Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidth

The research focuses on Raman effects from vibrational interactions for mixed solute and solvent in binary mixed liquid for vibrational exchange from anharmonic interactions from three and four body collisions of mixed solvents from shields and cages about excited molecule of solute. The Raman linew...

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Main Authors: Richard Brun Jr, Henry J. Meyer, Robert R. Alfano
Format: Article
Language:English
Published: Elsevier 2023-06-01
Series:Results in Physics
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S2211379723002863
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author Richard Brun Jr
Henry J. Meyer
Robert R. Alfano
author_facet Richard Brun Jr
Henry J. Meyer
Robert R. Alfano
author_sort Richard Brun Jr
collection DOAJ
description The research focuses on Raman effects from vibrational interactions for mixed solute and solvent in binary mixed liquid for vibrational exchange from anharmonic interactions from three and four body collisions of mixed solvents from shields and cages about excited molecule of solute. The Raman linewidth were measured and theoretically fitted by varying the mole fraction (X) of solute proportions with mixed solvents, one acting as a solute and the other as a solvent. The excitation of CH3 modes to the daughter modes and other mixed molecule modes show the effect of anharmonic many body collisions, dephasing and vibrational energy transfer. The Raman linewidth and intensity of the higher vibrational modes of solvents: Acetone and Methanol can rise in the presence of a second solvent of lower vibrational modes act as shield. Using various combinations of the solvents as acetone and methanol with carbon disulfide, and carbon tetrachloride can alter relaxation pathways due to the interruption of intermolecular energy decay routes of acetone and methanol by the low energy modes of carbon tetrachloride and carbon disulfide act as shields to energy transfer. Carbon tetrachloride is a stronger shielding agent than carbon disulfide for both acetone’s high and low energy modes due to acetone’s larger amphiphilic structure that is more resilient to structural hindrance of the linear carbon disulfide as opposed to the larger spherical carbon tetrachloride. Carbon disulfide is a stronger shielding agent than carbon tetrachloride for methanol except in the case of 1456 cm−1 energy mode due to the increased structural hindrance of carbon disulfide’s linear structure, which methanol is more susceptible to by its smaller molecular structure, preventing intermolecular interactions with other methanol molecules.
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spelling doaj.art-aca913ce40d342fdb0f31bc166cbcf582023-06-01T04:35:47ZengElsevierResults in Physics2211-37972023-06-0149106493Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidthRichard Brun Jr0Henry J. Meyer1Robert R. Alfano2Princeton University, Department of Electrical and Computer Engineering, Princeton, NJ 08540, USA; CUNY Institute for Ultrafast Spectroscopy and Lasers, Department of Physics and Electrical Engineering, The City College of New York, New York 10031, USA; Corresponding author.CUNY Institute for Ultrafast Spectroscopy and Lasers, Department of Physics and Electrical Engineering, The City College of New York, New York 10031, USACUNY Institute for Ultrafast Spectroscopy and Lasers, Department of Physics and Electrical Engineering, The City College of New York, New York 10031, USAThe research focuses on Raman effects from vibrational interactions for mixed solute and solvent in binary mixed liquid for vibrational exchange from anharmonic interactions from three and four body collisions of mixed solvents from shields and cages about excited molecule of solute. The Raman linewidth were measured and theoretically fitted by varying the mole fraction (X) of solute proportions with mixed solvents, one acting as a solute and the other as a solvent. The excitation of CH3 modes to the daughter modes and other mixed molecule modes show the effect of anharmonic many body collisions, dephasing and vibrational energy transfer. The Raman linewidth and intensity of the higher vibrational modes of solvents: Acetone and Methanol can rise in the presence of a second solvent of lower vibrational modes act as shield. Using various combinations of the solvents as acetone and methanol with carbon disulfide, and carbon tetrachloride can alter relaxation pathways due to the interruption of intermolecular energy decay routes of acetone and methanol by the low energy modes of carbon tetrachloride and carbon disulfide act as shields to energy transfer. Carbon tetrachloride is a stronger shielding agent than carbon disulfide for both acetone’s high and low energy modes due to acetone’s larger amphiphilic structure that is more resilient to structural hindrance of the linear carbon disulfide as opposed to the larger spherical carbon tetrachloride. Carbon disulfide is a stronger shielding agent than carbon tetrachloride for methanol except in the case of 1456 cm−1 energy mode due to the increased structural hindrance of carbon disulfide’s linear structure, which methanol is more susceptible to by its smaller molecular structure, preventing intermolecular interactions with other methanol molecules.http://www.sciencedirect.com/science/article/pii/S2211379723002863SolventsAcetoneCarbon disulfideCarbon tetrachlorideMethanolEnergy transfer
spellingShingle Richard Brun Jr
Henry J. Meyer
Robert R. Alfano
Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidth
Results in Physics
Solvents
Acetone
Carbon disulfide
Carbon tetrachloride
Methanol
Energy transfer
title Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidth
title_full Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidth
title_fullStr Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidth
title_full_unstemmed Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidth
title_short Caging of vibrational energy transfer and interactions in binary mixed solvents probed from Raman scattering linewidth
title_sort caging of vibrational energy transfer and interactions in binary mixed solvents probed from raman scattering linewidth
topic Solvents
Acetone
Carbon disulfide
Carbon tetrachloride
Methanol
Energy transfer
url http://www.sciencedirect.com/science/article/pii/S2211379723002863
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AT robertralfano cagingofvibrationalenergytransferandinteractionsinbinarymixedsolventsprobedfromramanscatteringlinewidth