Photodissociation of dicarbon: How nature breaks an unusual multiple bond

Jasmin Borsovszky; Klaas Nauta; Jun Jiang; Christopher S Hansen; Laura K McKemmish; Robert W Field; John F Stanton; Scott H Kable; Timothy W Schmidt

doi:10.1073/pnas.2113315118

Photodissociation of dicarbon: How nature breaks an unusual multiple bond

Proc Natl Acad Sci U S A. 2021 Dec 28;118(52):e2113315118. doi: 10.1073/pnas.2113315118.

Authors

Jasmin Borsovszky¹, Klaas Nauta¹, Jun Jiang², Christopher S Hansen¹, Laura K McKemmish¹, Robert W Field³, John F Stanton⁴, Scott H Kable⁵, Timothy W Schmidt⁵

Affiliations

¹ School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
² Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, Livermore, CA 94550.
³ Department of Chemistry, Massachussetts Institute of Technology, Cambridge, MA 02139.
⁴ Department of Chemistry, University of Florida, Gainesville, FL 32611.
⁵ School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia; s.kable@unsw.edu.au timothy.schmidt@unsw.edu.au.

Abstract

The dicarbon molecule (C₂) is found in flames, comets, stars, and the diffuse interstellar medium. In comets, it is responsible for the green color of the coma, but it is not found in the tail. It has long been held to photodissociate in sunlight with a lifetime precluding observation in the tail, but the mechanism was not known. Here we directly observe photodissociation of C₂ From the speed of the recoiling carbon atoms, a bond dissociation energy of 602.804(29) kJ·mol[Formula: see text] is determined, with an uncertainty comparable to its more experimentally accessible N₂ and O₂ counterparts. The value is within 0.03 kJ·mol^-1 of high-level quantum theory. This work shows that, to break the quadruple bond of C₂ using sunlight, the molecule must absorb two photons and undergo two "forbidden" transitions.

Keywords: comets; dicarbon; photodissociation.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.