Accurate Simulation of Resonance-Raman Spectra of Flexible Molecules: An Internal Coordinates Approach

Baiardi, Alberto; Bloino, Julien; Barone, Vincenzo

doi:10.1021/acs.jctc.5b00241

Cited by 54 publications

(91 citation statements)

References 106 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Here, the so‐called delocalized internal coordinates (DICs), which are obtained through a singular value decomposition of the Wilson B matrix, will be used. As already discussed in our previous works, DICs provide an efficient reduction of mode‐couplings also for nontrivial LAMs, as well as for systems characterized by complex topologies, especially in comparison with the widely used Z ‐matrix internal coordinates. When internal coordinates are used, a different, nonorthogonal transformation matrix between internal and normal coordinates is built and used to define the Duschinsky transformation .…”

Section: Theorymentioning

confidence: 91%

Computational simulation of vibrationally resolved spectra for spin‐forbidden transitions

et al. 2018

Self Cite

View full text Add to dashboard Cite

In this computational study, we illustrate a method for computing phosphorescence and circularly polarized phosphorescence spectra of molecular systems, which takes into account vibronic effects including both Franck-Condon and Herzberg-Teller contributions. The singlet and triplet states involved in the phosphorescent emission are described within the harmonic approximation, and the method fully takes mode-mixing effects into account when evaluating Franck-Condon integrals. Spin-orbit couplings, which are responsible for these otherwise forbidden phenomena, are accounted for by means of a relativistic two-component time-dependent density functional theory method. The model is applied to two types of chiral systems: camphorquinone, a rigid organic system that allows for an extensive benchmark, and some members of a class of iridium complexes. The merits and shortcomings of the methods are discussed, and some perspectives for future developments are offered.

show abstract

Section: Theorymentioning

confidence: 91%

Computational simulation of vibrationally resolved spectra for spin‐forbidden transitions

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…In our discussion, delocalized internal coordinates (DICs) will be used, which are well‐suited for the study of large‐size systems since they can be built using only the molecular topology. Moreover, they are more reliable than the widely used Z ‐matrix coordinates when dealing with nonsimple deformations associated to the electronic transition …”

Section: Theoretical Backgroundmentioning

confidence: 99%

Aiming at an accurate prediction of vibrational and electronic spectra for medium‐to‐large molecules: An overview

Bloino

Baiardi

Biczysko

2016

Int J of Quantum Chemistry

Self Cite

180

196

View full text Add to dashboard Cite

In this tutorial review, we present some effective methodologies available for the simulation of vibrational and vibrationally resolved electronic spectra of medium-to-large molecules. They have been integrated into a unified platform and extended to support a wide range of spectroscopies.The resulting tool is particularly useful in assisting the extensive characterization of molecules, often achieved by combining multiple types of measurements. A correct assessment of the reliability of theoretical calculations is a necessary prelude to the interpretation of their results. For this reason, the key concepts of the underlying theories will be first presented and then illustrated through the study of thiophene and its smallest oligomer, bithiophene. While doing so, a complete computational protocol will be detailed, with emphasis on the strengths and potential shortcomings of the models employed here. Guidelines are also provided for performing similar studies on different molecular systems, with comments on the more common pitfalls and ways to overcome them. Finally, extensions to other cases, like chiral spectroscopies or mixtures, are also discussed. K E Y W O R D Sanharmonic vibrational spectroscopy, computational spectroscopy, large amplitude motion, medium-to-large molecules, vibronic spectroscopy | I N T R O D U C T I O NMolecular properties are commonly probed with a wide panel of spectroscopies, which can be combined to offer a unique picture, reflection of the property, its environment, and the experimental conditions. [1][2][3][4][5][6][7][8] The wealth of information contained in the recorded spectrum or spectra can become complex to analyze in a purely phenomenological way and theoretical models can provide a valuable aid in understanding the origin of the features observed in the band-shapes. [9][10][11] As a matter of fact, the predictive and interpretative power of computational spectroscopy has been clearly demonstrated already for small molecular systems in the gas phase, by comparison with the most sophisticated experimental techniques. [1,[12][13][14] However, depending on the target system and the required accuracy, the theoretical spectroscopic models can vary greatly in complexity. The situation is even more challenging when considering their actual implementation, often done in ad hoc, standalone programs, whose levels of completion, versatility and ease of use may be very different. As a result, getting an extensive picture of the experimental spectra can become a challenge as it may require multiple packages with their own usage and peculiarities.Hence, to facilitate the simulation and interpretation of multiple spectra, several conditions need to be met. A first challenge is to provide a simple interface, lowering the barrier to the broad adoption of state-of-the-art methods able to produce accurate data for the problems at hand. [11,[15][16][17] This can be achieved by automatizing most aspects of the calculations. Due to the inherent complexity of some theoretical models, such ...

show abstract

“…Therefore, computationally oriented chemists can provide crucial information on these molecules, especially thanks to the very recent developments in this area [13][14][15][16]. Furthermore, Density Functional Theory (DFT) and its TimeDependent extension (TD-DFT) are increasingly used to get electronic and vibrational information from small-to large-size systems thanks to the strong improvements in hardware and software [17][18][19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Validation of a computational protocol to simulate near IR phosphorescence spectra for Ru(II) and Ir(III) metal complexes

Vazart

Latouche

2015

Theor Chem Acc

View full text Add to dashboard Cite

Accurate Simulation of Resonance-Raman Spectra of Flexible Molecules: An Internal Coordinates Approach

Cited by 54 publications

References 106 publications

Computational simulation of vibrationally resolved spectra for spin‐forbidden transitions

Computational simulation of vibrationally resolved spectra for spin‐forbidden transitions

Aiming at an accurate prediction of vibrational and electronic spectra for medium‐to‐large molecules: An overview

Validation of a computational protocol to simulate near IR phosphorescence spectra for Ru(II) and Ir(III) metal complexes

Contact Info

Product

Resources

About