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

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
Excited-State Absorption: Reference Oscillator Strengths, Wave Function, and TDDFT Benchmarks DOI
Jakub Širůček, Boris Le Guennic, Yann Damour

et al.

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

Published: April 14, 2025

Excited-state absorption (ESA) corresponds to the transition between two electronic excited states and is a fundamental process for probing understanding light-matter interactions. Accurate modeling of ESA indeed often required interpret time-resolved experiments. In this contribution, we present dataset 53 oscillator strengths in three different gauges associated vertical energies 71 21 small- medium-sized molecules from QUEST database. few cases, additionally investigated effect geometry relaxation on excited-state geometries. The reference values were obtained within quadratic response (QR) CC3 formalism using eight Dunning basis sets. We found that d-aug-cc-pVTZ set always adequate while its more compact double-ζ counterpart, d-aug-cc-pVDZ, performs well most cases. These QR-CC3 data allow us assess performance QR-TDDFT, with without applying Tamm-Dancoff approximation, panel global range-separated hybrids (B3LYP, BH&HLYP, CAM-B3LYP, LC-BLYP33, LC-BLYP47), as several lower-order wave function methods, i.e., QR-CCSD, QR-CC2, EOM-CCSD, ISR-ADC(2), ISR-ADC(3). show QR-TDDFT delivers acceptable errors CAM-B3LYP showing particular promise, especially largest our set, Franck-Condon (FC) region. also find ISR-ADC(3) exhibits excellent When optimal geometries, relative function-based approaches remains consistent trends observed However, TD(A)-DFT, accuracy varies significantly, exchange-correlation functionals significantly depends chosen geometry.

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