The Unexplored World of Cycloalkene–Water Complexes: Primary and Assisting Interactions Unraveled by Experimental and Computational Spectroscopy

Wang, Juan; Spada, Lorenzo; Chen, Junhua; Gao, Shuang; Alessandrini, Silvia; Feng, Gang; Puzzarini, Cristina; Gou, Qian; Grabow, Jens‐Uwe; Barone, Vincenzo

doi:10.1002/anie.201906977

Cited by 28 publications

(29 citation statements)

References 63 publications

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“…In the experimentally observed isomer ( I ), TFAP and water are linked by one O-H···O HB and one C-H···O wHB, thus leading to an estimated equilibrium dissociation energy of −22.4 kJ·mol −1 , with the electrostatic term being the largest contribution stabilizing the complex. The role of C-H···O wHBs in assisting stronger intermolecular interactions was already pointed out in the case of the cyclopentene-water complex [ 72 ], where the main interaction is O-H···π [ 72 ].…”

Section: Discussionmentioning

confidence: 99%

Rotational Spectroscopy Meets Quantum Chemistry for Analyzing Substituent Effects on Non-Covalent Interactions: The Case of the Trifluoroacetophenone-Water Complex

et al. 2020

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The most stable isomer of the 1:1 complex formed by 2,2,2-trifluoroacetophenone and water has been characterized by combining rotational spectroscopy in supersonic expansion and state-of-the-art quantum-chemical computations. In the observed isomer, water plays the double role of proton donor and acceptor, thus forming a seven-membered ring with 2,2,2-trifluoroacetophenone. Accurate intermolecular parameters featuring one classical O-H···O hydrogen bond and one weak C-H···O hydrogen bond have been determined by means of a semi-experimental approach for equilibrium structure. Furthermore, insights on the nature of the established non-covalent interactions have been unveiled by means of different bond analyses. The comparison with the analogous complex formed by acetophenone with water points out the remarkable role played by fluorine atoms in tuning non-covalent interactions.

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Section: Discussionmentioning

confidence: 99%

Rotational Spectroscopy Meets Quantum Chemistry for Analyzing Substituent Effects on Non-Covalent Interactions: The Case of the Trifluoroacetophenone-Water Complex

et al. 2020

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“…Since the double-hybrid B2PLYP functional [ 55 ] represents a good compromise between accuracy and computational cost for both structural and spectroscopic properties [ 56 , 57 , 58 ] and is able to provide a reliable description of reactive and non-reactive PESs [ 34 , 35 , 56 , 57 , 59 , 60 , 61 , 62 ], our strategy relies on it in order to provide the final description of the stationary points from a structural point of view. For this purpose, B2PLYP is usually employed in conjunction with a triple-zeta basis sets incorporating diffuse functions.…”

Section: Computational Methodologymentioning

confidence: 99%

The Role of State-of-the-Art Quantum-Chemical Calculations in Astrochemistry: Formation Route and Spectroscopy of Ethanimine as a Paradigmatic Case

et al. 2020

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The gas-phase formation and spectroscopic characteristics of ethanimine have been re-investigated as a paradigmatic case illustrating the accuracy of state-of-the-art quantum-chemical (QC) methodologies in the field of astrochemistry. According to our computations, the reaction between the amidogen, NH, and ethyl, C2H5, radicals is very fast, close to the gas-kinetics limit. Although the main reaction channel under conditions typical of the interstellar medium leads to methanimine and the methyl radical, the predicted amount of the two E,Z stereoisomers of ethanimine is around 10%. State-of-the-art QC and kinetic models lead to a [E−CH3CHNH]/[Z−CH3CHNH] ratio of ca. 1.4, slightly higher than the previous computations, but still far from the value determined from astronomical observations (ca. 3). An accurate computational characterization of the molecular structure, energetics, and spectroscopic properties of the E and Z isomers of ethanimine combined with millimeter-wave measurements up to 300 GHz, allows for predicting the rotational spectrum of both isomers up to 500 GHz, thus opening the way toward new astronomical observations.

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“…A reliable description of the relative stabilities is a crucial step that can substantially influence the final results because the simulated spectrum can be very sensitive to the Boltzmann population. Relying on previous investigations, 42 , 60 , 61 we employed the B2 level of theory also accounting for the solvent by means of the PCM approximation, 48 , 49 which allows to achieve accurate results at affordable computational cost. The results are collected in Table 3 , and Δ G PCM values were used to compute Boltzmann population at room temperature in order to get the final simulated spectra.…”

Section: Computational Characterization Of Lamsmentioning

confidence: 99%

Toward Fully Unsupervised Anharmonic Computations Complementing Experiment for Robust and Reliable Assignment and Interpretation of IR and VCD Spectra from Mid-IR to NIR: The Case of 2,3-Butanediol and trans-1,2-Cyclohexanediol

et al. 2020

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The infrared (IR) and vibrational circular dichroism (VCD) spectra of 2,3-butanediol and trans -1,2-cyclohexanediol from 900 to 7500 cm –1 (including mid-IR, fundamental CH and OH stretchings, and near-infrared regions) have been investigated by a combined experimental and computational strategy. The computational approach is rooted in density functional theory (DFT) computations of harmonic and leading anharmonic mechanical, electrical, and magnetic contributions, followed by a generalized second-order perturbative (GVPT2) evaluation of frequencies and intensities for all the above regions without introducing any ad hoc scaling factor. After proper characterization of large-amplitude motions, all resonances plaguing frequencies and intensities are taken into proper account. Comparison of experimental and simulated spectra allows unbiased assignment and interpretation of the most interesting features. The reliability of the GVPT2 approach for OH stretching fundamentals and overtones is confirmed by the remarkable agreement with a local mode model purposely tailored for the latter two regions. Together with the specific interest of the studied molecules, our results confirm that an unbiased assignment and interpretation of vibrational spectra for flexible medium-size molecules can be achieved by means of a nearly unsupervised reliable, robust, and user-friendly DFT/GVPT2 model.

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The Unexplored World of Cycloalkene–Water Complexes: Primary and Assisting Interactions Unraveled by Experimental and Computational Spectroscopy

Cited by 28 publications

References 63 publications

Rotational Spectroscopy Meets Quantum Chemistry for Analyzing Substituent Effects on Non-Covalent Interactions: The Case of the Trifluoroacetophenone-Water Complex

Rotational Spectroscopy Meets Quantum Chemistry for Analyzing Substituent Effects on Non-Covalent Interactions: The Case of the Trifluoroacetophenone-Water Complex

The Role of State-of-the-Art Quantum-Chemical Calculations in Astrochemistry: Formation Route and Spectroscopy of Ethanimine as a Paradigmatic Case

Toward Fully Unsupervised Anharmonic Computations Complementing Experiment for Robust and Reliable Assignment and Interpretation of IR and VCD Spectra from Mid-IR to NIR: The Case of 2,3-Butanediol and trans-1,2-Cyclohexanediol

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