Dynamics of radiationless transitions in large molecular systems: A Franck–Condon-based method accounting for displacements and rotations of all the normal coordinates

Borrelli, Raffaele; Peluso, Andrea

doi:10.1063/1.1609979

Cited by 126 publications

(130 citation statements)

References 83 publications

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“…48,49 In such cases a quantitative agreement can only be obtained by using a more sophisticated model including the non-adiabatic coupling between the two electronic states. 5,70 The assignment of the electronic transitions in the high energy region of the absorption spectrum poses several problems. According to TD-DFT results a significant number of transitions fall in that spectral region though only a few of them have a significant oscillator strength.…”

Section: Discussionmentioning

confidence: 99%

“…1,2 Fast growing research fields such as organic LED technology 3 and dye-sensitized solar cells (DSSC), 4 would strongly benefit from the application of robust and easy-to-use methodologies for the simulation of spectral lineshapes of organic dyes. The research in this field is quickly growing [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] (see also Borrelli et al 22 for a recent review) but standardize procedures have not yet been established, and specific computational strategies must be carefully designed and require validation and testing on several class of molecules. [23][24][25][26] In this paper we apply state of the art tools of computational spectroscopy to simulate the absorption and emission lineshapes of squaraine dyes in solution.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical and experimental determination of the absorption and emission spectra of a prototypical indolenine-based squaraine dye

Borrelli¹,

Ellena²,

Barolo³

2014

Phys. Chem. Chem. Phys.

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The spectroscopy of a prototypical indole-based squaraine dye is analysed theoretically using state-of-the-art methodologies for the simulation of spectral lineshapes, and experimentally using optical absorption and emission spectroscopies. Density functional theory and its time-dependent extension are used to determine the stability of several conformers, to compute their excitation energies, equilibrium geometries and vibrational frequencies, both in the ground and in their first excited singlet state. Finally the generating function approach is used to simulate the vibronic lineshape of the low energy valence ππ * excitation and emission spectra. Solvent effects are also computed and discussed by using the polarizable continuum model. The developed model correctly reproduces the main spectral features of the squaraine, and allows to identify the vibrational motions which mostly contribute to the observed lineshape.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical and experimental determination of the absorption and emission spectra of a prototypical indolenine-based squaraine dye

Borrelli¹,

Ellena²,

Barolo³

2014

Phys. Chem. Chem. Phys.

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“…The FC profiles are calculated using the MolFC program, which uses the optimized geometry and normal modes of the anion and neutral from BLYP/cc-pVDZ calculations as described above. MolFC 34 calculates the FC factors for selected active vibrational modes of the anion and neutral. The Duschinsky transformation is used to determine the rotation matrix J and the displacement vector K between the normal modes of the anion and neutral.…”

Section: Analysis and Discussionmentioning

confidence: 99%

Anion photoelectron imaging of deprotonated thymine and cytosine

Parsons

Sheehan

Yen

et al. 2007

Phys. Chem. Chem. Phys.

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We report the anion photoelectron spectra of deprotonated thymine and cytosine at 3.496 eV photodetachment energy using velocity-mapped imaging. The photoelectron spectra of both species exhibit bands resulting from detachment transitions between the anion ground state and the ground state of the neutral radical. Franck-Condon simulations identify the anion isomers that contribute to the observed photoelectron spectrum. For both thymine and cytosine, the photoelectron spectra are consistent with anions formed by removal of a proton from the N atom that normally attaches to the sugar in the nucleotide (N1). For deprotonated thymine, the photoelectron spectrum shows a band due to a ring breathing vibration excited during the photodetachment transition. The electron affinity for the dehydrogenated thymine radical is determined as 3.250 AE 0.015 eV. For deprotonated cytosine, the photoelectron spectrum lacks any resolved structure and the electron affinity of the dehydrogenated cytosine radical is determined to be 3.037 AE 0.015 eV. By combining the electron affinity with previously measured gas phase acidities of thymine and cytosine, we determine the bond dissociation energy for the N-H bond that is broken.

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“…Franck-Condon overlap integrals using the Duschinsky transformation 24 are calculated with a code developed by Peluso and co-workers. 25,26 Optimized structures and normal-mode frequencies are used as inputs for both neutral and cationic states.…”

Section: Methodsmentioning

confidence: 99%

Vibrational Spectroscopy of the Pyridazine Cation in the Ground State

2006

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Vibrational structure of the pyridazine cation in the ground state has been revealed by a vacuum-ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. The adiabatic ionization energy is precisely measured to be 70241 ( 6 cm -1 (8.7088 ( 0.0007 eV). The origin is very weakly observed, while a long progression of the ν 9 + (a 1 ) band of which the fundamental vibrational frequency is 647 cm -1 is predominantly observed. The ν 9 + (a 1 ) mode progression combined with one quantum of the ν 3 + (a 1 ) band at 1698 cm -1 is found to be even stronger. Many other weakly observed vibrational features of the pyridazine cation are identified in the vibrational energy of 0-3500 cm -1 . The structural change of pyridazine upon ionization, reflected in the vibrational spectrum obtained by the one-photon direct ionization process, is theoretically predicted by ab initio calculations. Ring distortion including contraction of the NdN bond should be responsible for strong excitations of ν 3 + and ν 9 + modes. Franck-Condon analysis is given for the comparison of the experiment and theory.

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Dynamics of radiationless transitions in large molecular systems: A Franck–Condon-based method accounting for displacements and rotations of all the normal coordinates

Cited by 126 publications

References 83 publications

Theoretical and experimental determination of the absorption and emission spectra of a prototypical indolenine-based squaraine dye

Theoretical and experimental determination of the absorption and emission spectra of a prototypical indolenine-based squaraine dye

Anion photoelectron imaging of deprotonated thymine and cytosine

Vibrational Spectroscopy of the Pyridazine Cation in the Ground State

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