Noncovalent Interactions and Internal Dynamics in Pyridine–Ammonia: A Combined Quantum‐Chemical and Microwave Spectroscopy Study

Spada, Lorenzo; Tasinato, Nicola; Vazart, Fanny; Barone, Vincenzo; Camináti, Walther; Puzzarini, Cristina

doi:10.1002/chem.201606014

Cited by 40 publications

(62 citation statements)

References 65 publications

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“…It is worth to note that the “cheap” computational protocol for geometry has been recently applied to the adduct formed by pyridine and NH 3 , thus demonstrating its applicability not only to isolated molecules but also to molecular complexes …”

Section: Quantum Chemical Approaches For Single Molecule Accuracymentioning

confidence: 99%

Tailor‐made computational protocols for precise characterization of small biological building blocks using QM and MM approaches

et al. 2018

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Computational modeling involving Quantum Mechanics (QM) and Molecular Mechanics (MM) calculations are widely utilized to unveil the atomic-molecular properties that underpin their inherent characteristic features. The choice over the either of the QM and MM methods or a multiscale composite approach is driven by the target property of interest, and of course, the molecular size. Often, tailor-made schemes need to be devised to match the specific study purpose. Herein, we provide a perspective of these approaches addressing their effectiveness in terms of the delicate balance between the accuracy and computational feasibility. We focus on representative examples to highlight how different approaches can be fruitfully exploited for modeling the conformational landscape, and possibly, the spectroscopic behavior of biochemical molecules, especially amino acids building blocks.

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Section: Quantum Chemical Approaches For Single Molecule Accuracymentioning

confidence: 99%

Tailor‐made computational protocols for precise characterization of small biological building blocks using QM and MM approaches

et al. 2018

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“…Then, equilibrium rotational constants are corrected for vibrational contributions evaluated at a lower level of theory (e.g., DFT with hybrid or double-hybrid functionals). 21,33,39 This approach has been profitably applied to a wide variety of molecules, 21,[35][36][37]64 and very recently, its efficacy has been demonstrated for molecular complexes as well. 39,64 VMS-ROT offers the possibility to exploit such an approach to obtain very accurate estimates of rotational constants.…”

Section: Rotational-spectroscopy Module Of Vms: Implementation and Tementioning

confidence: 99%

“…21,33,39 This approach has been profitably applied to a wide variety of molecules, 21,[35][36][37]64 and very recently, its efficacy has been demonstrated for molecular complexes as well. 39,64 VMS-ROT offers the possibility to exploit such an approach to obtain very accurate estimates of rotational constants. In fact, it is possible to start from an anharmonic calculation carried out at the DFT level, which provides vibrational contributions and then load an equilibrium molecular structure (stored, for example, in a conventional xyz format) determined through a composite scheme.…”

Section: Rotational-spectroscopy Module Of Vms: Implementation and Tementioning

confidence: 99%

“…As anticipated, VMS-ROT has been validated also for the analysis of rotational spectra of molecular complexes, focusing on the PYR•••NH 3 and DFM•••TBA dimers, which have been recently investigated by Spada et al 39,64 by means of an integrated experimental−theoretical approach joining Fourier Transform Microwave spectroscopy (FTMW) to state-of-the-art quantum-chemical calculations. Concerning the DFM•••TBA complex, the initial assignment has been carried out on the basis of the spectrum simulated by using the spectroscopic parameters computed at the B2PLYP-D3/m-aug-cc-pVTZ-dH level.…”

Section: Journal Of Chemical Theory and Computationmentioning

confidence: 99%

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VMS-Rot: A New Module of the Virtual Multifrequency Spectrometer for Simulation, Interpretation, and Fitting of Rotational Spectra

