Experimental and ab-initio calculated vcd spectra of the first OH-stretching overtone of (1R)-(−) and (1S)-(+)-endo-BORNEOL

Literature Information

Publication Date 2009-02-24
DOI 10.1039/B818432A
Impact Factor 3.676
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Abstract

The near infrared (NIR) absorption and NIR-vibrational circular dichroism (NIR-VCD) spectra of dilute solutions of the two enantiomers of endo-borneol have been measured in the first OH-stretching overtone region (1600–1300 nm). By density functional theory (DFT) we calculate mechanical parameters, i.e. the harmonic mechanical frequency and the anharmonicity constant for the OH stretching, and anharmonic electrical parameters; i.e. the dependence on OH-bond length of atomic polar tensors and atomic axial tensors. We evaluate transition integrals for the calculations of rotational and dipole strengths by Morse anharmonic wavefunctions depending on mechanical harmonic frequencies and mechanical anharmonicity parameters that are calculated ab initio. Experimental and calculated spectra compare quite well and this fact allows us to associate differently signed NIR-VCD features with different conformational states of the OH-bond. Absorption features for the fundamental and for the second overtone of the OH stretching are also compared with experiment.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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