First-principle computation of absorption and fluorescence spectra in solution accounting for vibronic structure, temperature effects and solvent inhomogenous broadening

Ferrer, Francisco J. Avila; Cerezo, Javier; Soto, Juan; Improta, Roberto; Santoro, Fabrizio

doi:10.1016/j.comptc.2014.03.003

Cited by 96 publications

(94 citation statements)

References 62 publications

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“…This gives the possibility to complete the calculation of the room‐temperature spectrum line shape in seconds or few minutes on standard workstations. A number of TD derivations have been presented in literature in the last decade, originally limited to FC spectra, and next generalized also to HT cases …”

Section: Methodsmentioning

confidence: 99%

Going beyond the vertical approximation with time‐dependent density functional theory

Santoro

Jacquemin

2016

WIREs Comput Mol Sci

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Since two decades, time-dependent density functional theory (TD-DFT) has been in the limelight due to its noteworthy efficiency. Indeed, in many cases, TD-DFT provides accurate excited-state properties for a relatively limited computational cost. Recently, there has been a rapidly growing interest in applications of TD-DFT (partly) exploring the excited-state potential energy surfaces. In this review, we summarize such TD-DFT investigations going beyond the vertical approximation and devoted to spectroscopic applications, with a focus on both 0-0 energies and vibrationally resolved absorption and emission spectra. We show how these quantities can be computed, considering various models for the latter, and illustrate their advantages compared to vertical estimates in terms of comparisons with experimental data.

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Section: Methodsmentioning

confidence: 99%

Going beyond the vertical approximation with time‐dependent density functional theory

Santoro

Jacquemin

2016

WIREs Comput Mol Sci

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197

233

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“…General expressions for the above autocorrelation function starting from a thermally populated initial state have been discussed elsewhere [18][19][20][21][22][23][24][25][26] , and the autocorrelation function for a 0 K state has been derived in Ref. [20].…”

Section: B Time-dependent Methodsmentioning

confidence: 99%

Vibrationally resolved electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy

Cosel

Cerezo

Kern-Michler

et al. 2017

The Journal of Chemical Physics

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Vibrationally resolved electronic absorption spectra including the effect of vibrational pre-excitation are computed in order to interpret and predict vibronic transitions that are probed in the Vibrationally Promoted Electronic Resonance (VIPER) experiment [L. J. G. W. van Wilderen et al., Angew. Chem., Int. Ed. 53, 2667 (2014)]. To this end, we employ time-independent and time-dependent methods based on the evaluation of Franck-Condon overlap integrals and Fourier transformation of time-domain wavepacket autocorrelation functions, respectively. The time-independent approach uses a generalized version of the FCclasses method [F. Santoro et al., J. Chem. Phys. 126, 084509 (2007)]. In the time-dependent approach, autocorrelation functions are obtained by wavepacket propagation and by the evaluation of analytic expressions, within the harmonic approximation including Duschinsky rotation effects. For several medium-sized polyatomic systems, it is shown that selective pre-excitation of particular vibrational modes leads to a redshift of the low-frequency edge of the electronic absorption spectrum, which is a prerequisite for the VIPER experiment. This effect is typically most pronounced upon excitation of modes that are significantly displaced during the electronic transition, such as ring distortion modes within an aromatic π-system. Theoretical predictions as to which modes show the strongest VIPER effect are found to be in excellent agreement with experiment.

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“…Here, we propose an MQC approach that goes beyond the simple idea of considering only local expansions of the PES around the molecule's stable conformers, yet it is still able to reduce the complexity of the problem to the calculation of a number of spectra on harmonic PES, which is nowadays standard . On the one hand, despite the slow coordinates are not treated at quantum level, the here proposed approach retains a quantum description of the high‐frequency modes, which are the only ones responsible for vibronic peaks visible in low‐ to intermediate‐resolution spectra, like those measured in solution.…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

“…Each point of the grid represents a constrained‐minimum on the GS, where all the DOFs are optimized, but the selected dihedrals. Room‐temperature vibronic spectra along the fast coordinates were computed with the TD method implemented in the development version of our code FC classes . To that end, we adopted a generalization of the vertical Hessian model, where both GS and ES PES are represented by a quadratic expansion at the molecular structure corresponding to the selected grid point.…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

“…If the molecule of interest is rigid, meaning that its potential energy surfaces (PESs) can be adequately described within the harmonic approximation, and if its electronic states are not affected by strong nonadiabatic couplings, the simulation of the ECD spectrum is now rather standard . Conversely, when the internal dynamics of the molecules is also characterized by slow, large amplitude motions, e.g., torsions around σ bonds, the accurate calculation of ECD spectra still presents significant challenges.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Toward a general mixed quantum/classical method for the calculation of the vibronic ECD of a flexible dye molecule with different stable conformers: Revisiting the case of 2,2,2‐trifluoro‐anthrylethanol

et al. 2018

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We extend a recently proposed mixed quantum/classical method for computing the vibronic electronic circular dichroism (ECD) spectrum of molecules with different conformers, to cases where more than one hindered rotation is present. The method generalizes the standard procedure, based on the simple Boltzmann average of the vibronic spectra of the stable conformers, and includes the contribution of structures that sample all the accessible conformational space. It is applied to the simulation of the ECD spectrum of (S)-2,2,2-trifluoroanthrylethanol, a molecule with easily interconvertible conformers, whose spectrum exhibits a pattern of alternating positive and negative vibronic peaks. Results are in very good agreement with experiment and show that spectra averaged over all the sampled conformational space can deviate significantly from the simple average of the contributions of the stable conformers. The present mixed quantum/classical method is able to capture the effect of the nonlinear dependence of the rotatory strength on the molecular structure and of the anharmonic couplings among the modes responsible for molecular flexibility. Despite its computational cost, the procedure is still affordable and promises to be useful in all cases where the ECD shape arises from a subtle balance between vibronic effects and conformational variety.

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First-principle computation of absorption and fluorescence spectra in solution accounting for vibronic structure, temperature effects and solvent inhomogenous broadening

Cited by 96 publications

References 62 publications

Going beyond the vertical approximation with time‐dependent density functional theory

Going beyond the vertical approximation with time‐dependent density functional theory

Vibrationally resolved electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy

Toward a general mixed quantum/classical method for the calculation of the vibronic ECD of a flexible dye molecule with different stable conformers: Revisiting the case of 2,2,2‐trifluoro‐anthrylethanol

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