Puzzarini¹,

Barone²,

Spada³

et al. 2018

Proceedings of the 73rd International Symposium on Molecular Spectroscopy

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The Virtual Multifrequency Spectrometer (VMS) is a tool that aims at integrating a wide range of computational and experimental spectroscopic techniques with the final goal of disclosing the static and dynamic physical− chemical properties "hidden" in molecular spectra. VMS is composed of two parts, namely, VMS-Comp, which provides access to the latest developments in the field of computational spectroscopy, and VMS-Draw, which provides a powerful graphical user interface (GUI) for an intuitive interpretation of theoretical outcomes and a direct comparison to experiment. In the present work, we introduce VMS-ROT, a new module of VMS that has been specifically designed to deal with rotational spectroscopy. This module offers an integrated environment for the analysis of rotational spectra: from the assignment of spectral transitions to the refinement of spectroscopic parameters and the simulation of the spectrum. While bridging theoretical and experimental rotational spectroscopy, VMS-ROT is strongly integrated with quantum-chemical calculations, and it is composed of four independent, yet interacting units: (1) the computational engine for the calculation of the spectroscopic parameters that are employed as a starting point for guiding experiments and for the spectral interpretation, (2) the fitting-prediction engine for the refinement of the molecular parameters on the basis of the assigned transitions and the prediction of the rotational spectrum of the target molecule, (3) the GUI module that offers a powerful set of tools for a visa -vis comparison between experimental and simulated spectra, and (4) the new assignment tool for the assignment of experimental transitions in terms of quantum numbers upon comparison with the simulated ones. The implementation and the main features of VMS-ROT are presented, and the software is validated by means of selected test cases ranging from isolated molecules of different sizes to molecular complexes. VMS-ROT therefore offers an integrated environment for the analysis of the rotational spectra, with the innovative perspective of an intimate connection to quantum-chemical calculations that can be exploited at different levels of refinement, as an invaluable support and complement for experimental studies.

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“…In fact, when large molecules or molecular complexes with different conformers and several low-lying vibrational states are to be investigated or when new chemical species that can be even unstable, like ions and radicals, are sought, then quantum-chemical calculations provide an invaluable tool to guide experiments as well as to assist the spectral analy-sis. 8 , 13 − 15 , 21 − 26 Nowadays, quantum-chemical calculations, ranging from density functional theory (DFT) or second-order Møller–Plesset perturbation theory (MP2) 27 to the most refined composite schemes based on the coupled-cluster ansatz, also accounting for basis-set effects, 28 − 34 play a fundamental role in modern approaches to rotational spectroscopy (see, e.g., refs ( 2 , 21 , and 35 − 39 ).).…”

Section: Introductionmentioning

confidence: 99%

VMS-ROT: A New Module of the Virtual Multifrequency Spectrometer for Simulation, Interpretation, and Fitting of Rotational Spectra

Licari

Tasinato

Spada

et al. 2017

J. Chem. Theory Comput.

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The Virtual Multifrequency Spectrometer (VMS) is a tool that aims at integrating a wide range of computational and experimental spectroscopic techniques with the final goal of disclosing the static and dynamic physical–chemical properties “hidden” in molecular spectra. VMS is composed of two parts, namely, VMS-Comp, which provides access to the latest developments in the field of computational spectroscopy, and VMS-Draw, which provides a powerful graphical user interface (GUI) for an intuitive interpretation of theoretical outcomes and a direct comparison to experiment. In the present work, we introduce VMS-ROT, a new module of VMS that has been specifically designed to deal with rotational spectroscopy. This module offers an integrated environment for the analysis of rotational spectra: from the assignment of spectral transitions to the refinement of spectroscopic parameters and the simulation of the spectrum. While bridging theoretical and experimental rotational spectroscopy, VMS-ROT is strongly integrated with quantum-chemical calculations, and it is composed of four independent, yet interacting units: (1) the computational engine for the calculation of the spectroscopic parameters that are employed as a starting point for guiding experiments and for the spectral interpretation, (2) the fitting-prediction engine for the refinement of the molecular parameters on the basis of the assigned transitions and the prediction of the rotational spectrum of the target molecule, (3) the GUI module that offers a powerful set of tools for a vis-à-vis comparison between experimental and simulated spectra, and (4) the new assignment tool for the assignment of experimental transitions in terms of quantum numbers upon comparison with the simulated ones. The implementation and the main features of VMS-ROT are presented, and the software is validated by means of selected test cases ranging from isolated molecules of different sizes to molecular complexes. VMS-ROT therefore offers an integrated environment for the analysis of the rotational spectra, with the innovative perspective of an intimate connection to quantum-chemical calculations that can be exploited at different levels of refinement, as an invaluable support and complement for experimental studies.

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Noncovalent Interactions and Internal Dynamics in Pyridine–Ammonia: A Combined Quantum‐Chemical and Microwave Spectroscopy Study

Cited by 40 publications

References 65 publications

Tailor‐made computational protocols for precise characterization of small biological building blocks using QM and MM approaches

Tailor‐made computational protocols for precise characterization of small biological building blocks using QM and MM approaches

VMS-Rot: A New Module of the Virtual Multifrequency Spectrometer for Simulation, Interpretation, and Fitting of Rotational Spectra

VMS-ROT: A New Module of the Virtual Multifrequency Spectrometer for Simulation, Interpretation, and Fitting of Rotational Spectra

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