Phase transitions in a metal-organic perovskite with an azetidinium cation, which exhibits giant polarizability, were investigated using differential scanning calorimetry (DSC) and (1)H nuclear magnetic resonance (NMR) measurements. The DSC results indicated successive phase transitions at 254 and 299 K. The temperature dependence of the spin-lattice relaxation time T(1) determined by NMR indicated that the activation energy for cation ring-puckering motion was 25 kJ mol(-1) in phase I (T > 299 K). The potential energy at the transition state of puckering is expected to decrease when the potential for the motion becomes asymmetric with decreasing temperature in phases II and III. A possible mechanism for the onset of an extraordinarily large dielectric anomaly is discussed.
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http://dx.doi.org/10.1021/jp310132a | DOI Listing |
J Chem Phys
July 2024
Sorbonne Université, CNRS, MONARIS, UMR 8233, 4 Place Jussieu, Paris F-75005, France.
In the continuity of a previous jet-cooled rovibrational study of trans and cis conformers of 2-furfural in the mid-infrared region (700-1750 cm-1) [Chawananon et al., Molecules 28 (10), 4165 (2023)], the present work investigates the far-infrared spectroscopy of 2-furfural using a long path absorption cell coupled to a high-resolution Fourier transform spectrometer and synchrotron radiation at the AILES beamline of the SOLEIL synchrotron. Guided by anharmonic calculations, vibrational energy levels and excited-state rotational constants are sufficiently predictive for a complete assignment of all fundamental and combination bands up to 700 cm-1, as well as the rovibrational analysis of 4 (1) low-frequency modes of trans-(cis-)2-furfural.
View Article and Find Full Text PDFChemphyschem
September 2024
College of Science, China University of Petroleum (East China), Qingdao, 266580, Shandong, China.
The design and application of molecular photoswitches have attracted much attention. Herein, we performed a detailed computational study on the photoswitch benzylidene-oxazolone system based on static electronic structure calculations and on-the-fly excited-state dynamic simulations. For the Z and E isomer, we located six and four minimum energy conical intersections (MECIs) between the first excited state (S) and the ground state (S), respectively.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2024
JILA, University of Colorado Boulder and National Institute of Standards and Technology, Boulder, Colorado 80309, USA.
Gas-phase cyclobutyl radical (c-CH) is generated at a rotational temperature of = 26(1) K in a slit-jet discharge mixture of 70% Ne/30% He and 0.5-0.6% cyclobromobutane (c-CHBr).
View Article and Find Full Text PDFPhys Chem Chem Phys
November 2023
Nano-Science Center & Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 KøbenhavnØ, Denmark.
The high photostability of DNAs and RNAs is inextricably related to the photochemical and photophysical properties of their building blocks, nucleobases and nucleosides, which can dissipate the absorbed UV light energy in a harmless manner. The deactivation mechanism of the nucleosides, especially the decay pathways of cytidine (Cyd), has been a matter of intense debate. In the current study, we employ high-level electronic structure calculations combined with excited state non-adiabatic dynamic simulations to provide a clear picture of the excited state deactivation of Cyd in both gas phase and aqueous solution.
View Article and Find Full Text PDFMolecules
June 2022
Institut für Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-Leibniz-Universität Hannover, Callinstraße 3A, 30167 Hannover, Germany.
Large amplitude motions (LAMs) form a fundamental phenomenon that demands the development of specific theoretical and Hamiltonian models. In recent years, along with the strong progress in instrumental techniques on high-resolution microwave spectroscopy and computational capacity in quantum chemistry, studies on LAMs have become very diverse. Larger and more complex molecular systems have been taken under investigation, ranging from series of heteroaromatic molecules from five- and six-membered rings to polycyclic-aromatic-hydrocarbon derivatives.
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