Unknown

Dataset Information

0

Intrinsic molecular vibration and rigorous vibrational assignment of benzene by first-principles molecular dynamics.


ABSTRACT: Vibrational assignment, which establishes the correspondence between vibrational modes and spectral frequencies, is a key step in any spectroscopic study. Due to the lack of experimental technique to directly observe the thermal vibration of atoms, the assignment is usually done by empirical trial-and-error method with considerable uncertainty. Here we demonstrate a successful study of intrinsic molecular vibration property based on first-principles molecular dynamics trajectory. A unified approach for calculating and assigning vibrational frequencies is developed and applied to solve some historical issues of benzene vibration. As a major achievement, the experimental frequencies of benzene a2g and b2u vibrations are reassigned, which breaks a deadlock in contemporary spectroscopic science and removes a cloud over the application of density-functional theory in organic chemistry. This work paves the way for the comprehensive realization of the first-principles spectroscopic research, and provides crucial clues to solve the century-old problems of Kekule resonance, ?-deformation, and aromaticity.

SUBMITTER: Wang S 

PROVIDER: S-EPMC7578012 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

altmetric image

Publications

Intrinsic molecular vibration and rigorous vibrational assignment of benzene by first-principles molecular dynamics.

Wang Shaoqing S  

Scientific reports 20201021 1


Vibrational assignment, which establishes the correspondence between vibrational modes and spectral frequencies, is a key step in any spectroscopic study. Due to the lack of experimental technique to directly observe the thermal vibration of atoms, the assignment is usually done by empirical trial-and-error method with considerable uncertainty. Here we demonstrate a successful study of intrinsic molecular vibration property based on first-principles molecular dynamics trajectory. A unified appro  ...[more]

Similar Datasets

| S-EPMC5340357 | biostudies-literature
| S-EPMC8756585 | biostudies-literature
| S-EPMC3058488 | biostudies-literature
| S-EPMC6744889 | biostudies-literature
| S-EPMC3511726 | biostudies-other
| S-EPMC4731798 | biostudies-other
| S-EPMC3596003 | biostudies-literature
| S-EPMC8658739 | biostudies-literature
| S-EPMC8388003 | biostudies-literature
| S-EPMC2586571 | biostudies-literature