π-D'-π-A-π-D chromophore, mixed donor/acceptor ligand Pd(II) double cage [3BF

Language: Английский

Citations

0