Intersystem crossing

When an electron in a molecule with a singlet ground state is excited (via absorption of radiation) to a higher energy level, either an excited singlet state or an excited triplet state will form. A singlet state is a molecular electronic state such that allelectron spins are paired. That is, the spin of the excited electron is still paired with the ground state electron (a pair of electrons in the same energy level must have opposite spins, per the Pauli exclusion principle). In a triplet state the excited electron is no longer paired with the ground state electron; that is, they are parallel (same spin). Since excitation to a triplet state involves an additional “forbidden” spin transition, it is less probable that a triplet state will form when the molecule absorbs radiation.

Intersystem crossing

Singlet and triplet energy levels.

When a singlet state nonradiatively passes to a triplet state, or conversely a triplet transitions to a singlet, that process is known as intersystem crossing. In essence, the spin of the excited electron is reversed. The probability of this process occurring is more favorable when the vibrational levels of the two excited states overlap, since little or no energy must be gained or lost in the transition. As the spin/orbital interactions in such molecules are substantial and a change in spin is thus more favourable, intersystem crossing is most common in heavy-atom molecules (e.g. those containing iodine or bromine). This process is called “spin-orbit coupling”. Simply-stated, it involves coupling of the electron spin with the orbital angular momentum of non-circular orbits. In addition, the presence of paramagnetic species in solution enhances intersystem crossing.

The radiative decay from an excited triplet state back to a singlet state is known as phosphorescence. Since a transition in spin multiplicity is observed, phosphorescence is another manifestation of intersystem crossing. The time scale of intersystem crossing is on the order of 10−8 to 10−3 s, one of the slowest forms of relaxation.

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