Illustrative direct ab initio calculations of surface Raman spectra

Literature Information

Publication Date 2005-01-10
DOI 10.1039/B415535A
Impact Factor 3.676
Authors

Patrik Johansson


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Abstract

Illustrative ab initio calculations of Raman spectra of pyridine (Pyr) and pyridine in metal–molecule complexes with silver (Ag+–Pyr, Ag5+–Pyr) have been undertaken. The Raman spectra were computed numerically in the standard Placzek approximation with the additional feature of a static external electric field, F, perturbation to the system Hamiltonian. F was allowed to change the system equilibrium geometry and symmetry as well as the polarisability, resulting in shifted vibration frequencies and changed Raman intensities. All calculations were done on a Hartree–Fock (HF) level using the 6-31+G* or the Sadlej p-VTZ basis sets for Pyr, and the Stevens–Krauss (SBKJC) VDZ ECP basis set for Ag. Raman enhancement factors over 5 orders of magnitude were obtained. The enhancement was analyzed as being due to polarization and charge transfer induced by the metal-molecule contact in the absence of F and in the presence of a strong F as due to increased polarisability derivatives along the surface normal. The use of the present method to qualitatively and quantitatively predict surface Raman spectra is discussed.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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