Journal Article10.1021/ACS.JPCC.6B03158
Sum Frequency Generation Spectroscopy and Molecular Dynamics Simulations Reveal a Rotationally Fluid Adsorption State of α-Pinene on Silica
Junming Ho,Brian T. Psciuk,Hilary M. Chase,Benjamin Rudshteyn,Mary Alice Upshur,Li Fu,Regan J. Thomson,Hong-fei Wang,Hong-fei Wang,Franz M. Geiger,Victor S. Batista +10 more
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TL;DR: In this article, a rotationally fluid state of α-pinene at fused silica/vapor interfaces is revealed by computational and experimental vibrational sum frequency generation (SFG) studies.
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Abstract: A rotationally fluid state of α-pinene at fused silica/vapor interfaces is revealed by computational and experimental vibrational sum frequency generation (SFG) studies. We report the first assignment of the vibrational modes in the notoriously congested C–H stretching region of α-pinene and identify its bridge methylene group on the four-membered ring (“βCH2”) as the origin of its dominant spectral feature. We find that the spectra are perfused with Fermi resonances that need to be accounted for explicitly in the computation of vibrational spectra of strained hydrocarbons such as α-pinene. The preferred orientations of α-pinene are consistent with optimization of van der Waals contacts with the silica surface that results in a bimodal distribution of highly fluxional orientations in which the βCH2 group points “towards” or “away from” the surface. Classical molecular dynamics simulations further provide rotational diffusion constants of 49 ± 1 ps and 2580 ± 60 ps, which are attributed to two broad types ...
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Citations
Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields
Philip J. Stephens,Frank J. Devlin,Cary F. Chabalowski,Michael J. Frisch +3 more
- 01 Feb 1995
TL;DR: In this paper, the unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio using DFT, MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set.
11.2K
CO 2 Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields
Melissa L. Clark,Aimin Ge,Pablo E. Videla,Benjamin Rudshteyn,Christopher J. Miller,Jia Song,Victor S. Batista,Tianquan Lian,Clifford P. Kubiak +8 more
TL;DR: It is found that electrocatalysts supported on Au electrodes have tilt angles of about 65-75° relative to the surface normal with one of the carbonyl ligands in direct contact with the surface.
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•Journal Article
Molecular Dynamics of Ionic Transport and Electrokinetic Effects in Realistic Silica Channels
TL;DR: In this article, a detailed atomistic model of a silica interface is presented, which captures the essential experimentally known properties of a Silica interface and provides an atomistic description of ionic transport and both electro-osmotic flow and streaming currents for a solution of monovalent and divalent (0.2 and 1.0 M CaCl sub 2 ) salts.
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Cloud Activation Potentials for Atmospheric α-Pinene and β-Caryophyllene Ozonolysis Products.
Ariana Gray Bé,Mary Alice Upshur,Pengfei Liu,Scot T. Martin,Franz M. Geiger,Regan J. Thomson +5 more
TL;DR: In this paper, the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from α-pinene and β-caryophyllene, respectively, were found to exhibit significantly higher surface activity than those prepared fro...
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Trimethylamine-N-oxide: its hydration structure, surface activity, and biological function, viewed by vibrational spectroscopy and molecular dynamics simulations
TL;DR: This article reviews, using vibrational spectroscopy and molecular dynamics simulations, recent studies on the structure and dynamics of TMAO with its surrounding water molecules and offers an outlook on the open questions on T MAO-protein and TmaO-urea interactions in aqueous environments.
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Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
TL;DR: In this article, the unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio using DFT, MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set.