Electric-Field-Induced Effects on the Dipole Moment and Vibrational Modes of the Centrosymmetric Indigo Molecule

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2020-12, Vol.124 (51), p.10856-10869
• Main Authors: Mollica Nardo, Viviana, Cassone, Giuseppe, Ponterio, Rosina Celeste, Saija, Franz, Sponer, Jiri, Tommasini, Matteo, Trusso, Sebastiano
• Format: Article
• Language: English
• Subjects: A: Spectroscopy, Molecular Structure, and Quantum Chemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.0c09791

Intense static electric fields can strongly perturb chemical bonds and induce frequency shifts of the molecular vibrations in the so-called vibrational Stark effect. Based on a density functional theory (DFT) approach, here, we report a detailed investigation of the influence of oriented external electric fields (OEEFs) on the dipole moment and infrared (IR) spectrum of the nonpolar centrosymmetric indigo molecule. When an OEEF as intense as ∼0.1 V Å–1 is applied, several modifications in the IR spectrum are observed. Besides the notable frequency shift of some modes, we observe the onset of new bandsforbidden by the selection rules in the zero-field case. Such a neat field-induced modification of the vibrational selection rules, and the subsequent variations of the peaks’ intensities in the IR spectrum, paves the way toward the design of smart tools employing centrosymmetric molecules as proxies for mapping local electric fields. In fact, here, we show that the ratio between the IR and the Raman intensities of selected modes is proportional to the square of the local field. This indicator can be used to quantitatively measure local fields, not only in condensed matter systems under standard conditions but also in field-emitting-tip apparatus.