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Camino directo a la fotodisociación molecular en superficies metálicas utilizando luz visible

Emiko Kazuma¹, Jaehoon Jung², Hiromu Ueba³

¹Surface and Interface Science Laboratory, RIKEN , Wako, Saitama 351-0198, Japan.

Journal of the American Chemical Society

|February 8, 2017

Resumen

La luz visible ahora puede romper los enlaces químicos en las superficies metálicas, un proceso que antes se creía imposible. Este avance en la fotodisociación molecular es impulsado por interacciones electrónicas únicas en la interfaz.

Área de la Ciencia:

Ciencias de la superficie
La fotoquímica
Ciencias de los materiales

Sus antecedentes:

La fotodisociación molecular inducida por la luz visible en sustratos metálicos es un reto.
La baja energía de fotones y la corta vida útil del estado excitado debido a la hibridación molécula-metal dificultan este proceso.

Objetivo del estudio:

Demostrar y explicar la fotodisociación molecular impulsada por la luz visible en sustratos metálicos monocristalinos.
Investigar el papel de las estructuras electrónicas interfaciales en la habilitación de este fenómeno.

Principales métodos:

Investigación experimental con el uso de microscopía de túnel de barrido.
Análisis teórico que emplea cálculos de la teoría funcional de la densidad.

Principales resultados:

El enlace S-S en el disulfuro de dimetilo en Cu{11} y Ag{11} se disoció con éxito utilizando luz visible.
La excitación electrónica directa de los orbitales moleculares derivados de HOMO (nS) a los derivados de LUMO (σ*SS) fue identificada como el mecanismo.
Se demostró que la hibridación molécula-metal disminuye la brecha de energía y aumenta la vida útil del estado excitado, facilitando la fotodisociación.

Conclusiones:

La fotodisociación molecular inducida por la luz visible en superficies metálicas es posible.
La estructura electrónica interfacial y la hibridación juegan un papel crucial en la habilitación de este proceso mediante el ajuste de los niveles de energía y las vidas de estado excitado.

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