The vibrational relaxation of the first excited bending state of DO induced by collision with He is studied at the close coupling level and using the Rigid Bender approximation. A new 4D potential energy surface is calculated and reported for this system. It is then used to determine the low-lying bound states of the DO-He van der Waals complex and to perform scattering calculations. Collision rates are determined for pure rotational transitions as well as for rovibrational transitions within the first excited bending state. The results are compared with those obtained for the collision of DO with other noble gases such as Ne and Ar. We also analyse the differences observed with respect to the HO+He collisions and compare our results with experiment.
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http://dx.doi.org/10.1002/cphc.202400353 | DOI Listing |
J Phys Chem B
January 2025
School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou 434023, China.
Chromophores incorporated into rigid polymer matrices may exhibit novel photophysical properties distinct from those in liquid solutions. In this work, we explored the decay path of the second ππ* state (2ππ*) of riboflavin in poly(vinyl alcohol) (PVA) solutions and films with various acidities. Highly efficient internal conversion from 2ππ* to the lowest ππ* state (1ππ*) induced by slight in-plane motion is demonstrated in all PVA solutions and films, irrespective of environmental acidity and rigidification.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
January 2025
School of Chemistry, University of East Anglia, Norwich NR4 7TJ, U.K.
Understanding the role of structural and environmental dynamics in the excited state properties of strongly coupled chromophores is of paramount importance in molecular photonics. Ultrafast, coherent, and multidimensional spectroscopies have been utilized to investigate such dynamics in the simplest model system, the molecular dimer. Here, we present a half-broadband two-dimensional electronic spectroscopy (HB2DES) study of the previously reported ultrafast symmetry-breaking charge separation (SB-CS) in the subphthalocyanine oxo-bridged homodimer μ-OSubPc.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Abteilung für Molekulare Physikalische Chemie, Clausius-Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Wegelerstraße 12, 53115 Bonn, Germany.
The binding of carbon dioxide to a transition metal is a complex phenomenon that involves a major redistribution of electron density between the metal center and the triatomic ligand. The chemical reduction of the ligand reveals itself unambiguously by an angular distortion of the CO-molecule as a result of the occupation of an anti-bonding π-orbital and a shift of its antisymmetric stretching vibration, ν, to lower wavenumbers. Here, we generate a carbon dioxide complex of the heavier group-10 metal, platinum, by ultrafast electronic excitation and cleavage of CO from the photolabile oxalate precursor, oxaliplatin, and monitored the ensuing primary dynamics with ultrafast mid-infrared spectroscopy.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Donostia International Physics Center (DIPC), 20018 Donostia, Euskadi, Spain.
We introduce a computational methodology for evaluating and analyzing spin-vibration couplings in molecular systems, enabling insights into the interplay between electronic spins and molecular vibrations. By mapping ab initio electronic structure calculations onto molecular spin Hamiltonians, our approach captures those vibrational interactions potentially driving spin relaxation process. Spin-vibration couplings, derived from Holstein and Peierls terms, highlight the pivotal role of vibrational mode symmetry in spin decoherence and efficient energy dissipation.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Department of Computational Sciences, School of Basic Sciences, Central University of Punjab, Bathinda 151401, India.
The effect of confinement on the tetrahedral ordering of liquid water plays a vital role in controlling their microscopic structure and dynamics as well as their spectroscopic properties. In this article, we have performed the classical molecular dynamics simulations of four different CTAB/water/chloroform reverse micelles with varied water content to study how the tetrahedral ordering of nanoscale water inside reverse micellar confinement influences the microscopic dynamics and the structural relaxation of water···water hydrogen bonds and its impact on the low-frequency intermolecular vibrational bands. We have noticed from the results obtained from simulated trajectories the lowering trends of tetrahedral ordering of water pools in reverse micellar confinements as we move from bulk to confined and strictly confined environments.
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