Anharmonic theoretical simulations of infrared spectra of halogenated organic compounds

Carnimeo, Ivan; Puzzarini, Cristina; Tasinato, Nicola; Stoppa, Paolo; Charmet, Andrea Pietropolli; Biczysko, Małgorzata; Cappelli, Chiara; Barone, Vincenzo

doi:10.1063/1.4817401

Cited by 74 publications

(112 citation statements)

References 89 publications

(133 reference statements)

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“…To choose the most suitable combination of exchange‐correlation functional and basis set, a preliminary group of the currently most popular functionals were selected (B3LYP, CAM‐B3LYP, PBE1PBE (PBE0), LC‐ ω PBE, M06‐2X, ω ‐B97X, and B2PLYP) and used to compute the vibrational and vibronic spectra, with thiophene as the reference molecule. The double‐ ζ basis set SNSD, which has been extensively validated for several spectroscopic properties in the ground and excited electronic states has been used, except for the double‐hybrid B2PLYP functional, since the latter has been shown to require a larger basis set . In this case, a modified version of maug‐cc‐pVTZ, where d functions on hydrogens have been removed, was employed.…”

Section: Methodsmentioning

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

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175

196

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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 ...

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Section: Methodsmentioning

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

175

196

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“…26,27 More recently second order vibrational perturbation theory (VPT2) generalized to include a variational treatment of leading resonances (GVPT2) [28][29][30] has been shown to deliver accurate frequencies and intensities for fundamentals, overtones and combination bands without the need of any scaling factor. 23,[31][32][33] Unfortunately, global hybrid functionals provide disappointing results for some moieties involving multiple bonds like C≡N, unless specific scaling factors are introduced. 1,34 The recent development of double hybrid functionals 35 and of their analytical second derivatives 35 has led to more reliable geometries and vibrational spectra for a large panel of organic and biological systems.…”

Section: Introductionmentioning

confidence: 99%

Accurate Infrared (IR) Spectra for Molecules Containing the C≡N Moiety by Anharmonic Computations with the Double Hybrid B2PLYP Density Functional

Vazart

Latouche

Cimino

et al. 2015

J. Chem. Theory Comput.

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Herein, we report a comprehensive benchmark of C≡N stretching vibrations computed at harmonic and anharmonic levels with the aim of proposing and validating a reliable computational strategy to get accurate results for this puzzling vibrational mode without any ad hoc scaling factor. Anharmonic calculations employing second-order vibrational perturbation theory provide very good results when performed using the B2PLYP double-hybrid functional, in conjunction with an extended basis set and supplemented by semiempirical dispersion contributions. For larger systems, B2PLYP harmonic frequencies, together with B3LYP anharmonic corrections, offer a very good compromise between accuracy and computational cost without the need of any empirical scaling factor.

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“…Therefore, it is not surprising that several investigations have appeared, aimed at assessing the performances of DFT for the solution of the vibrational problem, and properly tailored basis sets, as well as composite CC/DFT approaches have been proposed . Very recently, a benchmark study on the evaluation of the vibrational spectra of halogenated organic compounds beyond the harmonic approximation, for both transition frequencies and intensities, has been undertaken …”

Section: Introductionmentioning

confidence: 99%

What are the spectroscopic properties of HFC-32? Answers from DFT

Tasinato

2014

Int. J. Quantum Chem.

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Although coupled cluster theory coupled to large basis sets can reach impressive accuracies for thermochemical and spectroscopic properties, it is still limited to small/medium sized molecules. Density functional theory (DFT) represents the working option for systems composed of hundreds to thousands heavy atoms. In this context, investigations are required aimed at characterizing the performances of the different density functionals (DF). This work focuses on the study of DFT performances in the prediction of spectroscopic properties, with particular attention to the vibrational problem, by focusing on the CH2F2 molecule as a test case. An extensive and systematic investigation is performed on several DFT model chemistries by testing their predictions of molecular constants and vibrational frequencies and intensities against CCSD(T)/aug‐cc‐pCVQZ data. B3LYP, B3PW91, B97‐1, PBE0, TPSSh, M05, M05‐2X, and B2PLYP DFs are used in conjunction with a variety of basis sets. Anharmonic frequencies are derived from the VPT2 treatment of anharmonic‐ and hybrid CCSD(T)/DFT‐force fields. A software for VPT2 computations is also presented. © 2014 Wiley Periodicals, Inc.

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Anharmonic theoretical simulations of infrared spectra of halogenated organic compounds

Cited by 74 publications

References 89 publications

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

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

Accurate Infrared (IR) Spectra for Molecules Containing the C≡N Moiety by Anharmonic Computations with the Double Hybrid B2PLYP Density Functional

What are the spectroscopic properties of HFC-32? Answers from DFT

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