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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68081707%3A_____%2F20%3A00540047" target="_blank" >RIV/68081707:_____/20:00540047 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jpca.0c09791" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpca.0c09791</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.0c09791" target="_blank" >10.1021/acs.jpca.0c09791</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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 similar to 0.1 V angstrom(-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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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 similar to 0.1 V angstrom(-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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

124

Číslo periodika v rámci svazku

51

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

10856-10869

Kód UT WoS článku

000603402600022

EID výsledku v databázi Scopus

2-s2.0-85098779022